Positive photosensitive resin composition, photosensitive film, resist film, resist under film, resist permanent film, and method for producing film

Abstract

The invention provides a positive photosensitive resin composition, a photosensitive film, a resist film, a resist underlayer film, a resist permanent film, and a method for producing the film. The positive photosensitive resin composition contains the following components A to E. Component A: a novolac-type phenolic resin having an acetal group protecting group, the novolac-type phenolic resin containing a phenol structural unit derived from cresol and one or more aldehyde structural units derived from formaldehyde or salicylaldehyde; component B: a photoacid generator; component C: one or more resins selected from the group consisting of novolac phenolic resins, polyimide resins, and polybenzoxazole resins that do not have an acetal group protecting group; a component D: a naphthoquinone-type photosensitizer; and component E: a solvent.

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, and in particular to a positive photosensitive resin composition, a photosensitive film, a resist film, a resist underlayer film, a resist permanent film and a method for manufacturing the film. Background Art

[0002] In recent years, with the miniaturization of electronic devices, the high density of semiconductor packaging has been continuously promoted. In the past, in the formation of copper bumps or columns in the manufacture of semiconductor packaging for integrated circuits (IC) or large-scale integrated circuits (LSI), alkali-soluble resins (such as novolac-type phenolic resins) and positive photoresists for i-rays using naphthoquinone diazide compound-based photosensitizers were generally widely used. However, the miniaturization using i-rays is approaching its limit. In particular, in NAND memories, the three-dimensionalization of the storage layer for the purpose of large capacity has gradually become the mainstream. The three-dimensionalization of the storage layer requires an increase in the number of processing levels in the longitudinal direction, so the thickening of the resist film is required. In the thick film of tens of μm, in the exposure treatment of the photosensitive resin composition using the naphthoquinone diazide compound-based photosensitizer in the past, since there is not enough light to reach the bottom of the film, the resist layer at the bottom of the pattern will not cause alkali dissolution, and it is difficult to form a fine pattern with a high aspect ratio.

[0003] In view of the above-mentioned problem, a study has been conducted to replace the use of naphthoquinone diazide compound-based photosensitizers and use the chemically amplified positive photoresist used in the lithography using excimer lasers such as KrF, ArF, and EUV in the lithography using i-rays (e.g., Patent Document 1). When the photosensitive resin film using the chemically amplified positive photoresist is irradiated with light, an acid is generated from the photoacid generator, and the generated acid (proton) is used as an acid catalyst to separate the protective group of the acid-decomposable resin, thereby exposing the alkali-soluble group. In the chemically amplified positive photoresist, after the protective group is separated, the acid is catalytically regenerated, and other protective groups can be separated, so that a positive pattern with high alkali solubility can be produced even under a trace amount of light. Therefore, the alkali dissolution of the bottom of the film, which has become a problem in the production of thick films, can be achieved. However, in the positive photosensitive resin composition using the meta-cresol-based phenol novolac resin described in Patent Document 1, the sensitivity is still insufficient, and the residual film generation at the bottom of the pattern after development has not been solved.

[0004] Therefore, chemically amplified positive photosensitive resin compositions containing o-cresol and p-cresol in addition to m-cresol have been studied (for example, Patent Document 2).

[0005] [Prior art literature]

[0006] [Patent Document]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2003-149816

[0008] [Patent Document 2] Japanese Patent Application Publication No. 2019-203097 Summary of the invention

[0009] [Problems to be solved by the invention]

[0010] Even the photosensitive resin composition of Patent Document 2 has insufficient alkali solubility, and still generates a residual film at the bottom of the pattern after development due to insufficient sensitivity. With the increasing density of semiconductor packaging, it is required to develop a photosensitive resin composition that can develop a thick film pattern with a high aspect ratio with high sensitivity and without generating residue, and also has high heat resistance.

[0011] An object of the present invention is to provide a positive photosensitive resin composition which is excellent in thick film forming properties and can provide a resist film or the like having excellent developability, development contrast, and heat resistance.

[0012] [Technical means to solve the problem]

[0013] In order to solve the above-mentioned problems, the present inventors have conducted intensive research and found that the above-mentioned problems can be solved by combining the constituent components of a photosensitive resin composition using a naphthoquinonediazide compound-based photosensitizer with the constituent components of a chemically amplified photosensitive resin composition using a novolac-type phenol resin having a protective group, thereby completing the present invention.

[0014] That is, the present invention relates to a positive photosensitive resin composition comprising the following components (A) to (E).

[0015] A positive photosensitive resin composition comprises the following components (A) to (E).

[0016] (A) a novolac-type phenol resin comprising a phenol structural unit derived from cresol and one or more aldehyde structural units derived from formaldehyde or salicylaldehyde and having an acetal-based protective group

[0017] (B) Photoacid generator

[0018] (C) at least one resin selected from a novolac-type phenol resin having no acetal-based protective group, a polyimide resin, and a polybenzoxazole resin

[0019] (D) Naphthoquinone type photosensitizer

[0020] (E) Solvent

[0021] The present invention also relates to a photosensitive film obtained by drying the positive photosensitive resin composition.

[0022] The present invention also relates to a resist film obtained from the positive photosensitive resin composition.

[0023] The present invention also relates to a resist underlayer film obtained from a positive photosensitive resin composition.

[0024] The present invention also relates to a permanent resist film, which is obtained from a positive photosensitive resin composition.

[0025] [Effects of the Invention]

[0026] According to the present invention, there is provided a positive photosensitive resin composition which has high thick film forming properties and can provide a film having excellent developability, development contrast, and heat resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a GPC chart of the novolac-type phenol resin obtained in Synthesis Example 1.

[0028] Figure 2 This is a GPC chart of the novolac-type phenol resin obtained in Synthesis Example 2-1.

[0029] Figure 3 This is a GPC chart of the novolac-type phenol resin obtained in Synthesis Example 2-2.

[0030] Figure 4 This is a GPC chart of the novolac-type phenol resin obtained in Synthesis Example 2-3.

[0031] Figure 5 This is a GPC chart of the novolac-type phenol resin obtained in Synthesis Example 2-4.

[0032] Figure 6 This is a GPC chart of the novolac-type phenol resin obtained in Synthesis Example 2-5. DETAILED DESCRIPTION

[0033] The following describes the mode for carrying out the invention.

[0034] In addition, in this specification, "x to y" is a numerical range indicating "x or more and y or less." The upper limit value and the lower limit value described in the numerical range can be arbitrarily combined.

[0035] Furthermore, a combination of two or more of the various aspects of the present invention described below is also a aspect of the present invention.

[0036] [Positive photosensitive resin composition]

[0037] The positive photosensitive resin composition according to one embodiment of the present invention contains the following components (A) to (E).

[0038] (A) a novolac-type phenol resin comprising a phenol structural unit derived from cresol and one or more aldehyde structural units derived from formaldehyde or salicylaldehyde and having an acetal-based protective group

[0039] (B) Photoacid generator

[0040] (C) at least one resin selected from a novolac-type phenol resin having no acetal-based protective group, a polyimide resin, and a polybenzoxazole resin

[0041] (D) Naphthoquinone type photosensitizer

[0042] (E) Solvent

[0043] The components (A) and (B) are constituent components of a chemically amplified photosensitive resin composition, and the components (C) and (D) are constituent components of a photosensitive resin composition using a naphthoquinone diazide-based photosensitizer (hereinafter referred to as a naphthoquinone-type photosensitive resin composition). In this embodiment, by combining the constituent components of the chemically amplified photosensitive resin composition with the constituent components of the naphthoquinone-type photosensitive resin composition, alkali developability (sensitivity), heat resistance, and thick film forming properties that are not available in conventional chemically amplified photosensitive resin compositions can be exhibited.

[0044] ·Ingredients (A)

[0045] As component (A), a novolac type phenol resin having a protective group used in a chemically amplified photosensitive resin composition can be used. Specifically, a novolac type phenol resin comprising a phenol structural unit derived from cresol and an aldehyde structural unit derived from formaldehyde, and a novolac type phenol resin comprising a phenol structural unit derived from cresol and an aldehyde structural unit derived from salicylaldehyde can be mentioned.

[0046] Examples of the protecting group include acetal protecting groups.

[0047] In the case where the component (A) includes an aldehyde structural unit derived from formaldehyde, as the phenol structural unit, a phenol structural unit derived from m-cresol and / or a phenol structural unit derived from p-cresol is preferred.

