Chemically amplified positive photosensitive resin composition, cured film, and device having the cured film

Abstract

A chemically amplified positive photosensitive resin composition that is environmentally friendly and having good coating uniformity and storage stability, a cured film obtained thereof, and a device having the cured film are provided. A chemically amplified positive photosensitive resin composition includes: an acid dissociative resin (A), a photoacid generator (B) and a solvent (C). The photoacid generator (B) includes a fluorine-free photoacid generator (B-1). The fluorine content of the chemically amplified positive photosensitive resin composition is

Description

Technical Field

[0001] This invention relates to a chemically amplified positive photosensitive resin composition, and more particularly to a chemically amplified positive photosensitive resin composition having good coating uniformity and storage stability and being environmentally friendly, a hardened film made therefrom, and an element containing the hardened film. Prior Technology

[0002] Electronic components such as thin-film transistor liquid crystal display elements, organic electroluminescence devices (OLEDs), semiconductor elements, or photosensitive elements typically include interlayer insulating films or planarization films, which are usually formed using photosensitive compositions. To meet the requirements of patterning performance, positive photosensitive resin compositions containing acid-generating agents such as naphthoquinone diazide are commonly used (see Japanese Patent Application Publication No. 2001-354822), but in recent years other photosensitive compositions have been proposed.

[0003] For example, Japanese Patent Application Publication No. 2004-4669 discloses a positive chemical amplification material for forming a hardened film for display elements. This positive chemical amplification material exhibits higher sensitivity than the aforementioned positive photosensitive resin compositions using acid-generating agents such as naphthoquinone diazide. The positive chemical amplification material contains a crosslinking agent, an acid-generating agent, and an acid-dissociating resin. The acid-dissociating resin has protecting groups that can be dissociated by acid. Although the acid-dissociating resin itself is insoluble or sparingly soluble in alkaline aqueous solutions, it becomes soluble in alkaline aqueous solutions by dissociating the protecting groups through the action of acid. Furthermore, Japanese Patent Application Publication Nos. 2004-264623, 2011-215596, and 2008-304902 also disclose positive photosensitive compositions containing resins having acetal and / or ketal structures and epoxy groups, as well as acid-generating agents.

[0004] When used as a curing film material, such photosensitive resin compositions require excellent coating uniformity to form ideal patterns. Furthermore, good storage stability is also essential. Additionally, chemically amplified positive photosensitive resin compositions containing fluorine atoms have a significant environmental impact; with the increasing awareness of environmental protection in recent years, environmentally friendly alternative technologies are needed.

[0005] Therefore, how to improve the coating uniformity and storage stability of chemically amplified positive photosensitive resin compositions while also taking into account environmental friendliness is a problem that technicians in this field urgently need to solve. Summary of the Invention

[0006] In view of this, the object of the present invention is to provide a chemically amplified positive photosensitive resin composition with good coating uniformity and storage stability and environmental friendliness, a hardened film made therefrom, and an element containing the hardened film.

[0007] This invention provides a chemically amplified positive photosensitive resin composition, comprising: an acid-dissociating resin (A), a photoacid generator (B), and a solvent (C). The photoacid generator (B) includes a fluorine-free photoacid generator (B-1). The fluorine content of the chemically amplified positive photosensitive resin composition is below 500 ppm.

[0008] In one embodiment of the present invention, the fluorine content of the above-mentioned chemically amplified positive photosensitive resin composition is less than 300 ppm.

[0009] In one embodiment of the present invention, the fluorine content of the above-mentioned chemically amplified positive photosensitive resin composition is less than 100 ppm.

[0010] In one embodiment of the present invention, the fluorine content of the above-mentioned chemically amplified positive photosensitive resin composition is 0 ppm or more.

[0011] In one embodiment of the present invention, the acid-dissociable resin (A) is formed by copolymerization of monomer mixture 1. Monomer mixture 1 includes an unsaturated monomer (a-1) having an acid-dissociable group, an unsaturated monomer (a-2) having a structure as shown in formula (a2-1) or formula (a2-2) below, and an unsaturated monomer (a-3) having a maleimide group. Equation (a2-1) Equation (a2-2) In formula (a2-1) or formula (a2-2), R1, R2 and R3 independently represent hydrogen atoms or straight-chain alkyl or branched alkyl with 1 to 30 carbon atoms.

