Positive-type photosensitive resin composition, resist film, resist underlayer film, and resist permanent film

Abstract

To provide a positive photosensitive resin composition by which a resist film or the like having excellent thick film formability and excellent developability, development contrast and heat resistance is obtained.SOLUTION: A positive photosensitive resin composition contains the following components (A) to (E): (A) novolak type phenol resin which contains a phenol structural unit derived from cresol and one or more aldehyde structural units derived from formaldehyde or salicylaldehyde, and has acetal group-based protective group; (B) photoacid generator; (C) one or more kinds of resin selected from novolak type phenol resin, polyimide resin and polybenzoxazole resin which do not have acetal group-based protective group; (D) naphthoquinone-type photosensitive agent; and (E) solvent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a positive photosensitive resin composition, a resist film, a resist underlayer film, and a resist permanent film.

Background Art

[0002] In recent years, with the miniaturization of electronic devices, the high density of semiconductor packages has been progressing. Conventionally, for the formation of copper bumps and pillars in the manufacture of semiconductor packages for ICs and LSIs, a positive photoresist for i-line using an alkali-soluble resin (for example, novolak-type phenol resin) and a naphthoquinone diazide compound-based photosensitizer has been widely used. However, the miniaturization using i-line is approaching its limit. Particularly in NAND memories and the like, the three-dimensionalization of the memory layer is becoming the mainstream for the purpose of increasing the capacity. For the three-dimensionalization of the memory layer, an increase in the number of processing steps in the vertical direction is required, so a thickening of the resist film is demanded. In a thick film of several tens of μm, in the exposure process for the photosensitive resin composition using the conventional naphthoquinone diazide compound-based photosensitizer, sufficient light does not reach the bottom of the film, so the resist layer at the bottom of the pattern does not undergo alkali dissolution, and there is a problem that it is difficult to form a fine pattern with a high aspect ratio.

[0003] To address the above issues, instead of using naphthoquinone diazide compound-based photoresists, it has been considered to use chemically amplified positive-type photoresists, which are used in photolithography using excimer lasers such as KrF, ArF, and EUV, in i-line photolithography (for example, Patent Document 1). When light is irradiated onto a photosensitive resin film using a chemically amplified positive-type photoresist, acid is generated from the photoacid generator, and the generated acid (proton) acts as an acid catalyst, removing the protecting groups of the acid-degradable resin and exposing the alkali-soluble groups. In chemically amplified positive-type photoresists, after the removal of the protecting groups, the acid is catalytically regenerated and can remove other protecting groups, so that positive-type patterns with high alkali solubility can be produced even with a small amount of light. Therefore, alkali dissolution of the film bottom, which was a problem in thick film production, becomes possible. However, the positive-type photosensitive resin composition using m-cresol-based phenol novolac resin described in Patent Document 1 still lacks sensitivity, and the generation of residual film at the bottom of the pattern after development remains unresolved. Therefore, in addition to m-cresol, chemically amplified positive-type photosensitive resin compositions consisting of o-cresol and p-cresol are also being investigated (for example, Patent Document 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2003-149816 [Patent Document 2] Japanese Patent Publication No. 2019-203097 [Overview of the project] [Problems that the invention aims to solve]

[0005] Even the photosensitive resin composition described in Patent Document 2 does not have sufficient alkali solubility, and residual film still occurs at the bottom of the pattern after development due to insufficient sensitivity. With the increasing density of semiconductor packages, there is a need for the development of a photosensitive resin composition that can develop thick film patterns with high aspect ratios with high sensitivity without generating residue, and that also possesses high heat resistance.

[0006] The object of the present invention is to provide a positive-type photosensitive resin composition that yields a resist film or the like with excellent thick-film forming properties, as well as excellent developability, development contrast, and heat resistance. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the present inventors have found that the above problems can be solved by combining the components of a photosensitive resin composition using a naphthoquinone diazide compound-based photosensitive agent with the components of a chemically amplified photosensitive resin composition using a novolac-type phenol resin having a protecting group, and have completed the present invention.

[0008] In other words, the present invention relates to a positive-type photosensitive resin composition comprising the following components (A) to (E). A positive-type photosensitive resin composition comprising the following components (A) to (E). (A) A novolac-type phenolic resin comprising a phenolic structural unit derived from cresol and one or more aldehyde structural units derived from formaldehyde or salicylaldehyde, and having an acetal group protecting group. (B) Photoacid generator (C) One or more resins selected from novolac-type phenolic resins, polyimide resins, and polybenzoxazole resins that do not have acetal-based protecting groups. (D) Naphthoquinone-type photosensitive agent (E) Solvent

[0009] The present invention further relates to a photosensitive film obtained by drying a positive-type photosensitive resin composition. The present invention further relates to a resist film obtained from a positive-type photosensitive resin composition. The present invention further relates to a resist underlayer film obtained from a positive photosensitive resin composition. The present invention further relates to a resist permanent film obtained from a positive photosensitive resin composition.

Advantages of the Invention

[0010] According to the present invention, it is possible to provide a positive photosensitive resin composition from which a film having high thick film forming properties and excellent in developability, development contrast and heat resistance can be obtained.

Brief Description of the Drawings

[0011] [Figure 1] It is a GPC chart of the novolak type phenol resin obtained in Synthesis Example 1. [Figure 2] It is a GPC chart of the novolak type phenol resin obtained in Synthesis Example 2-1. [Figure 3] It is a GPC chart of the novolak type phenol resin obtained in Synthesis Example 2-2. [Figure 4] It is a GPC chart of the novolak type phenol resin obtained in Synthesis Example 2-3. [Figure 5] It is a GPC chart of the novolak type phenol resin obtained in Synthesis Example 2-4. [Figure 6] It is a GPC chart of the novolak type phenol resin obtained in Synthesis Example 2-6.

Modes for Carrying Out the Invention

[0012] Modes for carrying out the invention will be described below. In this specification, "x to y" represents a numerical range of "x or more and y or less". The upper limit value and the lower limit value described for the numerical range can be arbitrarily combined. Also, a mode in which two or more of the individual modes of the present invention described below are combined is also a mode of the present invention.

[0013] [Positive Photosensitive Resin Composition] The positive photosensitive resin composition according to an embodiment of the present invention contains the following components (A) to (E). (A) A novolak-type phenolic resin containing a phenolic structural unit derived from cresol and one or more aldehyde structural units derived from formaldehyde or salicylaldehyde, and having an acetal group-based protecting group (B) A photoacid generator (C) One or more resins selected from a novolak-type phenolic resin having no acetal group-based protecting group, a polyimide resin, and a polybenzoxazole resin (D) A naphthoquinone-type photosensitizer (E) A solvent

[0014] The above components (A) and (B) are components of a chemically amplified photosensitive resin composition, and the above components (C) and (D) are components of a photosensitive resin composition using a naphthoquinonediazide compound-based photosensitizer (hereinafter referred to as a naphthoquinone-type photosensitive resin composition). In this embodiment, by combining the components of the chemically amplified photosensitive resin composition and the components of the naphthoquinone-type photosensitive resin composition, alkali developability (sensitivity), heat resistance, and thick film forming properties, which are not present in conventional chemically amplified photosensitive resin compositions, can be exhibited.

[0015] · Component (A) As component (A), a novolak-type phenolic resin having a protecting group, which is used in a chemically amplified photosensitive resin composition, can be used. Specifically, a novolak-type phenolic resin containing a phenolic structural unit derived from cresol and an aldehyde structural unit derived from formaldehyde, and a novolak-type phenolic resin containing a phenolic structural unit derived from cresol and an aldehyde structural unit derived from salicylaldehyde can be mentioned. Examples of the protecting group include an acetal group-based protecting group.

[0016] When component (A) contains an aldehyde structural unit derived from formaldehyde, the phenol structural unit is preferably a phenol structural unit derived from m-cresol and / or a phenol structural unit derived from p-cresol.

[0017] When component (A) contains structural units (a1) derived from m-cresol, structural units (a4) derived from p-cresol, and structural units (a5) derived from formaldehyde, from the viewpoint of obtaining a positive-type photosensitive resin composition with excellent thick-film forming properties, it is preferable that the molar ratio of the above structural units (a1), (a4), and (a5) [(a1):(a4):(a5)] is 1.0:0.2 to 3.0:0.5 to 5.0.

[0018] In one embodiment, component (A) preferably comprises at least one of a phenol structural unit derived from m-cresol and a phenol structural unit derived from o-cresol, and an aldehyde structural unit derived from salicylaldehyde, and has an acetal group protecting group.