[0048] When component (A) contains a structural unit (a1) derived from m-cresol, a structural unit (a4) derived from p-cresol, and a structural unit (a5) derived from formaldehyde, from the viewpoint of obtaining a positive photosensitive resin composition having excellent thick film forming properties, it is preferred that the molar ratio of the structural unit (a1), the structural unit (a4), and the structural unit (a5) [(a1): (a4): (a5)] is 1.0: 0.2 to 3.0: 0.5 to 5.0.

[0049] In one embodiment, component (A) preferably includes 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-based protecting group.

[0050] From the viewpoint of obtaining a resist film having higher developability and heat resistance, etc., it is preferred that component (A) further contains an aldehyde structural unit derived from benzaldehyde in addition to the aldehyde structural unit derived from salicylaldehyde.

[0051] 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-based protecting group, and the molar ratio of the structural unit (a1), the structural unit (a2), and the structural unit (a3) ​​[(a1): (a2): (a3)] is 1.0: 0.3-0.8: 0.3-0.8. The molar ratio [(a1): (a2): (a3)] is more preferably 1.0: 0.35-0.75: 0.35-0.75, and further preferably 1.0: 0.4-0.65: 0.4-0.65.

[0052] As long as the effects of the present invention can be obtained, the component (A) may contain structural units other than the structural units derived from the above-mentioned cresol, formaldehyde, salicylaldehyde, and benzaldehyde.

[0053] As the structural unit other than the structural units derived from cresol, formaldehyde, salicylaldehyde and benzaldehyde, an aldehyde structural unit derived from acetaldehyde can be mentioned, and the component (A) preferably further contains an aldehyde structural unit (a6) derived from acetaldehyde.

[0054] For example, component (A) is preferably a novolac-type phenol resin 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 having an acetal-based protective group, wherein the molar ratio of the structural unit (a1), the structural unit (a2), and the structural unit (a6) [(a1): (a2): (a6)] is 1.0: 0.01 to 0.4: 0.6 to 0.99. The molar ratio [(a1): (a2): (a6)] is more preferably 1.0: 0.02 to 0.3: 0.7 to 0.98, and even more preferably 1.0: 0.05 to 0.2: 0.8 to 0.95.

[0055] In one embodiment, the total content of the structural units derived from the cresol, formaldehyde, salicylaldehyde, benzaldehyde and acetaldehyde in component (A) is substantially 100 mass%. In addition, the total content of the structural units (a1) to (a6) in component (A) is substantially 100 mass%. In addition, the so-called substantially 100 mass% refers to the case where structural units other than the structural units (a1) to (a6) are inevitably included.

[0056] The acetal group-based protecting group possessed by the component (A) is preferably a group represented by the following formula (1).

[0057] [Chemistry 1]

[0058]

[0059] (Where R 1 and R 2 Each of them 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;

[0060] R 3 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; R 3 Can be used with R 1 or R 2 Bond to form a ring;

[0061] *Bonded to the benzene ring constituting the main chain of the novolac type phenol resin)

[0062] In the component (A), at least part of the phenolic hydroxyl groups of the novolac-type phenol resin are protected by the acetal-based protecting group represented by the above formula (1). The acetal-based protecting group can be removed by an acid generated from a photoacid generator.

[0063] When component (A) has an acetal protective group, C 13 -Nuclear Magnetic Resonance (NMR) to confirm.

[0064] In the formula (1), examples of the linear alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0065] Examples of the branched alkyl group having 3 to 20 carbon atoms include isopropyl, sec-butyl, tert-butyl, neopentyl, isopentyl, 2-methylpentyl, 3-methylpentyl, and 2,3-dimethylbutyl.

[0066] Examples of the cyclic alkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The cyclic alkyl group may have a substituent such as the linear alkyl group described above.

[0067] Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, anthracenyl, etc. The aryl group may have a substituent such as the alkyl group described above.

[0068] Aralkyl refers to an alkyl group (C n H 2n+1 ) wherein one or more hydrogen atoms of the alkyl group are replaced by an aryl group. The aryl group may have a substituent such as the alkyl group. Specifically, phenylmethyl, tolylmethyl, xylylmethyl, naphthylmethyl, hydroxynaphthylmethyl, dihydroxynaphthylmethyl, phenylethyl, hydroxyphenylethyl, dihydroxyphenylethyl, tolylethyl, xylylethyl, naphthylethyl, hydroxynaphthylethyl, dihydroxynaphthylethyl may be mentioned. The number of carbon atoms is preferably 7 to 15, for example.

[0069] R 3 Can be used with R 1 or R 2 Examples of the ring include oxygen-containing heterocyclic rings such as a furan ring and a pyran ring.

[0070] Specific examples of the acetal protecting group represented by the formula (1) include 1-methoxyethoxy, 1-ethoxyethoxy, 1-propoxyethoxy, 1-butoxyethoxy, 2-methoxypropoxy, 2-ethoxypropoxy, 1-(2-methylpropoxy)ethoxy, 1-(1-propoxy)propoxy, 1-ethoxybutoxy, 1-(2-methoxyethoxy)ethoxy, 1-(2-acetoxyethoxy)ethoxy, tetrahydrofuran-2-yl, 1-[(1-adamantyloxy)ethoxy]ethyl, 1-[2-(1-adamantylcarbonyloxy)ethoxy]ethyl, tetrahydro-2-pyranyl, tetrahydro-2-furanyl, 1-(cyclohexyloxy)ethoxy, )ethoxy, 1-phenoxyethoxy, 1-(2-cyclohexyl)ethoxyethoxy, (1-adamantyloxy)ethoxy, (2-adamantyloxy)ethoxy, (1-adamantylmethoxy)ethoxy, (2-adamantylethoxy)ethoxy, 1-(1-bicyclo[2.2.1]heptyloxy)ethoxy, 1-(2-bicyclo[2.2.1]heptyloxy)ethoxy, 1-(1-bicyclo[2.2.1]heptyloxy)ethoxy, 1-(2-bicyclo[2.2.1]heptyloxy)ethoxy, 2-(1,7,7-trimethylbicyclo[2.2.1]heptyloxy)ethoxy, 2-(1-isopropyl-4-methylcyclohexyloxy)ethoxy and the like.

[0071] The protecting group represented by the formula (1) is preferably a 2-propoxyethoxy group.

[0072] The protection ratio of the phenolic hydroxyl groups in the novolac-type phenol resin in component (A) (the ratio of the bonds of the acetal-based protecting groups relative to the total amount of the phenolic hydroxyl groups in the novolac-type phenol resin) is 1 mol% to 50 mol%, preferably 2 mol% to 40 mol%, more preferably 5 mol% to 25 mol%, and further preferably 7.5 mol% to 15 mol%, from the viewpoint of making the dissolution rate in the alkaline developer appropriate.

[0073] The weight average molecular weight of the novolac type phenol resin as component (A) is preferably 1000 or more, more preferably 1,500 or more. In addition, it is preferably 7,000 or less, more preferably 6,000 or less, and further preferably 5,000 or less. When the weight average molecular weight is 1000 or more, it is preferred because it is highly heat-resistant. On the other hand, when the weight average molecular weight is 7,000 or less, it is preferred because it is highly sensitive. In addition, in this specification, the weight average molecular weight is measured according to the conditions described in the examples.

[0074] Component (A) can be synthesized by a known method, for example, by polycondensing cresol, formaldehyde or salicylaldehyde, and any benzaldehyde in an organic solvent in the presence of an acid catalyst to form a novolac-type phenol resin, and then reacting it with a compound that forms an acetal-based protective group.

[0075] Hereinafter, as an example, the synthesis of a novolac-type phenol resin (a) using m-cresol, salicylaldehyde, and benzaldehyde as monomers and the introduction of an acetal-based protective group will be described.

[0076] (Synthesis of novolac type phenol resin (a))

[0077] The novolac-type phenol resin (a) can be obtained, for example, by dissolving a raw material compound in a reaction solvent according to a conventional method and conducting a synthesis reaction using an acid catalyst.

[0078] As the reaction solvent used when producing the novolac type phenol resin (a), for example, there can be mentioned: methanol, ethanol, 1-propanol, 2-propanol, butanol, hexanol, ethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, toluene, etc. Among these, preferably one or more selected from ethanol, 1-propanol, and 2-propanol, more preferably ethanol or methyl isobutyl ketone.