[0012] In one embodiment of the present invention, the above-mentioned fluorine-free photoacid generator (B-1) has a structure as shown in the following formula (b1-1). Equation (b1-1) In formula (b1-1), A1 represents an alkyl or aryl group with 1 to 10 carbon atoms that is substituted or unsubstituted; A2 represents an alkyl group with 1 to 10 carbon atoms, an aryl group with 1 to 10 carbon atoms, or a nitrile group; A3 to A7 independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms that is substituted or unsubstituted with an ether group (-O-) or a thioether group (-S-), or an aryl group.

[0013] In one embodiment of the present invention, based on a total weight percentage of 100% by weight of the solid components of the chemically amplified positive photosensitive resin composition, the amount of acid-dissociating resin (A) used is 60% to 95% by weight, and the amount of photoacid generator (B) used is 0.3% to 3% by weight. Based on a total weight percentage of 100% by weight of the chemically amplified positive photosensitive resin composition, the amount of solvent (C) used is 15% to 60% by weight.

[0014] In one embodiment of the present invention, based on the total weight of the solid components of the chemically amplified positive photosensitive resin composition being 100% by weight, the amount of photoacid generator (B-1) used is 0.3% to 3% by weight.

[0015] In one embodiment of the invention, it further comprises a resin (D). The resin (D) is formed by copolymerization of monomer mixture 2. Monomer mixture 2 comprises an unsaturated monomer (d-1) having an alkoxysilyl group.

[0016] In one embodiment of the present invention, the total weight of the solid components of the chemically amplified positive photosensitive resin composition is 100% by weight, and the amount of resin (D) used is 4% to 39% by weight.

[0017] The present invention further provides a curing film, which is formed by coating a chemically amplified positive photosensitive resin composition as described above onto a substrate, followed by pre-baking, exposure, development, and post-baking treatments.

[0018] The present invention also provides an element having a hardened film, comprising a substrate and a hardened film as described above disposed on the substrate.

[0019] Based on the above, since the chemically amplified positive photosensitive resin composition of the present invention includes a specific fluorine-free photoacid generator (B-1) and controls the fluorine content to below 500 ppm, a chemically amplified positive photosensitive resin composition with good coating uniformity, storage stability and environmental friendliness can be obtained.

[0020] To make the above features and advantages of the present invention more apparent and understandable, specific embodiments are described in detail below. Implementation

[0021] [<] [Chemically amplified positive photosensitive resin composition] [>] This invention provides a chemically amplified positive photosensitive resin composition, comprising: an acid-dissociating resin (A), a photoacid generator (B), and a solvent (C), and optionally including a resin (D) and an additive (E). The various components of the chemically amplified positive photosensitive resin composition used in this invention will be described in detail below.

[0022] In the following text, "the solid components of the chemically amplified positive photosensitive resin composition" refers to the components other than the solvent (C); "the total weight of the solid components of the chemically amplified positive photosensitive resin composition" refers to the total weight of the components other than the solvent (C).

[0023] [[] [Acid dissociation] [Sexual resin()] [A] [)] []] The acid-dissociable resin (A) is formed by copolymerization of monomer mixture 1. Monomer mixture 1 includes an unsaturated monomer (a-1) having an acid-dissociable group, an unsaturated monomer (a-2) having a structure as shown in formula (a2-1) or formula (a2-2) below, and an unsaturated monomer (a-3) having a maleimide group. Furthermore, monomer mixture 1 may also include other unsaturated monomers (a-4).

[0024] [Unsaturated monomers with acid-dissociable groups] [a-1] [)] The unsaturated monomer (a-1) with an acid-dissociable group has a structure as shown in the following formula (a1-1): Equation (a1-1) In formula (a1-1), R8 and R9 independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alicyclic hydrocarbon group, or an aryl group, and R8 and R9 cannot both be hydrogen atoms; R10 represents a substituted or unsubstituted alkyl group, an alicyclic hydrocarbon group, an aralkyl group, or an aryl group; R8 and R10 can bond to each other and together with the carbon atom bonded to R8 and the oxygen atom bonded to R10 to form a cyclic ether structure; wherein the substituents of R8, R9, and R10 contain halogen atoms, hydroxyl groups, or organic groups.