[0019] From the viewpoint of obtaining a resist film with higher developability and heat resistance, it is preferable that component (A) further includes aldehyde structural units derived from benzaldehyde in addition to aldehyde structural units derived from salicylaldehyde. For example, component (A) comprises a structural unit (a1) derived from m-cresol, a structural unit (a2) derived from salicylaldehyde, and a structural unit (a3) ​​derived from benzaldehyde, and has an acetal group protecting group, with a molar ratio of the above structural units (a1), (a2), and (a3) ​​[(a1):(a2):(a3)] being 1.0:0.3~0.8:0.3~0.8. The above molar ratio [(a1):(a2):(a3)] is more preferably 1.0:0.35~0.75:0.35~0.75, and even more preferably 1.0:0.4~0.65:0.4~0.65.

[0020] As long as the effects of the present invention are obtained, component (A) may contain structural units other than those derived from cresol, formaldehyde, salicylaldehyde, and benzaldehyde as described above.

[0021] Other structural units besides those derived from cresol, formaldehyde, salicylaldehyde, and benzaldehyde include aldehyde structural units derived from acetaldehyde, and component (A) preferably further comprises aldehyde structural units (a6) derived from acetaldehyde. For example, component (A) is preferably a novolac-type phenol resin having an acetal group protecting group, comprising a phenol structural unit (a1) derived from m-cresol, an aldehyde structural unit (a2) derived from salicylaldehyde, and an aldehyde structural unit (a6) derived from acetaldehyde, and the molar ratio of the above structural units (a1), (a2), and (a4) [(a1):(a2):(a6)] is 1.0:0.01~0.4:0.6~0.99. The above molar ratio [(a1):(a2):(a6)] is more preferably 1.0:0.02~0.3:0.7~0.98, and even more preferably 1.0:0.05~0.2:0.8~0.95.

[0022] In one embodiment, the total content of structural units derived from cresol, formaldehyde, salicylaldehyde, benzaldehyde, and acetaldehyde in component (A) is substantially 100% by mass. Furthermore, the total content of structural units (a1) to (a6) in component (A) is substantially 100% by mass. Note that substantially 100% by mass means that structural units other than structural units (a1) to (a6) are inevitably included.

[0023] The acetal protecting group of component (A) is preferably a group represented by the following formula (1). [ka] (In the formula, R1 and R2 are each independently a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.) R3 is a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R3 may be bonded to R1 or R2 to form a ring. *This symbol is bonded to the benzene ring that constitutes the main chain of the novolac-type phenolic resin.

[0024] In component (A), at least a portion of the phenolic hydroxyl groups of the novolac-type phenolic resin are protected by an acetal group protecting group represented by formula (1) above. The acetal group protecting group can be removed by an acid generated from a photoacid generator. Component (A) having an acetal protecting group means that C 13 -This can be confirmed by NMR.

[0025] In formula (1), examples of linear alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Examples of branched alkyl groups having 3 to 20 carbon atoms include isopropyl group, sec-butyl group, tert-butyl group, neopentyl group, isopentyl group, 2-methylpentyl group, 3-methylpentyl group, and 2,3-dimethylbutyl group. Examples of cyclic alkyl groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl groups. Cyclic alkyl groups may have substituents such as the linear alkyl groups mentioned above. Examples of aryl groups having 6 to 20 carbon atoms include phenyl groups, naphthyl groups, and anthracenyl groups. The aryl group may have substituents such as the alkyl groups mentioned above.

[0026] The aralkyl group is an alkyl group (C n H 2n+1This refers to an alkyl group in which one or more hydrogen atoms are substituted with an aryl group. The aryl group may have substituents such as the alkyl groups mentioned above. Specifically, examples include phenylmethyl group, tolylmethyl group, xylmethyl group, naphthylmethyl group, hydroxynaphthylmethyl group, dihydroxynaphthylmethyl group, phenylethyl group, hydroxyphenylethyl group, dihydroxyphenylethyl group, tolylethyl group, xylylethyl group, naphthylethyl group, hydroxynaphthylethyl group, and dihydroxynaphthylethyl group. The number of carbon atoms is preferably 7 to 15, for example.

[0027] R3 may bond with R1 or R2 to form a ring. Examples of rings include oxygen-containing heterocycles such as furan rings and pyran rings.

[0028] Examples of acetal protecting groups represented by formula (1) above include, specifically, 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-propoxyethoxy group, 1-butoxyethoxy group, 2-methoxypropoxy group, 2-ethoxypropoxy group, 1-(2-methylpropoxy)ethoxy group, 1-(1-propoxy)propoxy group, 1-ethoxybutoxy group, 1-(2-methoxyethoxy)ethoxy group, 1-(2-acetoxyethoxy)ethoxy group, tetrahydrofuran-2-yl group, 1-[(1-adamantyloxy)ethoxy]ethyl group, 1-[2-(1-adamantanecarbonyloxy)ethoxy]ethyl group, tetrahydro-2-pyranyl group, tetrahydro-2-furyl group, 1-(cyclohexyloxy)ethoxy Examples include xy group, 1-phenoxyethoxy group, 1-(2-cyclohexyl)ethoxyethoxy group, (1-adamantyloxy)ethoxy group, (2-adamantyloxy)ethoxy group, (1-adamantylmethoxy)ethoxy group, (2-adamantylethoxy)ethoxy group, 1-(1-bicyclo[2.2.1]heptyloxy)ethoxy group, 1-(2-bicyclo[2.2.1]heptyloxy)ethoxy group, 1-(1-bicyclo[2.2.1]heptylmethoxy)ethoxy group, 1-(2-bicyclo[2.2.1]heptylmethoxy)ethoxy group, 2-(1,7,7-trimethylbicyclo[2.2.1]heptyloxy)ethoxy group, and 2-(1-isopropyl-4-methylcyclohexyloxy)ethoxy group. The protecting group represented by formula (1) above is preferably a 2-propoxyethoxy group.

[0029] In component (A), the protection rate of phenolic hydroxyl groups in the novolac-type phenolic resin (the ratio of acetal group-based protecting groups to the total amount of phenolic hydroxyl groups in the novolac-type phenolic resin) is 1 to 50 mol%, preferably 2 to 40 mol%, more preferably 5 to 25 mol%, and even more preferably 7.5 to 15 mol%, from the viewpoint of appropriate dissolution rate in alkaline developer.

[0030] The weight-average molecular weight of component (A), a novolac-type phenolic resin, is preferably 1,000 or more, more preferably 1,500 or more. It is also preferably 7,000 or less, more preferably 6,000 or less, and even more preferably 5,000 or less. A weight-average molecular weight of 1,000 or more is preferable because it provides high heat resistance. On the other hand, a weight-average molecular weight of 7,000 or less is preferable because it provides high sensitivity. In this specification, the weight-average molecular weight is measured according to the conditions described in the examples.

[0031] Component (A) can be synthesized by known methods. For example, it can be obtained by polycondensing cresol, formaldehyde or salicylaldehyde, and optionally benzaldehyde in an organic solvent in the presence of an acid catalyst to form a novolac-type phenolic resin, and then reacting it with a compound that forms an acetal group protecting group. Below, as an example, we will describe the synthesis of a novolac-type phenolic resin (a) using m-cresol, salicylaldehyde, and benzaldehyde as monomers, and the introduction of an acetal group protecting group.

[0032] (Synthesis of novolac-type phenolic resin (a)) Novolac-type phenolic resin (a) can be obtained, for example, by dissolving the raw material compounds in a reaction solvent according to a conventional method and carrying out a synthesis reaction using an acid catalyst.

[0033] Examples of reaction solvents used in the production of novolac-type phenolic resin (a) include methanol, ethanol, 1-propanol, 2-propanol, butanol, hexanol, ethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, and toluene. Among these, one or more selected from ethanol, 1-propanol, and 2-propanol are preferred, and ethanol or methyl isobutyl ketone is more preferred.

[0034] When producing a novolac-type phenolic resin (a) containing structural units derived from m-cresol, salicylaldehyde, and benzaldehyde, it is preferable to synthesize the resin by polycondensation of monomers in an organic solvent using an acid catalyst, with a molar ratio (m-cresol:salicylaldehyde:benzaldehyde) in the range of 1.0:0.3 to 0.8:0.3 to 0.8. The molar ratio (m-cresol:salicylic acid:benzaldehyde) is more preferably 1.0:0.35~0.75:0.35~0.75, and even more preferably 1.0:0.4~0.65:0.4~0.65.

[0035] When producing a novolac-type phenolic resin (a) containing structural units derived from m-cresol, salicylaldehyde, and acetaldehyde, it is preferable to synthesize the resin by polycondensation of monomers in an organic solvent using an acid catalyst, in a molar ratio (m-cresol:salicylaldehyde:acetaldehyde) of 1.0:0.01 to 0.4:0.6 to 0.99. The molar ratio (m-cresol:salicylic acid:acetaldehyde) is more preferably 1.0:0.02-0.3:0.7-0.98, and even more preferably 1.0:0.05-0.2:0.8-0.95.

[0036] From the viewpoint of reaction uniformity, the amount of the above-mentioned reaction solvent used is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, per 100 parts by mass of monomer. Furthermore, it is preferably 500 parts by mass or less, more preferably 300 parts by mass or less.