[0079] When producing a resin containing a structural unit derived from m-cresol, a structural unit derived from salicylaldehyde, and a structural unit derived from benzaldehyde as a novolac-type phenol resin (a), it is preferred to synthesize the monomers by polycondensation in an organic solvent at a molar ratio (m-cresol: salicylaldehyde: benzaldehyde) of 1.0:0.3 to 0.8:0.3 to 0.8 using an acid catalyst.

[0080] The molar ratio (m-cresol: salicylaldehyde: benzaldehyde) is more preferably 1.0: 0.35 to 0.75: 0.35 to 0.75, and even more preferably 1.0: 0.4 to 0.65: 0.4 to 0.65.

[0081] When producing a resin containing a structural unit derived from m-cresol, a structural unit derived from salicylaldehyde, and a structural unit derived from acetaldehyde as a novolac-type phenol resin (a), it is preferred to synthesize the monomers by polycondensation in an organic solvent at a molar ratio (m-cresol: salicylaldehyde: acetaldehyde) of 1.0:0.01 to 0.4:0.6 to 0.99 using an acid catalyst.

[0082] The molar ratio (m-cresol: salicylaldehyde: acetaldehyde) is more preferably 1.0: 0.02 to 0.3: 0.7 to 0.98, and even more preferably 1.0: 0.05 to 0.2: 0.8 to 0.95.

[0083] The amount of the reaction solvent used is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass or less, based on 100 parts by mass of the monomer, from the viewpoint of reaction uniformity.

[0084] Examples of the acid catalyst used in the production of the novolac type phenol 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. Of these, inorganic acids and p-toluenesulfonic acid are preferred, and p-toluenesulfonic acid is more preferred in order to further promote the reaction.

[0085] The amount of the acid catalyst added is not particularly limited, but is preferably 5 parts by mass or more, more preferably 20 parts by mass or more, and preferably 150 parts by mass or less, more preferably 100 parts by mass or less, based on 100 parts by mass of the monomer.

[0086] The reaction temperature when polycondensing the monomers is preferably 30° C. or higher, more preferably 40° C. or higher, and preferably 100° C. or lower, more preferably 80° C. or lower, in order to promote the reaction and efficiently increase the molecular weight.

[0087] The reaction time is preferably 4 hours or longer, more preferably 12 hours or longer, and preferably 32 hours or shorter, more preferably 24 hours or shorter.

[0088] (Introduction of acetal-based protecting group)

[0089] The method for introducing the acetal group-protecting group is not particularly limited, and for example, there can be mentioned a method in which the novolac resin (a) and a compound that forms an acetal group-protecting group are charged into a reaction solvent and reacted using an acid catalyst.

[0090] The acetal group-protecting group is generated by reacting the phenolic hydroxyl group in the novolac type phenol resin (a) with a compound that forms an acetal group-protecting group in the presence of an acid catalyst, thereby protecting the phenolic hydroxyl group in the novolac type phenol resin (a).

[0091] As the reaction solvent used for the introduction of the acetal-based protective group, the reaction solvent used for the synthesis of the novolac-type phenol resin (a) can be preferably used. As the reaction solvent used for the introduction of the acetal-based protective group, methyl isobutyl ketone is preferred.

[0092] The acid catalyst used for the introduction of the acetal-based protecting group is preferably the acid catalyst used for the synthesis of the novolac-type phenol resin (a). Among these, inorganic acids and p-toluenesulfonic acid are preferred, and p-toluenesulfonic acid is more preferred in order to further promote the reaction.

[0093] When an acetal-based protecting group is introduced, the reaction time is preferably 1 hour or longer, more preferably 2 hours or longer, and preferably 10 hours or shorter, more preferably 6 hours or shorter.

[0094] When the acetal-based protecting group is introduced, the reaction temperature can be the same as that in the synthesis of the novolac-type phenol resin (a).

[0095] In the present embodiment, the compound that forms the acetal group-based protecting group is preferably a compound represented by the following formula (2).

[0096] [Chemistry 2]

[0097]

[0098] (Where R 3 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;

[0099] R 4 ~R 6 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)

[0100] In formula (2), specific examples of the linear alkyl group having 1 to 20 carbon atoms, the branched alkyl group having 3 to 20 carbon atoms, the cyclic alkyl group having 3 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the aralkyl group having 7 to 20 carbon atoms are the same as those in formula (1).

[0101] R 3 , R 4 , R 5 and R 6 Any two of them can be bonded to form a ring, such as R 3 With R 6 Can bond to form cyclic ethers.

[0102] Examples of the compound represented by the formula (2) that forms an acetal-based protecting group include methyl vinyl (vinyl) ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclopentyl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl 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, [(adamantan-2-yl)methyl]vinyl ether 1-(vinyloxy)-1,1-bicyclohexane, 3,4-dihydropyran, etc. Among them, propyl vinyl ether is preferred.

[0103] In this embodiment, in terms of obtaining good developability (sensitivity) and development contrast, the amount of the compound represented by the formula (2) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the novolac type phenol resin (a). In addition, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less.

[0104] Component (B)

[0105] The photoacid generator as component (B) refers to a compound that generates an acid by causing bond cleavage by exposure. By containing the photoacid generator, the acetal group-based protective group is separated from component (A) in the exposed part by utilizing the acid generated by the photoacid generator. Through this reaction, since the phenolic hydroxyl group of the novolac type phenol resin (A) is exposed, a difference in alkali solubility can be generated between the unexposed part and the exposed part. In addition, through the synergistic effect with the component (D) described later, when the positive photosensitive resin composition is formed into a photosensitive film, etc., the developability (sensitivity) and development contrast can be improved.

[0106] The photoacid generator is not particularly limited, and a known photoacid generator can be used, for example, organic halogen compounds, sulfonates, onium salts (phosphonium salts, sulfonium salts, iodonium salts, etc.), diazonium salts, diazomethane compounds, nitrobenzyl compounds, disulfone compounds, triazine-based photoacid generators, etc.

[0107] In one embodiment, the photoacid generator is not naphthoquinone diazide.

[0108] Specific examples of the photo-acid generator include the following.

[0109] s-triazine derivatives containing a halogenated alkyl group, such as tris(trichloromethyl)-s-triazine, tris(tribromomethyl)-s-triazine, tris(dibromomethyl)-s-triazine, 2,4-bis(tribromomethyl)-6-p-methoxyphenyl-s-triazine, (2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine);

[0110] Halogen-substituted paraffin hydrocarbon compounds such as 1,2,3,4-tetrabromobutane, 1,1,2,2-tetrabromoethane, carbon tetrabromide, and triiodomethane; halogen-substituted cycloparaffin hydrocarbon compounds such as hexabromocyclohexane, hexachlorocyclohexane, and hexabromocyclododecane;

[0111] Benzene derivatives containing alkyl halide such as bis(trichloromethyl)benzene and bis(tribromomethyl)benzene; sulfone compounds containing alkyl halide such as tribromomethylphenyl sulfone and trichloromethylphenyl sulfone; halogen-containing sulfolane compounds such as 2,3-dibromosulfolane; isocyanurate compounds containing alkyl halide such as tris(2,3-dibromopropyl)isocyanurate;

[0112] Sulfonium salts such as triphenylsulfonium chloride, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl[4-(phenylthio)phenyl]sulfonium trifluoromethanesulfonate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium hexafluorophosphonate;

[0113] Iodine salts such as diphenyl iodine trifluoromethanesulfonate, diphenyl iodine p-toluenesulfonate, diphenyl iodine tetrafluoroborate, diphenyl iodine hexafluoroarsenate, and diphenyl iodine hexafluorophosphonate;

[0114] Sulfonate compounds such as methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, 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 diphenyl disulfone;

[0115] 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)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, cyclohexylsulfonyl-(2-trifluoromethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl Acyl-(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, sulfonyl)diazomethane, cyclopentylsulfonyl-(4-trifluoromethoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2,4,6-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,4-triethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2-methoxyphenylsulfonyl)diazomethane, phenylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane, phenylsulfonyl-(4-methoxyphenylsulfonyl)diazomethane, bis(2-methoxyphenylsulfonyl)diazomethane, bis(3-methoxyphenylsulfonyl)diazomethane, bis(4-methoxyphenylsulfonyl)diazomethane, phenylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane, Sulfone diazide compounds such as phenylsulfonyl-(2,4,6-triethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2,3,4-triethylphenylsulfonyl)diazomethane, 2,4-dimethylphenylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane, 2,4-dimethylphenylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2-fluorophenylsulfonyl)diazomethane, phenylsulfonyl-(3-fluorophenylsulfonyl)diazomethane, and phenylsulfonyl-(4-fluorophenylsulfonyl)diazomethane;