[0025] The acid-dissociative groups of the unsaturated monomer (a-1) containing acid-dissociative groups dissociate upon exposure by the acid generated from the photoacid generator (B) described later, and generate polar groups. Therefore, the acid-dissociative resin (A), which was originally insoluble or sparingly soluble in alkaline aqueous solutions, becomes soluble in alkaline aqueous solutions.

[0026] There are no particular limitations on the unsaturated monomer (a-1) containing an acid-dissociable group, as long as it has the structure shown in formula (a1-1). The unsaturated monomer (a-1) containing an acid-dissociable group can be easily dissociated by an acid.

[0027] The alicyclic hydrocarbon groups represented by R8 and R9 can be, for example, alicyclic hydrocarbon groups with 3 to 20 carbon atoms. Furthermore, these alicyclic hydrocarbon groups with 3 to 20 carbon atoms can be polycyclic. Examples of the aforementioned alicyclic hydrocarbon groups with 3 to 20 carbon atoms include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, borneol, norborneol, or adamantyl.

[0028] The aryl groups represented by R8 and R9 can be, for example, aryl groups with 6 to 14 carbon atoms. These aryl groups with 6 to 14 carbon atoms can be monocyclic, composed of linked monocyclic rings, or condensed rings. Examples of aryl groups with 6 to 14 carbon atoms include phenyl or naphthyl groups.

[0029] The substituents of the substituted alkyl, alicyclic hydrocarbon and aryl groups represented by R8 and R9 can be, for example, halogen atoms, hydroxyl groups or organic groups.

[0030] Organic groups can be, for example, nitro, cyano, carboxyl, carbonyl, alicyclic hydrocarbon groups (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, borneol, norborneol, or adamantyl), aryl (e.g., phenyl or naphthyl), alkoxy (e.g., methoxy, ethoxy, propoxy, n-butoxy, pentooxy, hexoxy, heptoxy, octoxy, etc., with 1 to 20 carbon atoms), acetyl (e.g., acetyl, propoxy, butyl, isobutyl, etc., with 2 to 20 carbon atoms), and acetyloxy (e.g., acetyloxy, propoxy, butoxy, tributoxy, tripentoxy, etc., with 2 to 10 carbon atoms). Substituents such as alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, etc., with 2 to 20 carbon atoms), haloalkyl (e.g., straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-tetradecyl, n-octadecyl; branched alkyl groups such as isopropyl, isobutyl, tributyl, neopentyl, 2-hexyl, 3-hexyl; alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, adamantyl, etc., obtained by substituting some or all of the hydrogen atoms of the above groups with halogen atoms), or hydroxyalkyl (e.g., hydroxymethyl, etc.).

[0031] The alkyl, alicyclic hydrocarbon, and aryl groups represented by R 10 may be the same as those represented by R 8 and R 9 above. Furthermore, the alkyl group represented by R 10 is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably methyl, ethyl, or n-propyl. The aralkyl group represented by R 10 may be, for example, benzyl, phenethyl, naphthylmethyl, or naphthylethyl.

[0032] The cyclic ether structure formed by the mutual bonding of R8 and R10 is preferably a cyclic ether structure with 3 to 20 ring members, more preferably a cyclic ether structure with 5 to 8 ring members, and especially preferably a tetrahydrofuran or tetrahydropyran.

[0033] As a structure represented by formula (a1-1), the following groups can be listed as examples. Equation (a1-1-1) Equation (a1-1-2) Equation (a1-1-3) Equation (a1-1-4) Equation (a1-1-5) Equation (a1-1-6) Equation (a1-1-7)