[0037] Examples of acid catalysts used in the production of novolac-type phenolic resin (a) include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and boric acid; and organic acids such as oxalic acid, acetic acid, and p-toluenesulfonic acid. Among these, inorganic acids and p-toluenesulfonic acid are preferred, and p-toluenesulfonic acid is more preferred, as they promote the reaction more effectively. The amount of acid catalyst added is not particularly limited, but is preferably 5 parts by mass or more, more preferably 20 parts by mass or more, per 100 parts by mass of monomer. It is also preferably 150 parts by mass or less, more preferably 100 parts by mass or less.

[0038] The reaction temperature for polycondensation of monomers is preferably 30°C or higher, more preferably 40°C or higher, in order to promote the reaction and efficiently increase the molecular weight. It is also preferably 100°C or lower, more preferably 80°C or lower. The reaction time is preferably 4 hours or more, more preferably 12 hours or more. It is also preferably 32 hours or less, more preferably 24 hours or less.

[0039] (Introduction of acetal protecting groups) The method for introducing the acetal protecting group is not particularly limited. For example, one method involves adding a novolac resin (a) and a compound that forms the acetal protecting group to a reaction solvent and reacting them using an acid catalyst. The acetal group protecting group is generated in an acid catalyst by the reaction of a compound that forms an acetal group protecting group with a phenolic hydroxyl group in the novolac-type phenolic resin (a), thereby protecting the phenolic hydroxyl group in the novolac-type phenolic resin (a).

[0040] As the reaction solvent used for introducing the acetal group protecting group, the reaction solvent used in the synthesis of the novolac-type phenol resin (a) described above can be suitably used. Methyl isobutyl ketone is preferred as the reaction solvent used for introducing the acetal group protecting group.

[0041] The acid catalyst used in introducing the acetal group protecting group is preferably the same acid catalyst used in the synthesis of the novolac-type phenolic resin (a) described above. Among these, inorganic acids and p-toluenesulfonic acid are preferred, and p-toluenesulfonic acid is more preferred, in order to further promote the reaction.

[0042] When introducing an acetal protecting group, the reaction time is preferably 1 hour or more, more preferably 2 hours or more. It is also preferably 10 hours or less, more preferably 6 hours or less. When introducing the acetal group protecting group, the reaction temperature can be the same as that used for the synthesis of the novolac-type phenolic resin (a) described above.

[0043] In this embodiment, the compound that forms the acetal protecting group is preferably a compound represented by the following formula (2). [ka] (In the formula, R3 is a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.) R4 to R6 are, independently, a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0044] In formula (2), specific examples of linear alkyl groups having 1 to 20 carbon atoms, branched alkyl groups having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms are the same as in formula (1) above. Any two of R3, R4, R5, and R6 may bond to form a ring; for example, R3 and R6 may bond to form a cyclic ether.

[0045] Compounds that form the acetal protecting group represented by formula (2) above include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclopentyl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, phenethyl vinyl ether, menthyl vinyl ether, 1-adamantyl vinyl ether, 2-adamantyl vinyl ether, [(adamantan-1-yl)methyl] vinyl ether, [(A Examples include damantan-2-yl)methyl vinyl ether, 1-methoxypropylene, 2-methoxy-2-butene, 2-methoxy-3-methyl-2-butene, 2-(ethenyloxy)bicyclo[2.2.1]heptane, 2-(ethenyloxy)-1,7,7-trimethylbicyclo[2.2.1]heptane, 2-[(vinyloxy)methyl]bicyclo[2.2.1]heptane, 2-[(vinyloxy)ethyl]bicyclo[2.2.1]heptane, 3-(ethenyloxy)-1,1-bicyclohexane, and 3,4-dihydropyran. Among these, propyl vinyl ether is preferred.

[0046] In this embodiment, the amount of the compound represented by formula (2) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, per 100 parts by mass of novolac-type phenolic resin (a), in order to obtain good developability (sensitivity) and development contrast. Also preferably 20 parts by mass or less, more preferably 15 parts by mass or less.

[0047] ·Component (B) Component (B), the photoacid generator, is a compound that generates acid by causing bond cleavage upon exposure. By including the photoacid generator, the acetal group protecting group is removed from component (A) in the exposed area by the acid produced by the photoacid generator. This reaction exposes the phenolic hydroxyl groups of the novolac-type phenolic resin (A), creating a difference in alkali solubility between the unexposed and exposed areas. Furthermore, through a synergistic effect with component (D), described later, the developability (sensitivity) and development contrast can be improved when the positive-type photosensitive resin composition is used as a photosensitive film.

[0048] The photoacid generator is not particularly limited, and known photoacid generators can be used. Examples include organic halogen compounds, sulfonic acid esters, onium salts (phosphonium salts, sulfonium salts, iodonium salts, etc.), diazonium salts, diazomethane compounds, nitrobenzyl compounds, disulfone compounds, and triazine-based photoacid generators. In one embodiment, the photoacid generator is not a naphthoquinone diazide compound.

[0049] Specific examples of photoacid generators include the following: Haloalkyl-containing s-triazine derivatives such as tris(trichloromethyl)-s-triazine, tris(tribromomethyl)-s-triazine, tris(dibromomethyl)-s-triazine, 2,4-bis(tribromomethyl)-6-p-methoxyphenyl-s-triazine, and (2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine);

[0050] Halogen-substituted paraffinic hydrocarbon compounds such as 1,2,3,4-tetrabromobutane, 1,1,2,2-tetrabromoethane, carbon tetrabromide, and iodoform; halogen-substituted cycloparaffinic hydrocarbon compounds such as hexabromocyclohexane, hexachlorocyclohexane, and hexabromocyclododecane;

[0051] Haloalkyl-containing benzene derivatives such as bis(trichloromethyl)benzene and bis(tribromomethyl)benzene; haloalkyl-containing sulfone compounds such as tribromomethylphenylsulfone and trichloromethylphenylsulfone; halogen-containing sulfolane compounds such as 2,3-dibromosulfolane; haloalkyl-containing isocyanurate compounds such as tris(2,3-dibromopropyl)isocyanurate;

[0052] Sulfonium salts such as triphenylsulfonium chloride, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl[4-(phenylthio)phenyl]sulfonium trifluoromethanesulfonate, triphenylsulfonium methanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium hexafluorophosphonate;

[0053] Iodonium salts such as diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroarsenate, and diphenyliodonium hexafluorophosphonate;

[0054] Methyl p-toluenesulfonate, ethyl p-toluenesulfonate, p-toluenesulfonate Sulfonic acid ester compounds such as butyl nitrate, phenyl p-toluenesulfonate, 1,2,3-tris(p-toluenesulfonyloxy)benzene, benzoin p-toluenesulfonate, methyl methanesulfonate, ethyl methanesulfonate, butyl methanesulfonate, 1,2,3-tris(methanesulfonyloxy)benzene, phenyl methanesulfonate, benzoin methanesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, butyl trifluoromethanesulfonate, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, phenyl trifluoromethanesulfonate, and benzoin trifluoromethanesulfonate; disulfone compounds such as diphenyldisulfone;

[0055] Bis(phenylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, cyclohexylsulfonyl-(2-methoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-methoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2-methoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-methoxyphenylsulfonyl) (Fonyl) diazomethane, cyclopentylsulfonyl-(4-methoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl-(2-fluorophenylsulfonyl) diazomethane, cyclohexylsulfonyl-(3-fluorophenylsulfonyl) diazomethane, cyclohexylsulfonyl-(4-fluorophenylsulfonyl) diazomethane, cyclopentylsulfonyl-(2-fluorophenylsulfonyl) diazomethane, cyclopentylsulfonyl-(3-fluorophenylsulfonyl) diazomethane, cyclopentylsulfonyl- (4-Fluorophenylsulfonyl)diazomethane, Cyclohexylsulfonyl-(2-chlorophenylsulfonyl)diazomethane, Cyclohexylsulfonyl-(3-chlorophenylsulfonyl)diazomethane, Cyclohexylsulfonyl-(4-chlorophenylsulfonyl)diazomethane, Cyclopentylsulfonyl-(2-chlorophenylsulfonyl)diazomethane, Cyclopentylsulfonyl-(3-chlorophenylsulfonyl)diazomethane, Cyclopentylsulfonyl-(4-chlorophenylsulfonyl)diazomethane, Cyclohexyl Diazomethane (2-trifluoromethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl (3-trifluoromethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl (4-trifluoromethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl (2-trifluoromethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl (3-trifluoromethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl (4-trifluoromethylphenylsulfonyl) diazomethane,Cyclohexylsulfonyl-(2-trifluoromethoxyphenylsulfonyl)diazomethane, Cyclohexylsulfonyl-(3-trifluoromethoxyphenylsulfonyl)diazomethane, Cyclohexylsulfonyl-(4-trifluoromethoxyphenylsulfonyl)diazomethane, Cyclopentylsulfonyl-(2-trifluoromethoxyphenylsulfonyl)diazomethane, Cyclopentylsulfonyl-(3-trifluoromethoxyphenylsulfonyl)diazomethane, Cyclopentylsulfonyl-(4-trifluoromethoxyphenylsulfonyl (2,4,6-trimethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl-(2,4,6-trimethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl-(2,3,4-triethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl-(2,3,4-triethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl-(2,4,6-trimethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl-(2,3,4- Trimethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl-(2,4,6-triethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl-(2,3,4-triethylphenylsulfonyl) diazomethane, phenylsulfonyl-(2-methoxyphenylsulfonyl) diazomethane, phenylsulfonyl-(3-methoxyphenylsulfonyl) diazomethane, phenylsulfonyl-(4-methoxyphenylsulfonyl) diazomethane, bis(2-methoxyphenylsulfonyl) diazomethane, bis(3-methoxyphenylsulfonyl) Phenylsulfonyl diazomethane, bis(4-methoxyphenylsulfonyl) diazomethane, phenylsulfonyl-(2,4,6-trimethylphenylsulfonyl) diazomethane, phenylsulfonyl-(2,3,4-trimethylphenylsulfonyl) diazomethane, phenylsulfonyl-(2,4,6-triethylphenylsulfonyl) diazomethane, phenylsulfonyl-(2,3,4-triethylphenylsulfonyl) diazomethane, 2,4-dimethylphenylsulfonyl-(2,4,6-trimethylphenylsulfonyl) diazomethane,Sulfone diazide compounds such as 2,4-dimethylphenylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2-fluorophenylsulfonyl)diazomethane, phenylsulfonyl-(3-fluorophenylsulfonyl)diazomethane, and phenylsulfonyl-(4-fluorophenylsulfonyl)diazomethane;