[0116] o-nitrobenzyl-p-toluenesulfonate and other o-nitrobenzyl ester compounds;

[0117] Sulfone hydrazide compounds such as N,N'-di(phenylsulfonyl)hydrazide;

[0118] The salt formed by sulfonium cations such as triarylsulfonium and triaralkylsulfonium and sulfonates such as fluoroalkanesulfonates, arenesulfonates, and alkanesulfonates is a sulfonium salt;

[0119] The salt formed by iodine cations such as diaryliodonium and sulfonates such as fluoroalkanesulfonates, arenesulfonates, and alkanesulfonates is called iodine salt;

[0120] Bissulfonyldiazomethane compounds such as bis(alkylsulfonyl)diazomethane, bis(cycloalkylsulfonyl)diazomethane, bis(perfluoroalkylsulfonyl)diazomethane, bis(arylsulfonyl)diazomethane, and bis(aralkylsulfonyl)diazomethane;

[0121] N-sulfonyloxyimide compounds formed by combining a dicarboxylic acid imide compound with a sulfonate such as a fluoroalkanesulfonate, an aromatic hydrocarbon sulfonate, or an alkanesulfonate;

[0122] Benzoin sulfonate (salt) compounds such as benzoin toluene sulfonate (salt), benzoin methane sulfonate (salt), and benzoin butane sulfonate (salt);

[0123] Polyhydroxy aromatic hydrocarbon sulfonate (salt) compounds obtained by replacing all hydroxyl groups of polyhydroxy aromatic hydrocarbon compounds with sulfonate (salt) such as fluoroalkane sulfonate (salt), aromatic hydrocarbon sulfonate (salt), alkane sulfonate (salt) and the like;

[0124] Nitrobenzyl sulfonate compounds such as nitrobenzyl fluorinated alkane sulfonate, nitrobenzyl aromatic sulfonate, and nitrobenzyl alkane sulfonate;

[0125] Fluorinated alkane benzyl sulfonate compounds such as (poly)fluoroalkane benzyl sulfonate, (poly)fluoroalkane benzyl sulfonate, (poly)fluoroalkane benzyl sulfonate, and (poly)fluoroalkane benzyl sulfonate;

[0126] Bis(arylsulfonyl)alkane compounds;

[0127] Bis-O-(arylsulfonyl)-α-dialkylglyoxime, bis-O-(arylsulfonyl)-α-dicycloalkylglyoxime, bis-O-(arylsulfonyl)-α-diarylglyoxime, bis-O-(alkylsulfonyl)-α-dialkylglyoxime, 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, bis-O-(arylsulfonyl)-α-dialkyldioxime, bis-O-(arylsulfonyl)-α-dicycloalkyldioxime, bis-O-(arylsulfonyl)-α-diaryldioxime, bis-O-(alkylsulfonyl)-α-dialkyldioxime, bis-O-(alkylsulfonyl)-α-dicycloalkyldioxime, bis-O-(alkylsulfonyl)-α-diaryldioxime, bis-O-(fluoroalkylsulfonyl)-α-dialkyldioxime, bis-O-(fluoroalkylsulfonyl)-α-dicycloalkyldioxime, bis-O-(fluoroalkylsulfonyl)-α-diaryldioxime and the like;

[0128] 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)arylenediacetonitrile, bis(alkylsulfonyloxyimino)arylenediacetonitrile, bis(fluoroalkylsulfonyloxyimino)arylenediacetonitrile, arylfluoroalkanone-O-(alkylsulfonyl)oxime, arylfluoroalkanone-O-(arylsulfonyl)oxime, and arylfluoroalkanone-O-(fluoroalkylsulfonyl)oxime.

[0129] The photoacid generator may be used alone or in combination of two or more.

[0130] The amount of the photoacid generator is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of component (A), from the viewpoint of obtaining good thick film forming properties of the positive photosensitive resin composition and good developability (sensitivity) and heat resistance when the positive photosensitive resin composition is made into a resist film or the like. In addition, it is preferably 20 parts by mass or less, more preferably 5 parts by mass or less.

[0131] Component (C)

[0132] Component (C) is one or more resins selected from the group consisting of novolac-type phenol resins having no acetal-based protective group, polyimide resins, and polybenzoxazole resins.

[0133] The positive photosensitive resin composition of this embodiment contains component (C) in addition to component (A) which is a novolac-type phenol resin having an acetal-based protective group, thereby obtaining a resist film having excellent thick film forming properties and excellent developability and heat resistance.

[0134] From the viewpoint of obtaining a positive photosensitive resin composition having excellent thick film forming properties, the novolac-type phenol resin having no acetal-based protective group as component (C) is preferably a novolac-type phenol resin containing a phenol structural unit derived from cresol and an aldehyde structural unit derived from formaldehyde.

[0135] From the viewpoint of obtaining a positive photosensitive resin composition having excellent thick film forming properties, the phenol structural unit derived from cresol contained in the novolac-type phenol resin having no acetal-based protecting group is more preferably a phenol structural unit (c1) derived from m-cresol and a phenol structural unit (c2) derived from p-cresol.

[0136] From the viewpoint of obtaining a positive photosensitive resin composition having excellent thick film forming properties, in a novolac-type phenol resin having no acetal-based protecting group, the molar ratio of the structural unit (c1) derived from m-cresol, the structural unit (c2) derived from p-cresol, and the structural unit (c3) derived from formaldehyde [(c1):(c2):(c3)] is preferably 1.0:0.2 to 3.0:0.5 to 5.0.

[0137] The novolac-type phenol resin having no acetal-based protecting group may contain structural units other than the structural unit (c1) derived from m-cresol, the structural unit (c2) derived from p-cresol, and the structural unit (c3) derived from formaldehyde. Examples of structural units other than (c1), (c2), and (c3) include structural units derived from phenols or aldehydes other than m-cresol, p-cresol, and formaldehyde.

[0138] Examples of the phenols include 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, and 3,4,5-trimethylphenol.

[0139] Examples of the aldehydes include paraformaldehyde, acetaldehyde, chloroacetaldehyde, 4-hydroxybenzaldehyde, and 3-hydroxybenzaldehyde.

[0140] The novolac type phenol resin without acetal-based protecting groups is obtained, for example, by polycondensing starting materials containing cresol and formaldehyde in an organic solvent using an acid catalyst. The novolac type phenol resin without acetal-based protecting groups can be synthesized under the same synthesis conditions as the novolac type phenol resin (A), except that the acetal-based protecting groups are not introduced. The organic solvent and acid catalyst used to synthesize the novolac type phenol resin without acetal-based protecting groups may be the same as or different from the organic solvent and acid catalyst used to synthesize the novolac type phenol resin (a).

[0141] The polyimide resin as the component (C) includes a polyimide resin precursor and may be at least one of a polyimide resin and a polyimide resin precursor.

[0142] Examples of the polyimide resin precursor include those obtained by reacting tetracarboxylic acid, the corresponding tetracarboxylic dianhydride or tetracarboxylic diester dichloride with diamine, the corresponding diisocyanate compound or trimethylsilylated diamine, and the like, and having a tetracarboxylic acid and / or derivative residue thereof and a diamine and / or derivative residue thereof.

[0143] As a polyimide resin precursor, a polyamic acid, a polyamic acid ester, a polyamic acid amide, or a polyisoimide is mentioned, for example.

[0144] Examples of the polyimide resin include polyimide resins obtained by dehydration ring closure of the polyamic acid, polyamic acid ester, polyamic acid amide or polyisoimide by heating or reaction with an acid or base, and having a tetracarboxylic acid and / or derivative residue thereof and a diamine and / or derivative residue thereof.

[0145] From the viewpoint of heat resistance, the tetracarboxylic dianhydride used for synthesizing the polyimide resin is preferably pyromellitic dianhydride. From the viewpoint of heat resistance, the diamine used for synthesizing the polyimide is preferably 4,4-diaminodiphenyl ether.

[0146] The polybenzoxazole resin as the component (C) includes a polybenzoxazole resin precursor and may be at least one of a polybenzoxazole resin and a polybenzoxazole resin precursor.

[0147] Examples of the polybenzoxazole resin precursor include those obtained by reacting dicarboxylic acid, a corresponding dicarboxylic acid dichloride or a dicarboxylic acid active diester with a bisaminophenol compound as a diamine, and have a dicarboxylic acid and / or derivative residue and a bisaminophenol compound and / or derivative residue.