[0034] Examples of unsaturated monomers containing acid-dissociable groups (a-1) include: 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-tert-butoxyethyl methacrylate, 1-(2-chloroethoxy)ethyl methacrylate, 1-(2-ethylhexyloxy)ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1-(2-cyclohexylethoxy)ethyl methacrylate, 1-benzyloxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, and 2-tetrahydrofuranyl methacrylate. methacrylate), 1-ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-tert-butoxyethyl acrylate, 1-(2-chloroethoxy)ethyl acrylate, 1-(2-ethylhexyloxy)ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, 1-(2-cyclohexylethoxy)ethyl acrylate, 1-benzyloxyethyl acrylate, 2-tetrahydropyranyl acrylate, 5,6-di(1-methoxyethoxycarbonyl)-2-norbornene, 5,6-di(1-(cyclohexyloxy)ethoxycarbonyl)-2-norbornene, 5,6-di(1-(benzyloxy)ethoxycarbonyl)-2-norbornene, p-1-ethoxyethoxystyrene or m-1-ethoxyethoxystyrene, p-1-methoxyethoxystyrene or m-1-methoxyethoxystyrene, p-1- Butoxyethoxystyrene or m-1-butoxyethoxystyrene, p-1-isobutoxyethoxystyrene or m-1-isobutoxyethoxystyrene, p-1-(1,1-dimethylethoxy)ethoxystyrene or m-1-(1,1-dimethylethoxy)ethoxystyrene, p-1-(2-chloroethoxy)ethoxystyrene or m-1-(2-chloroethoxy)ethoxystyrene, p-1-(2-ethylhexyloxy)ethoxystyrene or m-1-(2-ethylhexyloxy)ethoxystyrene, p-1-propoxyethoxystyrene or m-1-propoxyethoxystyrene, p-1-cyclohexyloxyethoxystyrene or m-1-cyclohexyloxyethoxystyrene, p-1-(2-cyclohexylethoxy)ethoxystyrene or m-1-(2-cyclohexylethoxy)ethoxystyrene, p-1-benzyloxyethoxystyrene or m-1-benzyloxyethoxystyrene, etc.

[0035] The unsaturated monomer (a-1) containing an acid-dissociable group is preferably 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 1-benzyloxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, or 2-tetrahydrofuranyl methacrylate, and more preferably 2-tetrahydropyranyl methacrylate or 2-tetrahydrofuranyl methacrylate.

[0036] Unsaturated monomers (a-1) containing acid-dissociable groups can be used alone or in combination.

[0037] The total weight of monomer mixture 1 is 100 parts by weight, and the amount of unsaturated monomer (a-1) containing acid-dissociable groups used is 10 parts by weight to 60 parts by weight, preferably 12 parts by weight to 55 parts by weight, and more preferably 15 parts by weight to 50 parts by weight.

[0038] [Unsaturated monomers() [a-2] [)] The unsaturated monomer (a-2) has a structure as shown in formula (a2-1) or formula (a2-2) below: Equation (a2-1) Equation (a2-2) In formula (a2-1) or formula (a2-2), R1, R2 and R3 independently represent hydrogen atoms or straight-chain alkyl or branched alkyl with 1 to 30 carbon atoms.

[0039] Examples of unsaturated monomers (a-2) include the following compounds. Equation (a2-1-1) Equation (a2-1-2) Equation (a2-1-3) Equation (a2-1-4) Equation (a2-2-1) Equation (a2-2-2) Equation (a2-2-3) Equation (a2-2-4) Equation (a2-2-5) Equation (a2-2-6)

[0040] Unsaturated monomers (a-2) can be used alone or in combination.

[0041] The total weight of monomer mixture 1 is 100 parts by weight, and the amount of unsaturated monomer (a-2) used is 2 to 25 parts by weight, preferably 3 to 23 parts by weight, and more preferably 4 to 20 parts by weight.

[0042] [Unsaturated monomers with maleic imine groups] [a-3] [)] The unsaturated monomer (a-3) having a maleicimine group has a structure as shown in the following formula (a3-1): Equation (a3-1) In formula (a3-1), R7 represents a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, a phenyl group with or without a substituent, a benzyl group, or a cycloalkyl group having 3 to 6 carbon atoms. The substituent may be an alkyl group having 1 to 5 carbon atoms.

[0043] Unsaturated monomers containing a maleimide group (a-3) include, for example: N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-chlorophenyl)maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide. Nitrogen-substituted or unsubstituted maleimides, including N-phenylmethylmaleimide, N-(2,4,6-tribromophenyl)maleimide, N-[3-(triethoxysilyl)propyl]maleimide, N-octadecenylmaleimide, N-dodecenylmaleimide, N-(2-methoxyphenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, and N-(1-hydroxyphenyl)maleimide.

[0044] The unsaturated monomer (a-3) having a maleimide group is preferably N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-laurylmaleimide, N-cyclohexylmaleimide or N-benzylmaleimide, etc., and more preferably N-phenylmaleimide or N-cyclohexylmaleimide.