[0056] o-nitrobenzyl ester compounds such as o-nitrobenzyl-p-toluenesulfonate; Sulfone hydrazide compounds such as N,N'-di(phenylsulfonyl)hydrazide; Sulfonium salts are salts of sulfonium cations such as triarylsulfonium and triarylsulfonium with sulfonates such as fluoroalkanesulfonates, arenesulfonates, and alkanesulfonates;

[0057] Iodonium salts are salts of iodonium cations such as diaryliodonium and sulfonates such as fluoroalkanesulfonates, arenesulfonates, and alkanesulfonates; Bisulfonyl diazomethane compounds such as bis(alkylsulfonyl)diazomethane, bis(cycloalkylsulfonyl)diazomethane, bis(perfluoroalkylsulfonyl)diazomethane, bis(arylsulfonyl)diazomethane, and bis(aralkylsulfonyl)diazomethane;

[0058] N-sulfonyl oxyimide compounds consisting of a dicarboxylic acid imide compound and a sulfonate such as a fluoroalkanesulfonate, arene sulfonate, or alkanesulfonate; Benzoin sulfonate compounds such as benzoin tosylate, benzoin mesylate, and benzoin butanesulfonate; Polyhydroxyarene sulfonate compounds are those in which all hydroxyl groups of a polyhydroxyarene compound are replaced with sulfonates such as fluoroalkane sulfonates, arene sulfonates, or alkane sulfonates;

[0059] Nitrobenzyl sulfonate compounds such as fluoroalkanesulfonic acid (poly)nitrobenzyl, arenesulfonic acid (poly)nitrobenzyl, and alkanesulfonic acid (poly)nitrobenzyl; Fluoroalkanebenzyl sulfonate compounds such as (poly)fluoroalkanebenzyl fluoroalkanesulfonic acid, (poly)fluoroalkanebenzyl arenesulfonic acid, and (poly)fluoroalkanebenzyl alkanesulfonic acid;

[0060] Bis(arylsulfonyl)alkane compounds; Bis-O-(arylsulfonyl)-α-dialkylglyoxime, bis-O-(arylsulfonyl)-α-dicycloalkylglyoxime, bis-O-(arylsulfonyl)-α-diarylglyoxime, bis-O-(alkylsulfonyl)-α-dicycloalkylglyoxime, bis-O-(alkylsulfonyl)-α-diarylglyoxime, bis-O-(fluoroalkylsulfonyl)-α-dialkylglyoxime, bis-O-(fluoroalkylsulfonyl)-α-dicycloalkylglyoxime, bis-O-(fluoroalkylsulfonyl)-α-diarylglyoxime, Oxime compounds such as bis-O-(arylsulfonyl)-α-dialkylnioxime, bis-O-(arylsulfonyl)-α-dicycloalkylnioxime, bis-O-(arylsulfonyl)-α-diarylnioxime, bis-O-(alkylsulfonyl)-α-dicycloalkylnioxime, bis-O-(alkylsulfonyl)-α-diarylnioxime, bis-O-(fluoroalkylsulfonyl)-α-dialkylnioxime, bis-O-(fluoroalkylsulfonyl)-α-dicycloalkylnioxime, and bis-O-(fluoroalkylsulfonyl)-α-diarylnioxime;

[0061] Modified oxime compounds such as arylsulfonyloxyiminoarylacetonitrile, alkylsulfonyloxyiminoarylacetonitrile, fluoroalkylsulfonyloxyiminoarylacetonitrile, ((arylsulfonyl)oxyimino-thiophene-ylidene)arylacetonitrile, ((alkylsulfonyl)oxyimino-thiophene-ylidene)arylacetonitrile, ((fluoroalkylsulfonyl)oxyimino-thiophene-ylidene)arylacetonitrile, bis(arylsulfonyloxyimino)aryldiacetonitrile, bis(alkylsulfonyloxyimino)aryldiacetonitrile, bis(fluoroalkylsulfonyloxyimino)aryldiacetonitrile, arylfluoroalkanone-O-(alkylsulfonyl)oxime, arylfluoroalkanone-O-(arylsulfonyl)oxime, and arylfluoroalkanone-O-(fluoroalkylsulfonyl)oxime.

[0062] The photoacid generator may be used alone, or two or more may be used in combination. The amount of photoacid generator added is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, per 100 parts by mass of component (A), from the viewpoint of obtaining good film-forming properties for the positive-type photosensitive resin composition and good developability (sensitivity) and heat resistance when the positive-type photosensitive resin composition is made into a resist film or the like. Furthermore, it is preferably 20 parts by mass or less, and more preferably 5 parts by mass or less.

[0063] ·Component (C) Component (C) is one or more resins selected from novolac-type phenolic resins, polyimide resins, and polybenzoxazole resins that do not have acetal-based protecting groups. The positive-type photosensitive resin composition of this embodiment, by including component (C) in addition to component (A), which is a novolac-type phenolic resin having an acetal group-based protecting group, can produce a resist film or the like with excellent thick-film formation properties, developability, and heat resistance.

[0064] From the viewpoint of obtaining a positive-type photosensitive resin composition with excellent thick-film forming properties, the novolac-type phenolic resin that does not have an acetal group protecting group, which is component (C), is preferably a novolac-type phenolic resin that contains a phenolic structural unit derived from cresol and an aldehyde structural unit derived from formaldehyde.

[0065] From the viewpoint of obtaining a positive-type photosensitive resin composition with excellent thick-film forming properties, it is more preferable that the novolac-type phenol resin without an acetal group protecting group contains, as phenol structural units derived from cresol, m-cresol (C1) and p-cresol (C2).

[0066] From the viewpoint of obtaining a positive-type photosensitive resin composition with excellent thick-film forming properties, in a novolac-type phenolic resin without an acetal group protecting group, it is preferable that the molar ratio [(c1):(c2):(c3)] of structural units derived from m-cresol (c1), p-cresol (c2), and formaldehyde (c3) is 1.0:0.2 to 3.0:0.5 to 5.0.

[0067] Novolac-type phenolic resins that do not have an acetal group protecting group may contain structural units other than the structural unit derived from m-cresol (c1), the structural unit derived from p-cresol (c2), and the structural unit derived from formaldehyde (c3). Examples of structural units other than (c1), (c2), and (c3) include structural units derived from phenols and aldehydes other than m-cresol, p-cresol, and formaldehyde.

[0068] Examples of the phenols mentioned above include 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, and 3,4,5-trimethylphenol.

[0069] Examples of the above-mentioned aldehydes include paraformaldehyde, acetaldehyde, chloroacetaldehyde, 4-hydroxybenzaldehyde, and 3-hydroxybenzaldehyde.

[0070] Novolac-type phenolic resins without acetal-based protecting groups can be obtained, for example, by polycondensation of starting materials containing cresol and formaldehyde in an organic solvent using an acid catalyst. Novolac-type phenolic resins without acetal-based protecting groups can be synthesized under the same synthesis conditions as novolac-type phenolic resin (A), except that acetal-based protecting groups are not introduced. The organic solvent and acid catalyst used in the synthesis of novolac-type phenolic resins without acetal-based protecting groups may be the same as or different from those used in the synthesis of novolac-type phenolic resin (a).