[0148] As a polybenzoxazole precursor, polyhydroxyamide is mentioned, for example.

[0149] Examples of the polybenzoxazole include those obtained by dehydration ring closure of a dicarboxylic acid and a bisaminophenol compound as a diamine by reaction with polyphosphoric acid; and those obtained by dehydration ring closure of the polyhydroxyamide by heating or reaction with anhydrous phosphoric acid, an alkali or a carbodiimide compound, which have a dicarboxylic acid and / or a derivative residue thereof, and a bisaminophenol compound and / or a derivative residue thereof.

[0150] From the viewpoint of heat resistance, the bisaminophenol used for synthesizing polybenzoxazole is preferably 3,3-hydroxybenzidine. From the viewpoint of heat resistance, the dicarboxylic acid used for synthesizing polybenzoxazole is preferably 4,4-biphenyldicarboxylic acid.

[0151] The amount of component (C) in the photosensitive resin composition of the present embodiment is preferably 30 parts by mass or more, more preferably 100 parts by mass or more, and preferably 1900 parts by mass or less, more preferably 900 parts by mass or less, based on 100 parts by mass of component (A).

[0152] Component (D)

[0153] The naphthoquinone type photosensitizer as component (D) refers to a compound having a quinone diazide group. The novolac type phenol resin as component (A) or component (C) has a high affinity with the photoacid generator or naphthoquinone type photosensitizer as component (B), so the positive photosensitive resin composition of this embodiment becomes a positive photosensitive resin composition with excellent developability.

[0154] Specifically, the component (D) acts as a dissolution inhibitor of the novolac type phenol resin of the component (A) and the component (C) before light irradiation, so the photosensitive film etc. obtained from the positive photosensitive resin composition of the present embodiment is not dissolved in an alkaline developer. After light irradiation, the component (D) causes photodecomposition in the exposed part, so the dissolution inhibitory effect of the novolac type phenol resin of the component (A) and the component (C) is lost, and the photosensitive film etc. obtained from the positive photosensitive resin composition of the present embodiment can be dissolved in an alkaline developer.

[0155] Specific examples of the compound having a quinonediazide group which can be used as component (D) include complete ester compounds, partial ester compounds, amides or partial amides of aromatic (poly)hydroxy compounds and sulfonic acids having a quinonediazide group such as naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid and o-anthraquinonediazidesulfonic acid.

[0156] Examples of the (poly)hydroxy compound 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;

[0157] 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 and the like;

[0158] 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, and bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, or methyl-substituted products thereof;

[0159] 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) Bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methane compounds or methyl-substituted products thereof such as bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-4-hydroxyphenylmethane, 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.

[0160] These naphthoquinone type photosensitizers may be used alone or in combination of two or more.

[0161] In terms of forming a positive photosensitive resin composition with excellent developability (photosensitivity), the amount of component (D) in the photosensitive resin composition of the present embodiment is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of component (C). In addition, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less.

[0162] ·Ingredient (E)

[0163] As the solvent of component (E), there can be mentioned: polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, etc.; ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, etc.; esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, etc.; alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, etc.; aromatic hydrocarbons such as toluene and xylene, etc. These solvents may be used alone or in combination of two or more.

[0164] In terms of obtaining a uniform coating film by a coating method such as a spin coating method by utilizing the fluidity of the composition, the amount of the solvent in the positive photosensitive resin composition of the present embodiment is preferably an amount such that the solid content concentration in the composition is 5% by mass or more. In addition, it is preferably an amount such that the solid content concentration in the composition is 65% by mass or less.

[0165] Other ingredients

[0166] In one embodiment, in addition to the components (A) to (E) described above, various additives may be added to the positive photosensitive resin composition within a range that does not hinder the effects of the present invention. Examples of additives include fillers, pigments, surfactants such as leveling agents, adhesion enhancers, dissolution promoters, and the like.

[0167] The positive photosensitive resin composition of this embodiment can be prepared by stirring and mixing the components (A) to (E) and various additives as needed to form a uniform liquid using a common method. For example, in one embodiment, the positive photosensitive resin composition can be prepared by mixing the components (A) and (C) in the component (E), and then further mixing the components (B) and (D).

[0168] In one embodiment, the positive photosensitive resin composition can be set to a so-called two-liquid positive photosensitive resin composition composed of a chemically amplified photosensitive resin composition (F) containing component (A), component (B) and component (E1) solvent, and a naphthoquinone photosensitive resin composition (G) containing component (C), component (D) and component (E2) solvent.

[0169] When the positive photosensitive resin composition is used as a two-component positive photosensitive resin composition, it is preferred that the component (F) and the component (G) are uniformly mixed before use.

[0170] The solvent component (E1) and the solvent component (E2) contained in each of the chemically amplified photosensitive resin composition (F) and the naphthoquinone type photosensitive resin composition (G) may be the same or different.

[0171] In one embodiment, when the positive photosensitive resin composition consists of component (F) and component (G), the mixing ratio [(F): (G)] is preferably 5:95 to 50:50, more preferably 15:85 to 30:70 in terms of mass ratio from the viewpoint of thick film forming property, developability and heat resistance.

[0172] When solid additives such as fillers and pigments are mixed in this composition, it is preferred to use a dispersing device such as a dissolver, a homogenizer, a three-roll mill, etc. to disperse and mix. In addition, in order to remove coarse particles or impurities, a mesh filter, a membrane filter, etc. can also be used to filter this composition.

[0173] The positive photosensitive resin composition of the present embodiment can be suitably used for applications such as positive photoresists, organic underlayer films, thick film resists (bump forming resists), interlayer insulating films, liquid crystal alignment films, and heat resistance imparting agents.

[0174] ·Method for producing membrane

[0175] The positive 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, the resist underlayer film and the resist permanent film are sometimes collectively referred to as a resist film, etc.) in the same manner as a general positive photosensitive resin composition.

[0176] Specifically, by applying the positive photosensitive resin composition of the present invention onto an object to be photolithographically processed and pre-baking the composition, a film of the photosensitive resin composition (photosensitive film) from which the solvent has been removed can be obtained.

[0177] In one embodiment, the method for manufacturing a film includes the following steps: mixing a chemically amplified photosensitive resin composition (F) comprising the component (A), the component (B) and the component (E) with a naphthoquinone-type photosensitive resin composition (G) comprising the component (C), the component (D) and the component (E) to prepare a positive photosensitive resin composition.

[0178] The prepared positive photosensitive resin composition is applied to an object. Examples of the coating method include spin coating, roller coating, flow coating, dip coating, spray coating, and blade coating. Prebaking, for example, requires heating at a temperature of 60° C. to 150° C. for 30 seconds to 600 seconds. In addition, the positive photosensitive resin composition of the present invention can be appropriately selected as a glass substrate, a silicon substrate, an aluminum substrate, a silicon carbide substrate, a silicon nitride substrate, a gallium nitride substrate, a transparent conductive film, a copper substrate, a copper-plated substrate, and the like as the coating object.

[0179] By utilizing the catalytic reaction of the acid generated by exposing the photosensitive film, a reaction is generated in which the acetal-based protecting group is separated from component (A), and the solubility of the exposed portion in the alkaline developer is greatly increased. As the light source used in the exposure, for example, infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams can be cited. Among these light sources, ultraviolet light is preferred, and g-rays (wavelength 436nm) and i-rays (wavelength 365nm) of a high-pressure mercury lamp are suitable.

[0180] After the exposure, a heat treatment may be performed at about 100° C. to 150° C. in order to promote the reaction of releasing the acetal-based protective group from the component (A).

[0181] The photosensitive film obtained from the positive photosensitive resin composition of the present invention can be patterned with high resolution because the exposed portion has high alkali solubility and a large difference in alkali solubility from the unexposed portion. Therefore, it can be suitably used for resist films, etc. In addition, in the present application, the resist film, etc. includes both the photosensitive film before exposure and the non-photosensitive film after exposure.

[0182] Examples of the alkaline developer used in post-exposure development include inorganic alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water; 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 piperidine.

[0183] Alcohol, surfactant, etc. may be appropriately added to the alkaline developer 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 tetramethylammonium hydroxide aqueous solution is generally used.

[0184] When the positive photosensitive resin composition of the present invention is used for an anti-etching underlayer film (bottom anti-reflection coating (Bottom Anti-Reflection Coating, BARC) film), the positive photosensitive resin composition of the present invention can be used directly as a composition for an anti-etching underlayer film. In addition, various additives such as other resin components, surfactants, dyes, fillers, cross-linking agents, and dissolution promoters can be added as needed.