[0045] Examples of unsaturated monomers (a-3) having maleic imine groups include the following compounds. Equation (a3-1-1) Equation (a3-1-2) Equation (a3-1-3) Equation (a3-1-4) Equation (a3-1-5) Equation (a3-1-6) Equation (a3-1-7) Equation (a3-1-8) Equation (a3-1-9) Equation (a3-1-10)

[0046] Unsaturated monomers (a-3) with maleic imine groups can be used alone or in combination.

[0047] Based on the total weight of monomer mixture 1 being 100 parts by weight, the amount of unsaturated monomer (a-3) having maleic imine group used is 1 to 15 parts by weight, preferably 1.5 to 13 parts by weight, and more preferably 2 to 11 parts by weight.

[0048] [Other unsaturated monomers()] [a-4] [)] Other unsaturated monomers (a-4) may include unsaturated carboxylic acid monomers, unsaturated monomers containing lactone structures, unsaturated monomers containing epoxy groups, alkyl (meth)acrylates, alicyclic (meth)acrylates, aryl (meth)acrylates, unsaturated dicarboxylic acid diesters, hydroxyalkyl (meth)acrylates, polyethers of (meth)acrylates, aromatic vinyl compounds, and other unsaturated monomers other than those mentioned above.

[0049] Unsaturated carboxylic acid monomers refer to compounds containing a carboxylic acid group or carboxylic anhydride and an unsaturated bond for polymerization. Their structure is not particularly limited and may include, but is not limited to, unsaturated monocarboxylic acid compounds, unsaturated dicarboxylic acid compounds, unsaturated dicarboxylic acid anhydride compounds, polycyclic unsaturated carboxylic acid compounds, polycyclic unsaturated dicarboxylic acid compounds, or polycyclic unsaturated dicarboxylic acid anhydride compounds.

[0050] Examples of unsaturated monocarboxylic acid compounds include: (meth)acrylic acid, butenoic acid, α-chloroacrylic acid, ethylacrylic acid, cinnamic acid, 2-(meth)acryloxyethoxysuccinate, 2-(meth)acryloxyethoxyhexahydrophthalic acid ester, 2-(meth)acryloxyethoxyphthalic acid ester, or ω-carboxylated polycaprolactone polyol monoacrylate (trade name ARONIX M-5300, manufactured by Toa Synthetic), etc.

[0051] Examples of unsaturated dicarboxylic acid compounds include: maleic acid, fumaric acid, methyl fumaric acid, itaconic acid, or citraconic acid.

[0052] The unsaturated dicarboxylic acid anhydride compound can be an anhydride compound of the aforementioned unsaturated dicarboxylic acid compounds.

[0053] Examples of polycyclic unsaturated carboxylic acid compounds include: 5-carboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, or 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, etc.

[0054] Examples of polycyclic unsaturated dicarboxylic acid compounds include: 5,6-dicarboxylic acid bicyclic [2.2.1]hept-2-ene.

[0055] The polycyclic unsaturated dicarboxylic acid anhydride compound is the anhydride compound of the aforementioned polycyclic unsaturated dicarboxylic acid compound.

[0056] The preferred unsaturated carboxylic acid monomers are acrylic acid, methacrylic acid, maleic anhydride, 2-methacryloxyethoxysuccinate, or 2-methacryloxyethoxyhexahydrophthalic acid.

[0057] Unsaturated carboxylic acid monomers can be used alone or in combination.

[0058] Unsaturated monomers containing lactone structures have structures as shown in the following formula (a4-1): Equation (a4-1) In formula (a4-1), R11 represents a hydrogen atom or an alkyl group; R12 represents an alkyl group with 1-8 carbon atoms, a cycloalkyl group with 3-7 carbon atoms, an alkoxy group with 1-8 carbon atoms, an alkoxycarbonyl group with 2-8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid-decomposing group; R14 represents a single bond or a divalent linkage group; R13 represents a group containing... The structure can be a single ring or multiple rings; b1 represents an integer greater than 0, and when b1 is greater than 1, the complex number of R12 can be the same or different.

[0059] The alkyl group represented by R 11 is preferably a straight-chain or branched alkyl group with 1 to 3 carbon atoms, and more preferably a methyl group. The alkyl group may have substituents, and the substituents are preferably hydroxyl groups or halogen atoms (especially fluorine atoms).