[0071] The polyimide resin, which is component (C), also includes polyimide resin precursors, and it is sufficient if it is at least one of the polyimide resin and the polyimide resin precursor. Examples of polyimide resin precursors include those obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic acid dianhydride, or a tetracarboxylic acid diester dichloride with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine, and having tetracarboxylic acid and / or its derivative residues and diamine and / or its derivative residues. Examples of polyimide resin precursors include polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide.

[0072] Examples of polyimide resins include those obtained by dehydrating and cyclizing the above-mentioned polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide by heating or a reaction using an acid or base, and which have tetracarboxylic acid and / or its derivative residues and diamine and / or its derivative residues. The tetracarboxylic dianhydride used in the synthesis of polyimide resins is preferably pyromellitic anhydride from the viewpoint of heat resistance. The diamine used in the synthesis of polyimide is preferably 4,4-diaminodiphenyl ether from the viewpoint of heat resistance.

[0073] The polybenzoxazole resin, which is component (C), also includes a polybenzoxazole resin precursor, and it is sufficient if it is at least one of the polybenzoxazole resin and the polybenzoxazole resin precursor. Examples of polybenzoxazole resin precursors include those obtained by reacting a dicarboxylic acid, a corresponding dicarboxylic acid dichloride, or a dicarboxylic acid active diester with a diamine such as a bisaminophenol compound, and having residues of a dicarboxylic acid and / or its derivatives, and a bisaminophenol compound and / or its derivatives. Examples of polybenzoxazole precursors include polyhydroxyamides.

[0074] Examples of polybenzoxazoles include those obtained by dehydrating and cyclizing a dicarboxylic acid and a bisaminophenol compound as a diamine using polyphosphate, or those obtained by dehydrating and cyclizing the above-mentioned polyhydroxyamide by heating or using anhydrous phosphoric acid, a base, or a carbodiimide compound, and have dicarboxylic acid and / or derivative residues and bisaminophenol compounds and / or derivative residues. The bisaminophenol used in the synthesis of polybenzoxazoles is preferably 3,3-hydroxybenzidine from the viewpoint of heat resistance. The dicarboxylic acid used in the synthesis of polybenzoxazoles is preferably 4,4-biphenyldicarboxylic acid from the viewpoint of heat resistance.

[0075] In the photosensitive resin composition of this embodiment, the amount of component (C) is preferably 30 parts by mass or more, more preferably 100 parts by mass or more, per 100 parts by mass of component (A). Furthermore, it is preferably 1900 parts by mass or less, and more preferably 900 parts by mass or less.

[0076] ·Component (D) The naphthoquinone-type photosensitive agent, component (D), refers to a compound having a quinone diazide group. Since the novolac-type phenolic resins of components (A) and (C) have high affinity for the photoacid generator and naphthoquinone-type photosensitive agent, component (B), the positive-type photosensitive resin composition of this embodiment is a positive-type photosensitive resin composition with excellent developability.

[0077] Specifically, component (D) acts as a dissolution inhibitor for the novolac-type phenolic resins of components (A) and (C) until light irradiation occurs, so the photosensitive film etc. obtained from the positive-type photosensitive resin composition of this embodiment does not dissolve in the alkaline developer. After light irradiation, component (D) undergoes photodegradation in the exposed area, so it loses its dissolution inhibitory effect on the novolac-type phenolic resins of components (A) and (C), and the photosensitive film etc. obtained from the positive-type photosensitive resin composition of this embodiment becomes soluble in the alkaline developer.

[0078] Specific examples of compounds having a quinone diazide group that can be used as component (D) include, for example, complete ester compounds, partial ester compounds, amidates, or partial amidates of aromatic (poly)hydroxy compounds with sulfonic acids having a quinone diazide group, such as naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, orthoanthraquinone diazide sulfonic acid.

[0079] Aromatic (poly)hydroxy compounds include polyhydroxybenzophenone compounds such as 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,2',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, and 2,3,3',4,4',5'-hexahydroxybenzophenone;

[0080] Bis[(poly)hydroxyphenyl]alkane compounds such as bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 4,4'-{1-[4-〔2-(4-hydroxyphenyl)-2-propyl〕phenyl]ethylidene}bisphenol, 3,3'-dimethyl-{1-[4-〔2-(3-methyl-4-hydroxyphenyl)-2-propyl〕phenyl]ethylidene}bisphenol;

[0081] Tris(hydroxyphenyl)methane compounds such as tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, or their methyl-substituted derivatives;

[0082] Bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, Bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, Bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, Bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, Bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, Bis(5-cyclohexyl-4-hydroxy-2 -methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-4-hydroxy Examples include bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methane compounds or their methyl-substituted derivatives, such as phenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, and bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane. These naphthoquinone-type photosensitizers may be used individually or in combination of two or more types.

[0083] In the photosensitive resin composition of this embodiment, the amount of component (D) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, per 100 parts by mass of component (C), in order to obtain a positive-type photosensitive resin composition with excellent developability (photosensitivity). Furthermore, it is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less.

[0084] ·Component (E) Examples of solvents that constitute component (E) include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone; esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons such as toluene and xylene. These solvents may be used individually or in combination of two or more.

[0085] The amount of solvent blended in the positive-type photosensitive resin composition of this embodiment is such that the solid content concentration in the composition is preferably 5% by mass or more, in order to obtain a uniform coating film by a coating method such as spin coating, which ensures the fluidity of the composition. Furthermore, it is preferably 65% ​​by mass or less.

[0086] Other ingredients In one embodiment, the positive-type photosensitive resin composition may contain various additives in addition to the components (A) to (E) described above, as long as they do not impede the effects of the present invention. Examples of additives include fillers, pigments, surfactants such as leveling agents, adhesion improvers, and dissolution accelerators.

[0087] The positive-type photosensitive resin composition of this embodiment can be prepared by stirring and mixing the above-mentioned components (A) to (E), and various additives as needed, in a conventional manner to obtain a homogeneous liquid. For example, in one embodiment, the positive-type photosensitive resin composition can be prepared by mixing components (A) and (C) in component (E), and then further mixing in components (B) and (D).

[0088] In one embodiment, the positive-type photosensitive resin composition may be a so-called two-component positive-type photosensitive resin composition comprising a chemically amplified photosensitive resin composition (F) containing component (A), component (B), and component (E1) solvent, and a naphthoquinone-type photosensitive resin composition (G) containing component (C), component (D), and component (E2) solvent. When using a positive-type photosensitive resin composition as a two-component positive-type photosensitive resin composition, it is preferable to uniformly mix components (F) and (G) before use.

[0089] The solvent components (E1) and (E2) contained in the chemically amplified photosensitive resin composition (F) and the naphthoquinone-type photosensitive resin composition (G) may be the same or different.

[0090] In one embodiment, when the positive-type photosensitive resin composition consists of component (F) and component (G), the mixing ratio [(F):(G)] is preferably 5:95 to 50:50 by mass, and more preferably 15:85 to 30:70, from the viewpoint of thick film formation, developability, and heat resistance.

[0091] When solid additives such as fillers and pigments are incorporated into the composition, it is preferable to disperse and mix them using a dispersion device such as a dissolver, homogenizer, or three-roll mill. Furthermore, the composition can be filtered using a mesh filter, membrane filter, or the like to remove coarse particles and impurities.

[0092] The positive-type photosensitive resin composition of this embodiment can be suitably used in applications such as positive-type photoresists, organic underlayer films, thick-film resists (bump-forming resists), interlayer insulating films, liquid crystal alignment films, and heat-resistant additives.

[0093] • Membrane manufacturing method The positive-type photosensitive resin composition of the present invention can be formed into a photosensitive film, a resist film, a resist underlayer film, a resist permanent film, etc. (hereinafter, the resist film, resist underlayer film, and resist permanent film may be collectively referred to as a resist film, etc.) in the same manner as a general positive-type photosensitive resin composition. Specifically, by applying the positive-type photosensitive resin composition of the present invention to an object to be photolithographed and pre-baking it, a film of the photosensitive resin composition (photosensitive film) from which the solvent has been removed is obtained.

[0094] In one embodiment, the method for producing the film includes the step of mixing a chemically amplified photosensitive resin composition (F) containing the above-mentioned components (A), (B), and (E) with a naphthoquinone-type photosensitive resin composition (G) containing the above-mentioned components (C), (D), and (E) to prepare a positive-type photosensitive resin composition.

[0095] The prepared positive-type photosensitive resin composition is applied to the target object. Application methods include spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating, etc. Pre-baking can be performed, for example, by heating at a temperature of 60°C to 150°C for 30 seconds to 600 seconds. Furthermore, the positive-type photosensitive resin composition of the present invention can be applied to various substrates, such as glass substrates, silicon substrates, aluminum substrates, silicon carbide substrates, silicon nitride substrates, gallium nitride substrates, transparent conductive films, copper substrates, and copper-plated substrates, as appropriate.