[0185] As other resin components, for example, various novolac resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenolic compounds, modified novolac resins of phenolic hydroxyl-containing compounds and alkoxy-containing aromatic compounds, phenol aralkyl resins (Xylock resins), naphthol aralkyl resins, trimethylolmethane resins, tetrahydroxyphenylethane resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, aminotriazine-modified phenol resins, and various vinyl polymers can be listed.

[0186] When other resin components are used, the ratio of the positive photosensitive resin composition of the present invention to other resins can be arbitrarily set according to the application. For example, the other resin is preferably 0.5 to 100 parts by mass relative to 100 parts by mass of the total of component (A) and component (C).

[0187] The resist underlayer film composition can be prepared by blending the above components and mixing them using a stirrer, etc. When the resist underlayer film composition contains a filler or a pigment, it can be adjusted by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three-roll mill.

[0188] In order to form a resist underlayer film from a resist underlayer film composition, there is a method, for example, in which the resist underlayer film composition is applied to an object to be photolithographically processed such as a silicon substrate, dried at a temperature of 100° C. to 200° C., and then cured by heating at a temperature of 250° C. to 400° C. Subsequently, a normal photolithography operation is performed on the underlayer film to form a resist pattern, and a dry etching process is performed using a halogen plasma gas or the like, thereby forming a resist pattern using a multilayer resist method.

[0189] When the positive photosensitive resin composition of the present invention is used for resist permanent film applications, in addition to the components (A) to (E) of the present invention, other resins, surfactants, dyes, fillers, crosslinking agents, dissolution accelerators and other additives may be added as needed. Examples of the other resins used herein include the same resins as those that can be used in the resist underlayer film composition.

[0190] In the photolithography method using the resist permanent film composition, for example, other resin components and additive components are dissolved and dispersed in the positive photosensitive resin composition of the present invention, applied to the object to be photolithographically processed, and pre-baked at a temperature of 60° C. to 150° C. The coating method at this time may be any of spin coating, roll coating, flow coating, dip coating, spray coating, and blade coating. Next, the target resist pattern is exposed through a predetermined mask, and the exposed portion is dissolved with an alkaline developer, thereby forming a resist pattern.

[0191] The permanent anti-etching film of this embodiment can be suitably used in, for example, packaging adhesive layers of solder resists, packaging materials, bottom filling materials, circuit elements, and the like, and adhesive layers between integrated circuit elements and circuit substrates, for semiconductor devices. In addition, for thin displays represented by liquid crystal displays (LCD) and organic light-emitting diodes (OELD), it can be suitably used in thin-film transistor protective films, liquid crystal color filter protective films, black matrices, spacers, and the like.

[0192] [Example]

[0193] The present invention will be described in further detail below with reference to specific examples. The weight average molecular weight (Mw) of the synthesized resin is measured under the following gel permeation chromatography (GPC) measurement conditions.

[0194] [GPC measurement conditions]

[0195] Measuring device: "HLC-8220GPC" manufactured by Tosoh Corporation

[0196] Pipe column: "Shodex KF802" manufactured by Showa Denko Co., Ltd.: 8.0 mm φ × 300 mm

[0197] + "Shodex KF802" manufactured by Showa Denko Co., Ltd.: 8.0 mm φ × 300 mm

[0198] + "Shodex KF803" manufactured by Showa Denko Co., Ltd.: 8.0 mm φ × 300 mm

[0199] + "Shodex KF804" manufactured by Showa Denko Co., Ltd.: 8.0 mm φ × 300 mm

[0200] Column temperature: 40℃

[0201] Detector: RI (differential refractometer)

[0202] Data processing: "GPC-8020 Model II Version 4.30" manufactured by Tosoh Co., Ltd.

[0203] Development solvent: tetrahydrofuran

[0204] Flow rate: 1.0mL / min

[0205] Sample: A tetrahydrofuran solution containing 0.5% by mass in terms of resin solid content was filtered through a microfilter.

[0206] Injection volume: 0.1mL

[0207] Standard sample: Monodisperse polystyrene as follows

[0208] (Standard sample: monodisperse polystyrene)

[0209] "A-500" manufactured by Tosoh Co., Ltd.

[0210] "A-2500" manufactured by Tosoh Co., Ltd.

[0211] "A-5000" manufactured by Tosoh Co., Ltd.

[0212] "F-1" manufactured by Tosoh Co., Ltd.

[0213] "F-2" manufactured by Tosoh Co., Ltd.

[0214] "F-4" manufactured by Tosoh Co., Ltd.

[0215] "F-10" manufactured by Tosoh Co., Ltd.

[0216] "F-20" manufactured by Tosoh Co., Ltd.

[0217] [Novolac-type phenol resin having no acetal-based protective group (component (C))]

[0218] Synthesis Example 1 (Novolac-type phenol resin (C-1))

[0219] Under a dry nitrogen flow, 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 placed in a 2000 ml four-necked flask equipped with a cooling tube, and dissolved in 528 g of methyl isobutyl ketone as a reaction solvent. Then, the reaction solution was stirred for 4 hours while being refluxed by a hooded heater to react. After the reaction, water was added and the solution was separated and washed 5 times. After removing the methyl isobutyl ketone by reduced pressure distillation at 60°C using an evaporator, vacuum drying was performed to obtain 212 g of a novolac-type phenol resin (C-1) in the form of a light red powder. The weight average molecular weight (Mw) of the novolac-type phenol resin (C-1) is 10,600.

[0220] The GPC chart of the novolac type phenol resin (C-1) is shown in Figure 1 .

[0221] [Novolac-type phenol resin having an acetal-based protective group (component (A))]

[0222] Synthesis Example 2-1 (Novolac-type phenol resin (A-1))

[0223] Into a 2000ml four-necked flask equipped with a cooling tube, 164g (1.52mol) of m-cresol, 95.5g (0.90mol) of benzaldehyde, 73g (0.60mol) of salicylaldehyde, and 8g of p-toluenesulfonic acid were placed and dissolved in 300g of ethanol as a reaction solvent. Then, the mixture was heated to 80°C using a hooded heater and stirred under reflux for 16 hours to react. After the reaction, ethyl acetate and water were added and the mixture was separated and washed 5 times. After the solvent was removed by reduced pressure distillation from the residual resin solution, vacuum drying was performed to obtain 281g of a novolac-type phenol resin powder (a-1) as a light red powder.

[0224] Next, into a 500ml four-necked flask, 80g of the obtained novolac type phenol resin powder (a-1), 8g of propyl vinyl ether, and 0.1g of p-toluenesulfonic acid were placed, and dissolved in 120g of methyl isobutyl ketone as a reaction solvent. Then, the mixture was stirred at 40°C for 4 hours using a hooded heater to react. After the reaction, 0.4g of dimethylaminoethanol was added, and after sufficient stirring, ethyl acetate and water were added, and the mixture was separated and washed 5 times. After the solvent was removed by reduced pressure distillation from the residual resin solution, vacuum drying was performed to obtain 79g of a novolac type phenol resin (A-1) having an acetal protective group as a light red powder.

[0225] Using C 13 -NMR confirmed that the novolac-type phenol resin (A-1) had an acetal-based protective group.

[0226] The Mw of the obtained novolac-type phenol resin (A-1) was 2,990.

[0227] The GPC chart of the novolac type phenol resin (A-1) is shown in Figure 2 .

[0228] Synthesis Example 2-2 (Novolac-type phenol resin (A-2))

[0229] Except that the loading amount of the starting materials was set to 164 g (1.52 mol) of m-cresol, 80 g (0.75 mol) of benzaldehyde, and 92 g (0.75 mol) of salicylaldehyde, 76 g of a novolac-type phenol resin (A-2) having an acetal-based protective group was obtained in the same manner as in Synthesis Example 2-1. The Mw of the novolac-type phenol resin (A-2) was 3,230.

[0230] The GPC chart of the novolac type phenol resin (A-2) is shown in Figure 3 .

[0231] Synthesis Example 2-3 (Novolac-type phenol resin (A-3))

[0232] Except that the loading amount of the starting materials was set to 164 g (1.52 mol) of m-cresol, 64 g (0.60 mol) of benzaldehyde, and 110 g (0.90 mol) of salicylaldehyde, 81 g of a novolac-type phenol resin (A-3) having an acetal-based protective group was obtained in the same manner as in Synthesis Example 2-1. The Mw of the novolac-type phenol resin (A-3) was 3,990.