[0060] R 12 is preferably an alkyl or cyano group having 1 to 4 carbon atoms.

[0061] Examples of divalent linkages in R 14 include: straight-chain alkyl groups, branched alkyl groups, cyclic alkyl groups, aryl groups, -O-, -COO-, -S-, -NR"-, -CO-, -NR"CO-, or -SO 2-, or groups containing combinations of the aforementioned functional groups, wherein R" can be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and preferably a hydrogen atom. The divalent linkage in R 14 preferably contains at least one of -O-, -COO-, -S-, -NH-, and -CO-, or groups combining these groups with -(CH 2) d-, wherein d represents an integer from 1 to 10, preferably an integer from 1 to 6, and more preferably an integer from 1 to 4.

[0062] R 13 is preferably a monocyclic structure. When R 13 represents a monocyclic structure, it is preferably a lactone structure forming a 5- to 7-membered ring, and more preferably a 5- or 6-membered ring. When R 13 represents a polycyclic structure, it is preferably another ring structure, forming a bicyclic or spirocyclic structure with a condensed ring on the lactone structure. Other ring structures may include, for example, cyclic hydrocarbon groups with 3 to 20 carbon atoms, or heterocyclic groups with 3 to 20 carbon atoms. The heterocyclic group is not particularly limited, and may include those in which one or more of the atoms constituting the ring are heteroatoms, or aromatic heterocyclic groups. In addition, the heterocyclic group is preferably a 5- or 6-membered ring, and more preferably a 5-membered ring. Specifically, the heterocyclic group preferably contains at least one oxygen atom, for example: oxocyclic pentane ring, oxane ring, dioxane ring, etc.

[0063] b1 is preferably an integer from 0 to 4, more preferably an integer from 0 to 2, and even more preferably 0. When b1 represents an integer greater than 2, the multiple R12s may be the same or different. In addition, the multiple R12s may also be bonded to each other to form a ring, but it is preferred that they are not bonded to each other to form a ring.

[0064] The unsaturated monomer containing a lactone structure is preferably a compound as shown in formula (a4-2) below. Equation (a4-2) In formula (a4-2), R11' is a hydrogen atom or an alkyl group; R12' is an alkyl group with 1-8 carbon atoms, a cycloalkyl group with 3-7 carbon atoms, an alkoxy group with 1-8 carbon atoms, an alkoxycarbonyl group with 2-8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid-decomposing group; b2 represents an integer greater than 0, and when b2 is greater than 1, the multiple R12's can be the same or different; R14' is a single bond or a divalent linkage group; R13' contains... It has a monocyclic or polycyclic structure; R 15' is an oxygen atom or -NR"-, and R" is a hydrogen atom or an alkyl group.

[0065] The alkyl group represented by R 11' is preferably a straight-chain or branched alkyl group with 1 to 3 carbon atoms, and more preferably a methyl group. The alkyl group may have substituents, and the substituents are preferably hydroxyl or halogen atoms, and more preferably fluorine atoms.

[0066] R 12' is preferably an alkyl or cyano group having 1 to 4 carbon atoms.

[0067] Examples of divalent linkages in R 14' include: straight-chain alkyl groups, branched alkyl groups, cyclic alkyl groups, aryl groups, -O-, -COO-, -S-, -NR"-, -CO-, -NR"CO-, -SO 2-, etc., or combinations of the aforementioned functional groups, wherein R" can be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. The divalent linkage in R 14' is preferably a group containing at least one of -COO- and -CO-, or a group combining these groups with -(CH 2) d-, where d represents an integer from 1 to 10, preferably an integer from 1 to 6, and more preferably an integer from 1 to 4. R 14' is particularly preferably a single bond.

[0068] R 13' is preferably a monocyclic structure. When R 13' represents a monocyclic structure, it is preferably a lactone structure forming a 5- to 7-membered ring, and more preferably a 5- or 6-membered ring. When R 13' represents a polycyclic structure, it is preferably another ring structure, forming a bicyclic or spirocyclic structure with condensation on the lactone structure. Other ring structures may include cyclic hydrocarbon groups with 3 to 20 carbon atoms, or heterocyclic groups with 3 to 20 carbon atoms. The heterocyclic group is not particularly limited, and may include those in which one or more atoms constituting the ring are heteroatoms, or aromatic heterocyclic groups. In addition, the heterocyclic group is preferably a 5- or 6-membered ring, and more preferably a 5-membered ring. Specifically, the heterocyclic group preferably contains at least one oxygen atom, for example: oxocyclic pentane ring, oxane ring, dioxane ring, etc.