[0096] The catalytic reaction of the acid generated by exposure to the photosensitive film causes the elimination of the acetal group-based protecting group from component (A), significantly increasing the solubility of the exposed area in the alkaline developer. Examples of light sources used for exposure include infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams. Among these light sources, ultraviolet light is preferred, and the g-line (wavelength 436 nm) and i-line (wavelength 365 nm) of a high-pressure mercury lamp are particularly suitable. After exposure, the material may be heat-treated at around 100°C to 150°C to promote the elimination reaction of the acetal protecting group from component (A).

[0097] The photosensitive film obtained from the positive-type photosensitive resin composition of the present invention has high alkali solubility in the exposed areas and a large difference in alkali solubility between the exposed and unexposed areas, enabling high-resolution patterning. Therefore, it can be suitably used for resist films and the like. In this application, resist films and the like include both photosensitive films before exposure and non-photosensitive films after exposure.

[0098] Examples of alkaline developers used for development after exposure include inorganic alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; and alkaline aqueous solutions of cyclic amines such as pyrrole and pyreridine. Alkaline developers may be used with alcohol, surfactants, etc., added as needed. The alkali concentration of the alkaline developer is usually preferably in the range of 2 to 5% by mass, and a 2.38% by mass aqueous solution of tetramethylammonium hydroxide is commonly used.

[0099] When using the positive-type photosensitive resin composition of the present invention for resist underlayer (BARC film) applications, the positive-type photosensitive resin composition of the present invention may be used as is as a resist underlayer composition, or various additives such as other resin components, surfactants, dyes, fillers, crosslinking agents, and dissolution accelerators may be added as needed.

[0100] Other resin components include, for example, various novolac resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenolic compounds, modified novolac resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, phenol aralkyl resins (Zyloc resins), naphthol aralkyl resins, trimethylol methane resins, tetraphenyloleethane resins, biphenyl-modified phenolic resins, biphenyl-modified naphthol resins, aminotriazine-modified phenolic resins, and various vinyl polymers. When other resin components are used, the blending ratio of the positive-type photosensitive resin composition of the present invention to the other resin can be arbitrarily set depending on the application. For example, it is preferable that the other resin is in a ratio of 0.5 to 100 parts by mass to 100 parts by mass of the total of components (A) and (C).

[0101] The resist underlayer composition can be prepared by blending the above components and mixing them using a stirrer or the like. Furthermore, if the resist underlayer composition contains fillers or pigments, it can be prepared by dispersing or mixing them using a dispersion device such as a dissolver, homogenizer, or three-roll mill.

[0102] To form a resist underlayer from a resist underlayer composition, for example, the above-mentioned resist underlayer composition is applied to an object to be photolithographed, such as a silicon substrate, dried under a temperature of 100 to 200°C, and then further heat-cured under a temperature of 250 to 400°C. Subsequently, a resist pattern can be formed on this underlayer by performing a normal photolithography operation, and then a resist pattern can be formed by a multilayer resist method by dry etching with a halogen-based plasma gas or the like.

[0103] When the positive-type photosensitive resin composition of the present invention is used for resist permanent film applications, in addition to components (A) to (E) of the present invention, other additives such as other resins, surfactants, dyes, fillers, crosslinking agents, and dissolution accelerators may be added as needed. Examples of other resins used here include those similar to those that can be used in resist underlayer film compositions.

[0104] A photolithography method using a resist permanent film composition involves, for example, dissolving and dispersing other resin components and additive components in the positive-type photosensitive resin composition of the present invention, coating it onto the object to be photolithographed, and pre-baking it at a temperature of 60 to 150°C. The coating method at this time can be any of the following: spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating, etc. Next, the target resist pattern is exposed through a predetermined mask, and the exposed area is dissolved with an alkaline developer to form the resist pattern.

[0105] The resist permanent film of this embodiment can be suitably used, for example, in semiconductor devices as a solder resist, package material, underfill material, package adhesive layer for circuit elements, and adhesive layer between integrated circuit elements and circuit boards, and in thin-film displays such as LCDs and OLEDs as a thin-film transistor protective film, liquid crystal color filter protective film, black matrix, spacer, etc. [Examples]

[0106] The present invention will be explained in more detail below with specific examples. The weight-average molecular weight (Mw) of the synthesized resin was measured under the GPC measurement conditions described below. [GPC measurement conditions] Measurement device: Tosoh Corporation "HLC-8220 GPC" Column: Showa Denko Corporation "Shodex KF802": 8.0mm diameter × 300mm +Showa Denko Corporation "Shodex KF802": 8.0mm diameter × 300mm +Showa Denko Corporation "Shodex KF803": 8.0mm diameter × 300mm +Showa Denko Corporation "Shodex KF804": 8.0mm diameter x 300mm Column temperature: 40℃ Detector: RI (Differential Refractometer) Data processing: Tosoh Corporation's "GPC-8020 Model II Version 4.30" Developing solvent: tetrahydrofuran Flow rate: 1.0mL / min Sample: A tetrahydrofuran solution containing 0.5% by mass (based on resin solids content) filtered through a microfilter. Injection volume: 0.1mL Standard sample: Monodisperse polystyrene (see below) (Standard sample: monodisperse polystyrene) "A-500" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation Tosoh Corporation's "F-10" F-20 manufactured by Tosoh Corporation

[0107] [Novolac-type phenolic resin without acetal group protecting group (component (C))] Synthesis Example 1 (Novolac-type phenolic resin (C-1)) Under a stream of dry nitrogen, 140 g (1.3 mol) of m-cresol, 76 g (0.7 mol) of p-cresol, 162 g (2.0 mol) of 37 wt% formaldehyde aqueous solution, and 1 g (0.01 mol) of oxalic acid dihydrate were charged into a 2000 ml four-necked flask equipped with a condenser. These were dissolved in 528 g of methyl isobutyl ketone as the reaction solvent. The reaction was then stirred for 4 hours under reflux using a mantle heater. After the reaction, water was added, and the mixture was washed five times. Methyl isobutyl ketone was removed by vacuum distillation at 60°C using an evaporator, and then vacuum drying was performed to obtain 212 g of pale red powdered phenol novolac resin (C-1). The weight-average molecular weight (Mw) of the novolac-type phenol resin (C-1) was 10,600. Figure 1 shows the GPC chart for novolac-type phenolic resin (C-1).

[0108] [Novolac-type phenolic resin having an acetal group protecting group (component (A))] Synthesis Example 2-1 (Novolac-type phenolic resin (A-1)) In a 2000 ml four-necked flask equipped with a condenser, 164 g (1.52 mol) of m-cresol, 95.5 g (0.90 mol) of benzaldehyde, 73 g (0.60 mol) of salicylaldehyde, and 8 g of p-toluenesulfonic acid were charged and dissolved in 300 g of ethanol as the reaction solvent. The reaction was then carried out with stirring under reflux at 80°C using a mantle heater for 16 hours. After the reaction, ethyl acetate and water were added and the mixture was subjected to five separatory washes. After removing the solvent from the remaining resin solution under reduced pressure, the mixture was vacuum dried to obtain 281 g of pale red novolac-type phenolic resin powder (a-1).

[0109] Next, 80 g of the obtained phenol novolac resin powder (a-1), 8 g of propyl vinyl ether, and 0.1 g of p-toluenesulfonic acid were charged into a 500 ml four-necked flask and dissolved in 120 g of methyl isobutyl ketone as the reaction solvent. The reaction was then carried out with stirring at 40°C for 4 hours using a mantle heater. After the reaction, 0.4 g of dimethylaminoethanol was added and stirred well, then ethyl acetate and water were added and the mixture was subjected to five liquid-liquid washes. After removing the solvent from the remaining resin solution under reduced pressure, the mixture was vacuum-dried to obtain 79 g of pale red powder novolac-type phenol resin (A-1) having an acetal group protecting group. C 13 -NMR confirmed that the novolac-type phenolic resin (A-1) has an acetal group protecting group. The Mw of the obtained novolac-type phenolic resin (A-1) was 2,990. The GPC chart for novolac-type phenolic resin (A-1) is shown in Figure 2.

[0110] Synthesis Example 2-2 (Novolac-type phenolic resin (A-2)) Except for using 164 g (1.52 mol) of m-cresol, 80 g (0.75 mol) of benzaldehyde, and 92 g (0.75 mol) of salicylaldehyde as starting materials, the same procedure as in Synthesis Example 2-1 was used to obtain 76 g of novolac-type phenolic resin (A-2) having an acetal protecting group. The Mw of novolac-type phenolic resin (A-2) was 3,230. The GPC chart for novolac-type phenolic resin (A-2) is shown in Figure 3.