[0233] The GPC chart of the novolac type phenol resin (A-3) is shown in Figure 4 .

[0234] Synthesis Example 2-4 (Novolac-type phenol resin (A-4))

[0235] Except that the loading amount of the starting materials was set to 164 g (1.52 mol) of m-cresol, 48 g (0.45 mol) of benzaldehyde, and 128 g (1.05 mol) of salicylaldehyde, 81 g of powder of a novolac-type phenol resin (A-4) having an acetal-based protective group was obtained in the same manner as in Synthesis Example 2-1. The Mw of the novolac-type phenol resin (A-4) was 4,150.

[0236] The GPC chart of the novolac type phenol resin (A-4) is shown in Figure 5 .

[0237] Synthesis Example 2-5 (Novolac-type phenol resin (A-5))

[0238] The starting materials were charged in an amount of 164 g (1.52 mol) of m-cresol, 59 g (0.45 mol) of secondary aldehyde, and 18 g (0.15 mol) of salicylaldehyde. In the same manner as in Synthesis Example 2-1, 55 g of a powder of a novolac-type phenol resin (A-5) having an acetal-based protective group was obtained. The Mw of the novolac-type phenol resin (A-5) was 2,430.

[0239] Synthesis Example 2-6 (Novolac-type phenol resin (A-6))

[0240] 80 g of a novolac phenol resin powder (A-6) having an acetal protective group was obtained in the same manner as in Synthesis Example 2-1 except that the novolac phenol resin powder (C-1) was used instead of the novolac phenol resin powder (A-1). The weight average molecular weight (Mw) of the novolac phenol resin powder (A-6) having an acetal protective group was 13,740.

[0241] The GPC chart of the novolac type phenol resin (A-6) is shown in Figure 6 .

[0242] Synthesis Example 2-7 (Novolac-type phenol resin (A-7))

[0243] 74 g of a novolac-type phenol resin (A-7) having an acetal-based protective group was obtained in the same manner as in Synthesis Example 2-1 except that o-cresol was used as the starting material instead of m-cresol. The Mw of the novolac-type phenol resin (A-7) was 3,330.

[0244] Comparative Synthesis Example 1-1 (Novolac-type phenol resin (A-8))

[0245] 77 g of novolac-type phenol resin powder (A-8) was obtained by the same method as in Synthesis Example 2-1 except that salicylaldehyde (2-hydroxybenzaldehyde) was changed to 3-hydroxybenzaldehyde.

[0246] The Mw of the novolac-type phenol resin powder (A-8) was 12,760.

[0247] Comparative Synthesis Example 1-2 (Novolac-type phenol resin (A-9))

[0248] 79 g of novolac-type phenol resin powder (A-9) was obtained by the same method as in Synthesis Example 2-1 except that salicylaldehyde (2-hydroxybenzaldehyde) was changed to 4-hydroxybenzaldehyde.

[0249] The Mw of the novolac-type phenol resin powder (A-9) was 2,150.

[0250] Comparative Synthesis Example 1-3 (Novolac-type phenol resin (A-10))

[0251] 81 g of a novolac-type phenol resin powder (A-10) was obtained by the same method as in Synthesis Example 2-1 except that salicylaldehyde (2-hydroxybenzaldehyde) was changed to benzaldehyde.

[0252] The Mw of the novolac-type phenol resin powder (A-10) was 4,980.

[0253] Comparative Synthesis Example 1-4 (Novolac-type phenol resin (A-11))

[0254] A gel resin (A-11) was obtained by the same method as in Synthesis Example 2-1 except that m-cresol was replaced with phenol. The resin (A-11) was not dissolved in the solvent and could not be evaluated.

[0255] Comparative Synthesis Example 1-5 (Novolac-type phenol resin (A-12))

[0256] Suspension resin (A-12) was obtained by the same method as in Synthesis Example 2-1 except that m-cresol was replaced with 2,5-dimethylphenol. Resin (A-12) had poor solubility in the solvent and could not be evaluated.

[0257] Comparative Synthesis Example 1-6 (Novolac-type phenol resin (A-13))

[0258] 78 g of novolac-type phenol resin powder (A-13) was obtained by the same method as in Synthesis Example 2-1 except that m-cresol was changed to catechol.

[0259] The Mw of the novolac-type phenol resin powder (A-13) was 9,690.

[0260] [Polyimide precursor (component (C))]

[0261] Synthesis Example 3-1 (Polyimide resin precursor (C-2))

[0262] Under a dry nitrogen stream, 125 g (0.023 mol) of pyromellitic dianhydride and 115 g (0.023 mol) of 4,4-diaminodiphenyl ether were placed in a 2,000 ml four-necked flask equipped with a cooling tube, dissolved in 1,602 g of N-methyl-2-pyrrolidone, and stirred at 100° C. for 4 hours to react. After the reaction was completed, 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 a polyimide resin precursor (C-2) powder.

[0263] [Polybenzoxazole resin precursor (component (C))]

[0264] Synthesis Example 3-2 (Polybenzoxazole resin precursor (C-3))

[0265] Under a dry nitrogen flow, 60 g (0.164 mole) of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3,-hexafluoropropane and 34 g (0.157 mole) of 3,3-dihydroxybenzidine were placed in a 2,000 ml four-necked flask equipped with a cooling tube, and dissolved in 650 g of N,N-dimethylacetamide. Then, 140 g of pyridine was added, and a mixed solution of 265 g of cyclohexanone and 60 g (0.296 mole) of dichloroisophthalic acid was added dropwise for 2 hours while stirring at 0°C, and the mixture was reacted at room temperature for 12 hours. After the reaction was completed, 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 a polybenzoxazole resin precursor (C-3) powder.

[0266] [Positive photosensitive resin composition]

[0267] Example 1

[0268] (1) Preparation of chemically amplified photosensitive resin composition (composition F)

[0269] 1.98 g of novolac-type phenol resin (A-1) powder and 0.02 g of a photoacid generator (TFE-triazine, manufactured by Sanwa Chemical Co., Ltd.) were dissolved in 8.0 g of propylene glycol monomethyl ether (PGME), and the mixture was precisely filtered using a 0.1 μm polytetrafluoroethylene (PTFE) disk filter to obtain a chemically amplified photosensitive resin composition (solid content concentration 20%).

[0270] (2-1) Preparation of naphthoquinone type photosensitive resin composition (composition G-1)

[0271] 1.8 g of a novolac-type phenol resin (C-1) and 0.2 g of a naphthoquinone-type photosensitizer (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 disk filter to obtain a naphthoquinone-type photosensitive resin composition (G-1) (solid content concentration 20%).

[0272] (2-2) Preparation of naphthoquinone type photosensitive resin composition (composition G-2)

[0273] 1.8 g of a polyimide resin precursor (C-2) and 0.2 g of a naphthoquinone type photosensitizer (Toyo Gosei Kogyo Co., Ltd.: P-200) were dissolved in 8.0 g of γ-butyrolactone, and the mixture was microfiltered using a 0.1 μm PTFE disk filter to obtain a naphthoquinone type photosensitive resin composition (G-2) (solid content concentration 20%).

[0274] (2-3) Preparation of naphthoquinone type photosensitive resin composition (composition G-3)

[0275] 1.8 g of a polybenzoxazole resin precursor (C-3) and 0.2 g of a naphthoquinone-type photosensitizer (Toyo Gosei Kogyo Co., Ltd.: P-200) were dissolved in 8.0 g of γ-butyrolactone, and the mixture was precisely filtered using a 0.1 μm PTFE disk filter to obtain a naphthoquinone-type photosensitive resin composition (G-3) (solid content concentration 20%).

[0276] (3) Preparation of positive photosensitive resin composition

[0277] Example 1

[0278] 0.3 g of the composition F obtained in (1) and 1.7 g of the composition (G-1) obtained in (2) were fully mixed to obtain a positive photosensitive resin composition.

[0279] Example 2 to Example 9, Comparative Example 1 to Comparative Example 4

[0280] In the preparation of the chemically amplified photosensitive resin composition (composition F), the novolac-type phenol resin (A-1) is changed to a novolac-type phenol resin (A-2) to a novolac-type phenol resin (A-12) shown in Table 1 or Table 2, and the mixing ratio (composition F: composition G (weight ratio)) of the chemically amplified photosensitive resin composition (composition F) and the naphthoquinone-type photosensitive resin composition (composition G) is changed to that shown in Table 1 or Table 2. Except for this, a positive photosensitive resin composition is prepared in the same manner as in Example 1.