[0069] b2 is preferably an integer from 0 to 4, more preferably an integer from 0 to 2, and especially preferably 0. When b2 represents an integer greater than 2, the multiple R12's may be the same or different. In addition, the multiple R12's may also be bonded to each other to form a loop, but it is preferred that they are not bonded to each other to form a loop.

[0070] R 15' is preferably an oxygen atom. If R 15' is -NR"-, R" can be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom.

[0071] The unsaturated monomer containing a lactone structure is preferably a structure represented by any of the following formulas (a4-3-1) to (a4-3-21). Equation (a4-3-1) Equation (a4-3-2) Equation (a4-3-3) Equation (a4-3-4) Equation (a4-3-5) Equation (a4-3-6) Equation (a4-3-7) Equation (a4-3-8) Equation (a4-3-9) Equation (a4-3-10) Equation (a4-3-11) Equation (a4-3-12) Equation (a4-3-13) Equation (a4-3-14) Equation (a4-3-15) Equation (a4-3-16) Equation (a4-3-17) Equation (a4-3-18) Equation (a4-3-19) Equation (a4-3-20) Equation (a4-3-21) In formulas (a4-2-1) to (a4-3-21), R 16 represents an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 3 to 7 carbon atoms, an alkoxy group with 1 to 8 carbon atoms, an alkoxycarbonyl group with 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid-decomposing group. When s is greater than 1, the multiple R 16s may be the same or different.

[0072] The structures represented by formulas (a4-2-1) to (a4-3-21) may or may not have R 16, but are preferably without R 16 (i.e., s is 0). R 16 is preferably an alkyl or cyano group having 1 to 4 carbon atoms.

[0073] s is preferably an integer from 0 to 4, more preferably an integer from 0 to 2, and especially preferably 0. When s represents an integer greater than 2, the multiple R 16s can be the same or different. In addition, the multiple R 16s can also be bonded to each other to form a loop, but it is preferred that they are not bonded to each other to form a loop.

[0074] The unsaturated monomer containing the lactone structure is preferably one containing the structure shown in formula (a4-3-1), formula (a4-3-4), formula (a4-3-5), formula (a4-3-6), formula (a4-3-13), formula (a4-3-14) or formula (a4-3-17), and more preferably one containing the structure shown in formula (a4-3-1), formula (a4-3-4) or formula (a4-3-17).

[0075] Unsaturated monomers containing lactone structures, for example, can be listed as compounds as shown in formulas (a4-4-1) to (a4-4-21) below. Equation (a4-4-1) Equation (a4-4-2) Equation (a4-4-3) Equation (a4-4-4) Equation (a4-4-5) Equation (a4-4-6) Equation (a4-4-7) Equation (a4-4-8) Equation (a4-4-9) Equation (a4-4-10) Equation (a4-4-11) Equation (a4-4-12) Equation (a4-4-13) Equation (a4-4-14) Equation (a4-4-15) Equation (a4-4-16) Equation (a4-4-17) Equation (a4-4-18) Equation (a4-4-19) Equation (a4-4-20) Equation (a4-4-21) In formulas (a4-4-1) to (a4-4-2), the definition of R 17 is the same as that of R 11' mentioned above, and will not be repeated here. In formula (a4-4-18), Me represents methyl.

[0076] The unsaturated monomer containing a lactone structure is preferably a compound as shown in formulas (a4-5-1) to (a4-5-11). Equation (a4-5-1) Equation (a4-5-2) Equation (a4-5-3) Equation (a4-5-4) Equation (a4-5-5) Equation (a4-5-6) Equation (a4-5-7) Equation (a4-5-8) Equation (a4-5-9) Equation (a4-5-10) Equation (a4-5-11)

[0077] Unsaturated monomers containing lactone structures can be used alone or in combination.