[0111] Synthesis Example 2-3 (Novolac-type phenolic resin (A-3)) Except for using 164 g (1.52 mol) of m-cresol, 64 g (0.60 mol) of benzaldehyde, and 110 g (0.90 mol) of salicylaldehyde as starting materials, 81 g of novolac-type phenolic resin (A-3) having an acetal group protecting group was obtained in the same manner as in Synthesis Example 2-1. The Mw of novolac-type phenolic resin (A-3) was 3,990. The GPC chart for novolac-type phenolic resin (A-3) is shown in Figure 4.

[0112] Synthesis Example 2-4 (Novolac-type phenolic resin (A-4)) Except for using 164 g (1.52 mol) of m-cresol, 48 g (0.45 mol) of benzaldehyde, and 128 g (1.05 mol) of salicylaldehyde as starting materials, the same procedure as in Synthesis Example 2-1 was used to obtain 81 g of powder of novolac-type phenolic resin (A-4) having an acetal group protecting group. The Mw of novolac-type phenolic resin (A-4) was 4,150. The GPC chart for novolac-type phenolic resin (A-4) is shown in Figure 5.

[0113] Synthesis Example 2-5 (Novolac-type phenolic resin (A-5)) Except for using 164 g (1.52 mol) of m-cresol, 59 g of para-aldehyde (para-aldehyde is a trimer of acetaldehyde, 0.45 mol), and 18 g (0.15 mol) of salicylaldehyde as starting materials, 55 g of powder of novolac-type phenolic resin (A-5) having an acetal protecting group was obtained in the same manner as in Synthesis Example 2-1. The Mw of novolac-type phenolic resin (A-5) was 2,430.

[0114] Synthesis Example 2-6 (Novolac-type phenolic resin (A-6)) Except for using the aforementioned novolac-type phenolic resin powder (C-1) instead of novolac-type phenolic resin powder (A-1), 80 g of novolac-type phenolic resin powder (A-6) with an acetal-based protecting group was obtained in the same manner as in Synthesis Example 2-1. The weight-average molecular weight (Mw) of novolac-type phenolic resin powder (A-6) with an acetal-based protecting group was 13,740. The GPC chart for novolac-type phenolic resin (A-6) is shown in Figure 6.

[0115] Synthesis Example 2-7 (Novolac-type phenolic resin (A-7)) Except for using o-cresol instead of m-cresol as the starting material, 74 g of novolac-type phenolic resin (A-7) having an acetal protecting group was obtained in the same manner as in Synthesis Example 2-1. The Mw of novolac-type phenolic resin (A-7) was 3,330.

[0116] Comparative Synthesis Example 1-1 (Novolac-type phenolic resin (A-8)) Except for replacing salicylaldehyde (2-hydroxybenzaldehyde) with 3-hydroxybenzaldehyde, 77 g of novolac-type phenolic resin powder (A-8) was obtained using the same method as in Synthesis Example 2-1. The Mw of the novolac-type phenolic resin powder (A-8) was 12,760.

[0117] Comparative Synthesis Example 1-2 (Novolac-type phenolic resin (A-9)) Except for replacing salicylaldehyde (2-hydroxybenzaldehyde) with 4-hydroxybenzaldehyde, the same method as in Synthesis Example 2-1 was used to obtain 79 g of novolac-type phenolic resin powder (A-9). The Mw of the novolac-type phenolic resin powder (A-9) was 2,150.

[0118] Comparative Synthesis Example 1-3 (Novolac-type phenolic resin (A-10)) Except for replacing salicylaldehyde (2-hydroxybenzaldehyde) with benzaldehyde, 81 g of novolac-type phenolic resin powder (A-10) was obtained using the same method as in Synthesis Example 2-1. The Mw of the novolac-type phenolic resin powder (A-10) was 4,980.

[0119] Comparative Synthesis Example 1-4 (Novolac-type phenolic resin (A-11)) The synthesis was carried out using the same method as in Synthesis Example 2-1, except that m-cresol was replaced with phenol, and a gel-like resin (A-11) was obtained. Resin (A-11) was insoluble in the solvent and could not be evaluated.

[0120] Comparative Synthesis Example 1-5 (Novolac-type phenolic resin (A-12)) The synthesis was carried out using the same method as in Synthesis Example 2-1, except that m-cresol was replaced with 2,5-xylenol, and a suspension resin (A-12) was obtained. Resin (A-12) had poor solubility in solvents and could not be evaluated.

[0121] Comparative Synthesis Example 1-6 (Novolac-type phenolic resin (A-13)) 78 g of phenol novolac resin powder (A-13) was obtained using the same method as in Synthesis Example 2-1, except that m-cresol was replaced with catechol. The Mw of the novolac-type phenolic resin powder (A-13) was 9,690.

[0122] [Polyimide precursor (component (C))] Synthesis Example 3-1 (Polyimide resin precursor (C-2)) Under a stream of dry nitrogen, 125 g (0.023 mol) of pyromellitic anhydride and 115 g (0.023 mol) of 4,4-diaminodiphenyl ether were dissolved in 1,602 g of N-methyl-2-pyrrolidone in a 2,000 ml four-necked flask equipped with a condenser, and the mixture was stirred at 100°C for 4 hours. After the reaction was complete, the solution was added to 2,000 g of water, and the precipitate of the polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 80°C for 72 hours to obtain polyimide resin precursor (C-2) powder.

[0123] [Polybenzoxazole resin precursor (component (C))] Synthesis Example 3-2 (Polybenzoxazole resin precursor (C-3)) Under a stream of dry nitrogen, 60 g (0.164 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3,-hexafluoropropane and 34 g (0.157 mol) of 3,3-dihydroxybenzidine were dissolved in 650 g of N,N-dimethylacetamide in a 2,000 ml four-necked flask equipped with a condenser. Then, 140 g of pyridine was added, and while stirring at 0°C, a mixture of 265 g of cyclohexanone and 60 g (0.296 mol) of isophthalic acid dichloride was added dropwise over 2 hours, and the mixture was allowed to react at room temperature for 12 hours. After the reaction was complete, the solution was added to 10,000 g of water, and the precipitate of the polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 80°C for 72 hours to obtain polybenzoxazole resin precursor (C-3) powder.

[0124] [Positive-type photosensitive resin composition] Example 1 (1) Preparation of a chemically amplified photosensitive resin composition (Composition F) 1.98 g of novolac-type phenolic resin (A-1) powder and 0.02 g of photoacid generator (manufactured by Sanwa Chemical Co., Ltd.: TFE-triazine) were dissolved in 8.0 g of propylene glycol monomethyl ether (PGME), and the mixture was microfiltered using a 0.1 μm PTFE disc filter to obtain a chemically amplified photosensitive resin composition (solid content concentration 20%).

[0125] (2-1) Preparation of naphthoquinone-type photosensitive resin composition (composition G-1) 1.8 g of novolac-type phenolic resin (C-1) and 0.2 g of naphthoquinone-type photosensitive agent (Toyo Gosei Kogyo Co., Ltd.: P-200) were dissolved in 8.0 g of PGME, and the mixture was microfiltered using a 0.1 μm PTFE disc filter to obtain naphthoquinone-type photosensitive resin composition (G-1) (solid content concentration 20%).

[0126] (2-2) Preparation of naphthoquinone-type photosensitive resin composition (composition G-2) 1.8 g of polyimide resin precursor (C-2) and 0.2 g of naphthoquinone-type photosensitive agent (Toyo Gosei Kogyo Co., Ltd.: P-200) were dissolved in 8.0 g of gamma-butyrolactone, and the mixture was microfiltered using a 0.1 μm PTFE disc filter to obtain naphthoquinone-type photosensitive resin composition (G-2) (solid content concentration 20%).

[0127] (2-3) Preparation of naphthoquinone-type photosensitive resin composition (composition G-3) 1.8 g of polybenzoxazole resin precursor (C-3) and 0.2 g of naphthoquinone-type photosensitizer (Toyo Gosei Kogyo Co., Ltd.: P-200) were dissolved in 8.0 g of gamma butyrolactone, and the mixture was microfiltered using a 0.1 μm PTFE disc filter to obtain naphthoquinone-type photosensitive resin composition (G-3) (solid content concentration 20%).

[0128] (3) Preparation of positive-type photosensitive resin composition Example 1 0.3 g of composition F obtained in (1) above and 1.7 g of composition (G-1) obtained in (2-1) above were thoroughly mixed to obtain a positive-type photosensitive resin composition.

[0129] Examples 2-12, Comparative Examples 1-4 In the preparation of the chemically amplified photosensitive resin composition (Composition F), the novolac-type phenolic resin (A-1) and the naphthoquinone-type photosensitive resin composition (G-1) were changed to the novolac-type phenolic resins (A-2) to (A-13) and the naphthoquinone-type photosensitive resin composition (G-2) or (G-3) shown in Table 1 or 2, and the mixing ratio of the chemically amplified photosensitive resin composition (Composition F) and the naphthoquinone-type photosensitive resin composition (Composition G) (Composition F:Composition G (weight ratio)) was changed as shown in Table 1 or 2. Otherwise, a positive-type photosensitive resin composition was prepared in the same manner as in Example 1.