[0281] Comparative Example 5

[0282] A chemically amplified photosensitive resin composition was obtained in the same manner as in Example 1(1), except that the phenol novolac resin (A-1) was replaced with the phenol novolac resin (A-2). The obtained chemically amplified photosensitive resin composition was used alone as a positive photosensitive resin composition.

[0283] Comparative Example 6

[0284] The naphthoquinone type photosensitive resin composition prepared in Example 1 (2) was used alone as a positive type photosensitive resin composition.

[0285] [evaluate]

[0286] Resist films were produced using the positive photosensitive resin compositions prepared in Examples and Comparative Examples, and thick film forming properties, alkali solubility of the resist films, development contrast, and heat resistance were evaluated.

[0287] (1) Thick film forming properties

[0288] The positive photosensitive resin composition was applied to a 5-inch silicon wafer using a spin coater to a thickness of about 3 μm 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 confirm the presence or absence of cracks. The evaluation criteria for thick film forming properties are as follows.

[0289] 0: No cracks

[0290] ×: Cracked

[0291] Tables 1 and 2 show the evaluation results.

[0292] (2) Alkali developability

[0293] The positive photosensitive resin composition was applied to a 5-inch silicon wafer with a thickness of about 1 μm using a spin coater and dried on a hot plate at 110° C. for 60 seconds to obtain a photosensitive film. The photosensitive film was then exposed to ultraviolet light (UV) at 50 mJ / cm using an ultraviolet (UV) exposure device (UVE-1001SD manufactured by Sanei Electric Manufacturing Co., Ltd.). 2 After exposure, post exposure baking (PEB) was performed on a hot plate at 130°C for 90 seconds. The obtained wafer with resist film was 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 film thickness of the resist film before and after immersion in the developer was measured, and the difference was divided by 60 to obtain the value obtained as the alkali solubility ADR1. The evaluation criteria are as follows.

[0294] ○: ADR1 is 200 or more

[0295] ×: ADR1 is less than 200

[0296] The evaluation results are shown in Tables 1 and 2. In addition, the numerical values ​​in parentheses in Tables 1 and 2 are values ​​of ADR1.

[0297] (3) Development contrast

[0298] In the above (2), the value measured in the same manner without performing exposure of the resist film is set as The value of ADR1 / ADR2 was defined as development contrast. The evaluation criteria were as follows.

[0299] ○: Development contrast is 10 or more

[0300] ×: Development contrast is less than 10

[0301] Tables 1 and 2 show the evaluation results.

[0302] (4) Heat resistance

[0303] After applying the positive photosensitive resin composition on a silicon wafer with a diameter of 5 inches using a spin coater, it was dried at 110°C for 60 seconds to obtain a film with a thickness of 1 μm. The film was scraped and the glass transition temperature (Tg) was measured. In addition, Tg was measured using a differential scanning calorimeter (manufactured by TA Instruments Co., Ltd.: differential scanning calorimeter (DSC) Q100) in a nitrogen atmosphere at a temperature range of -100°C to 200°C and a heating rate of 10°C / minute. The evaluation criteria are as follows.

[0304] ○: Tg is 120°C or higher

[0305] ×: Tg is less than 120℃

[0306] The evaluation results are shown in Tables 1 and 2. In addition, the numerical values ​​in parentheses in Tables 1 and 2 are Tg values.

[0307] [Table 1]

[0308]

[0309] [Table 2]

[0310]

[0311] In Tables 1 and 2, the molar ratio of the structural units of component (A) "(a1) / (a2) / (a3)" is the molar ratio of the structural unit (a1) derived from m-cresol, the structural unit (a2) derived from salicylaldehyde, and the structural unit (a3) ​​derived from benzaldehyde.

[0312] In Table 1, the molar ratio of the structural units of component (A) "(a1) / (a4) / (a5)" is the molar ratio of the structural unit (a1) derived from m-cresol, the structural unit (a4) derived from p-cresol, and the structural unit (a5) derived from formaldehyde.

[0313] In Table 1, the molar ratio of the structural units of component (A) "(a1) / (a2) / (a6)" is the molar ratio of the structural unit (a1) derived from m-cresol, the structural unit (a2) derived from salicylaldehyde, and the structural unit (a6) derived from acetaldehyde.

[0314] The results in Tables 1 and 2 show that the positive photosensitive resin composition of the present invention is excellent in thick film forming property. In addition, it is found that the resist film using the positive photosensitive resin composition of the present invention is excellent in alkali solubility, development contrast and heat resistance.

Claims

1. A positive photosensitive resin composition comprising the following components A to E, Component A: a novolac-type phenolic resin comprising a phenol structural unit derived from cresol and one or more aldehyde structural units derived from formaldehyde or salicylaldehyde, and having an acetal-based protective group; Ingredient B: photoacid generator; Component C: one or more resins selected from novolac-type phenol resins, polyimide resins, and polybenzoxazole resins that do not have an acetal-based protective group; Ingredient D: naphthoquinone type photosensitizer; Ingredient E: solvent.

2. The positive photosensitive resin composition according to claim 1, wherein The component A is a novolac-type phenol resin comprising 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 having an acetal-based protective group.

3. The positive photosensitive resin composition according to claim 1, wherein The component A further comprises an aldehyde structural unit derived from benzaldehyde.

4. The positive photosensitive resin composition according to claim 1, wherein The component A is a novolac-type phenol resin 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, and having an acetal-based protective group, The molar ratio of the structural unit a1, the structural unit a2 and the structural unit a3, i.e., a1:a2:a3, is 1.0:0.3-0.8:0.3-0.

8.

5. The positive photosensitive resin composition according to claim 1, wherein The component A further comprises aldehyde structural units derived from acetaldehyde.

6. The positive photosensitive resin composition according to claim 1, wherein The component A is a novolac-type phenol resin 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 having an acetal-based protective group, The molar ratio of the structural unit a1, the structural unit a2 and the structural unit a6, i.e., a1:a2:a6, is 1.0:0.01-0.4:0.6-0.

99.

7. The positive photosensitive resin composition according to claim 1, wherein The acetal group protecting group is a group represented by the following formula (1): 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; *Bonded to the benzene ring constituting the main chain of the novolac type phenol resin.

8. The positive photosensitive resin composition according to claim 4, wherein The component A is obtained by reacting a novolac type phenolic resin with a compound forming an acetal group-based protective group, wherein the novolac type phenolic resin is obtained by polycondensing m-cresol, salicylaldehyde and benzaldehyde in an organic solvent at a molar ratio of m-cresol: salicylaldehyde: benzaldehyde in the range of 1.0:0.3-0.8:0.3-0.8 using an acid catalyst.

9. The positive photosensitive resin composition according to claim 6, wherein The compound forming the acetal-based protecting group is a compound represented by the following formula (2): 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 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. 10 . The positive photosensitive resin composition according to claim 7 , wherein the compound forming the acetal-based protecting group is propyl vinyl ether. 11 . The positive photosensitive resin composition according to claim 1 , 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.

12. The positive photosensitive resin composition according to claim 1 is composed of a chemically amplified photosensitive resin composition comprising component A, component B and component E1, i.e., a solvent, and a naphthoquinone photosensitive resin composition comprising component C, component D and component E2, i.e., a solvent. 13 . A photosensitive film obtained by drying the positive photosensitive resin composition according to claim 1 . 14 . A resist film obtained from the positive photosensitive resin composition according to claim 1 . 15 . A resist underlayer film obtained from the positive photosensitive resin composition according to claim 1 . 16 . A resist permanent film obtained from the positive photosensitive resin composition according to claim 1 .

17. A method for producing a film, comprising: A step of preparing a positive photosensitive resin composition by mixing a chemically amplified photosensitive resin composition comprising the following components A, B and E and a naphthoquinone photosensitive resin composition comprising the following components C, D and E, and a step of forming a film of the positive photosensitive resin composition, Component A: a novolac-type phenolic resin comprising a phenol structural unit derived from cresol and one or more aldehyde structural units derived from formaldehyde or salicylaldehyde, and having an acetal-based protective group; Ingredient B: photoacid generator; Component C: one or more resins selected from novolac-type phenol resins, polyimide resins, and polybenzoxazole resins that do not have an acetal-based protective group; Ingredient D: naphthoquinone type photosensitizer; Ingredient E: solvent.

Images