[0130] Comparative Example 5 A chemically amplified photosensitive resin composition was obtained in the same manner as in Example 1(1), except that novolac-type phenolic resin (A-1) was replaced with novolac-type phenolic resin (A-2). The obtained chemically amplified photosensitive resin composition was used alone as a positive-type photosensitive resin composition.

[0131] Comparative Examples 6-8 The naphthoquinone-type photosensitive resin compositions (G-1) to (G-3) prepared in Example 1(2) were used individually as positive-type photosensitive resin compositions.

[0132] [evaluation] Resist films were prepared using the positive-type photosensitive resin compositions prepared in the examples and comparative examples, and their thick-film forming ability, alkali solubility of the resist films, development contrast, and heat resistance were evaluated.

[0133] (1) Thick film formability A positive-type photosensitive resin composition was applied to a 5-inch silicon wafer to a thickness of approximately 3 μm using a spin coater and dried on a hot plate at 110°C for 60 seconds. The photosensitive film formed on the wafer surface was observed using an optical microscope to check for the presence or absence of cracks. The evaluation criteria for thick film formation performance are as follows. ○: No cracks ×: Crack present The evaluation results are shown in Tables 1 and 2.

[0134] (2) Alkaline developability A positive-type photosensitive resin composition was coated onto a 5-inch silicon wafer to a thickness of approximately 1 μm using a spin coater, and dried on a hot plate at 110°C for 60 seconds to obtain a photosensitive film. Subsequently, the photosensitive film was exposed to UV light at 50 mJ / cm² using a UV exposure apparatus (UVE-1001SD, manufactured by San-ei Electric Works Co., Ltd.). 2 The wafers were exposed to light, and after exposure, they were baked (PEB) on a hot plate at 130°C for 90 seconds. The resulting wafers with the resist film were immersed in a developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried on a hot plate at 110°C for 60 seconds. The thickness of the resist film was measured before and after immersion in the developer, and the difference was divided by 60 to obtain the alkali solubility ADR1 (Å / s). The evaluation criteria are as follows. ○: ADR1 is 200 or higher ×: ADR1 is less than 200 The evaluation results are shown in Tables 1 and 2. The numbers in parentheses in Tables 1 and 2 represent the ADR1 values.

[0135] (3) Development contrast In (2) above, the value measured similarly without exposure of the resist film was defined as ADR2 (Å / s), and the ADR1 / ADR2 value was used as the development contrast. The evaluation criteria are as follows. ○: Development contrast is 10 or higher ×: Development contrast less than 10 The evaluation results are shown in Tables 1 and 2.

[0136] (4) Heat resistance A positive-type photosensitive resin composition was coated onto a 5-inch diameter silicon wafer using a spin coater, and then dried at 110°C for 60 seconds to obtain a film with a thickness of 1 μm. This film was scraped off, and the glass transition temperature (Tg) was measured. The Tg was measured using a differential thermal scanning calorimeter (DSC Q100, manufactured by T.A. Instruments Co., Ltd.) under nitrogen atmosphere conditions, temperature range -100 to 200°C, and heating rate of 10°C / min. The evaluation criteria are as follows. ○: Tg is 120℃ or higher ×: Tg is less than 120℃ The evaluation results are shown in Tables 1 and 2. The numbers in parentheses in Tables 1 and 2 represent the Tg values.

[0137] [Table 1]

[0138] [Table 2]

[0139] In Tables 1 and 2, the molar ratio of structural units of component (A) "(a1) / (a2) / (a3)" represents the molar ratio of structural unit (a1) derived from m-cresol, structural unit (a2) derived from salicylaldehyde, and structural unit (a3) ​​derived from benzaldehyde. In Table 1, the molar ratio of structural units of component (A) "(a1) / (a4) / (a5)" represents the molar ratio of structural unit (a1) derived from m-cresol, structural unit (a4) derived from p-cresol, and structural unit (a5) derived from formaldehyde. In Table 1, the molar ratio of structural units of component (A) "(a1) / (a2) / (a6)" represents the molar ratio of structural unit (a1) derived from m-cresol, structural unit (a2) derived from salicylaldehyde, and structural unit (a6) derived from acetaldehyde.

[0140] The results in Tables 1 and 2 show that the positive-type photosensitive resin composition of the present invention exhibits excellent thick-film formation properties. Furthermore, the resist film produced using the positive-type photosensitive resin composition of the present invention exhibits excellent alkali solubility, development contrast, and heat resistance.

Claims

1. A positive-type photosensitive resin composition comprising the following components (A) to (E), wherein the amount of component (C) is 100 parts by mass or more and 1900 parts by mass or less per 100 parts by mass of component (A). (A) comprising a phenol structural unit (a1) derived from m-cresol, an aldehyde structural unit (a2) derived from salicylaldehyde, and an aldehyde structural unit (a3) ​​derived from benzaldehyde, A novolac-type phenolic resin having an acetal-based protecting group, wherein the molar ratio of the structural units (a1), (a2), and (a3) ​​[(a1):(a2):(a3)] is 1.0:0.3 to 0.8:0.3 to 0.

8. (B) Photoacid generator (C) One or more resins selected from novolac-type phenolic resins, polyimide resins, and polybenzoxazole resins that do not have acetal-based protecting groups. (D) Naphthoquinone type photosensitive agent (E) Solvent

2. A positive-type photosensitive resin composition comprising the following components (A) to (E), wherein the amount of component (C) is 100 parts by mass or more and 1900 parts by mass or less per 100 parts by mass of component (A). (A) comprising a phenol structural unit (a1) derived from m-cresol, an aldehyde structural unit (a2) derived from salicylaldehyde, and an aldehyde structural unit (a6) derived from acetaldehyde, A novolac-type phenolic resin having an acetal-based protecting group, wherein the molar ratio of the structural units (a1), (a2), and (a6) [(a1):(a2):(a6)] is 1.0:0.01 to 0.4:0.6 to 0.

99. (B) Photoacid generator (C) One or more resins selected from novolac-type phenolic resins, polyimide resins, and polybenzoxazole resins that do not have acetal-based protecting groups. (D) Naphthoquinone type photosensitive agent (E) Solvent

3. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the acetal group protecting group is a group represented by the following formula (1). 【Transformation 3】 (In the formula, R １ and R ２ Each of these is independently a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ３ R is a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. ３ R １ or R ２ It may also combine with other elements to form a ring. *This symbol is bonded to the benzene ring that constitutes the main chain of the novolac-type phenolic resin.

4. The positive-type photosensitive resin composition according to claim 1, wherein component (A) is obtained by reacting a compound that forms an acetal group-based protecting group with a novolac-type phenol resin obtained by polycondensation of m-cresol, salicylaldehyde, and benzaldehyde in an organic solvent with an acid catalyst in a molar ratio (m-cresol:salicylic acid:benzaldehyde) in the range of 1.0:0.3 to 0.

8.

5. The positive-type photosensitive resin composition according to claim 4, wherein the compound forming the acetal group protecting group is a compound represented by the following formula (2). 【Chemistry 4】 (In the formula, R ３ These are linear alkyl groups having 1 to 20 carbon atoms, branched alkyl groups having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms. R ４ to R ６ is each independently a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

6. The compound according to claim 4, wherein the compound forming the acetal group protecting group is a propyl vinyl ether.

7. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the component (C) is a novolac-type phenol resin comprising a phenol structural unit derived from cresol and an aldehyde structural unit derived from formaldehyde.

8. The positive-type photosensitive resin composition according to claim 1 or 2, wherein component (C) comprises a structural unit (c1) derived from m-cresol, a structural unit (c2) derived from p-cresol, and a structural unit (c3) derived from formaldehyde, the molar ratio of the structural units [(c1):(c2):(c3)] is 1.0:0.2 to 3.0:0.5 to 5.0, and is a novolac-type phenolic resin that does not have an acetal group protecting group.

9. The component (D) is Aromatic (poly)hydroxy compounds and With a sulfonic acid having a quinone diazide group selected from naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, and orthoanthraquinone diazide sulfonic acid, The positive-type photosensitive resin composition according to claim 1 or 2, which is a complete ester compound, a partial ester compound, an amidate, or a partial amidate.

10. The positive-type photosensitive resin composition according to claim 1 or 2, comprising a chemically amplified photosensitive resin composition containing the aforementioned components (A), (B), and solvent (E1), and a naphthoquinone-type photosensitive resin composition containing the aforementioned components (C), (D), and solvent (E2).

11. A photosensitive film obtained by drying the positive-type photosensitive resin composition according to claim 1 or 2.

12. A resist film obtained from the positive-type photosensitive resin composition according to claim 1 or 2.

13. A resist underlayer film obtained from the positive-type photosensitive resin composition according to claim 1 or 2.

14. A permanent resist film obtained from the positive-type photosensitive resin composition according to claim 1 or 2.

Images