[0078] Examples of epoxy-containing unsaturated monomers include: epoxy-containing (meth)acrylate compounds, epoxy-containing α-alkyl acrylate compounds, epoxy propylene ether compounds, vinyl unsaturated monomers with oxetane as shown in the following formulas (a4-6), and any combination of the above monomers. Equation (a4-6) In formulas (a4-6), R51 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R52 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R53, R54, R55 and R56 each independently represent a hydrogen atom, a fluorine atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms or a perfluoroalkyl group having 1 to 4 carbon atoms; and a is an integer from 1 to 6.

[0079] Examples of epoxy-containing (meth)acrylate compounds include: glycidyl (meth)acrylate, 2-methyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, or 3,4-epoxycyclohexyl methyl (meth)acrylate.

[0080] Examples of α-alkyl acrylate compounds containing epoxy groups include: α-ethyl acrylate glycidyl acrylate, α-n-propyl acrylate glycidyl acrylate, α-n-butyl acrylate glycidyl acrylate, or α-ethyl acrylate 6,7-epoxyheptyl acrylate.

[0081] Examples of glycidyl ether compounds include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

[0082] Examples of vinyl unsaturated monomers with oxocyclic butyl groups as shown in formula (a4-6) include: methacrylate compounds, acrylate compounds, or unsaturated monomers as shown in formulas (a4-6-1) to (a4-6-4) below. Equation (a4-6-1) Equation (a4-6-2) Equation (a4-6-3) Equation (a4-6-4)

[0083] Examples of methacrylate compounds include: 3-(methacryloyl oxymethyl)oxetane (OXMA), 3-(methacryloyl oxymethyl)-3-ethyloxetane (EOXMA), and 3-(methacryloyl oxymethyl)-3-methyloxetane (EOXMA). 3-(methacryloxymethyl)-3-methyloxetane (MOXMA), 3-(methacryloxymethyl)-2-methyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloxymethyl)-2-phenyloxetane, 3-(methacryloxymethyl)-2,2-difluorooxetane, 3-(methacryloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(methacryloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(methacryloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(methacryloxymethyl)-2-methyloxetane (MOXMA), 3-(methacryloxymethyl)-2-methyloxetane, ... Compounds including 3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-3-ethyloxetane, 2-ethyl-3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-2-trifluoromethyloxetane, 3-(methacryloxyethyl)-2-pentafluoroethyloxetane, 3-(methacryloxyethyl)-2-phenyloxetane, 2,2-difluoro-3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-2,2,4-trifluorooxetane, or 3-(methacryloxyethyl)-2,2,4,4-tetrafluorooxetane.

[0084] Examples of acrylate compounds include: 3-(acryloxymethyl)oxetane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(acryloxymethyl)-3-methyloxetane, 3-(acryloxymethyl)-2-methyloxetane, 3-(acryloxymethyl)-2-trifluoromethyloxetane, 3-(acryloxymethyl)-2-pentafluoroethyloxetane, 3-(acryloxymethyl)-2-phenyloxetane, 3-(acryloxymethyl)-2,2-difluorooxetane, 3-(acryloxymethyl)-2,2,4-trifluorooxetane, 3-(acryloxymethyl)- Compounds of 2,2,4,4-tetrafluorooxetane, 3-(acryloxyethyl)oxetane, 3-(acryloxyethyl)-3-ethyloxetane, 2-ethyl-3-(acryloxyethyl)oxetane, 3-(acryloxyethyl)-2-trifluoromethyloxetane, 3-(acryloxyethyl)-2-pentafluoroethyloxetane, 3-(acryloxyethyl)-2-phenyloxetane, 2,2-difluoro-3-(acryloxyethyl)oxetane, 3-(acryloxyethyl)-2,2,4-trifluorooxetane, or 3-(acryloxyethyl)-2,2,4,4-tetrafluorooxetane, etc.

[0085] The epoxy-containing unsaturated monomer may further include other vinyl unsaturated monomers with oxetane groups, such as: 3-methyl-3-(vinyloxymethyl)oxetane (MOXV), 3-ethyl-3-(vinyloxymethyl)oxetane (EOXV), 3-propyl-3-(vinyloxymethyl)oxetane, 3-methyl-3-(2-vinyloxyethyl)oxetane, 3-ethyl-3-(2-vinyloxyethyl)oxetane, 3-propyl-3-(2-vinyloxyethyl)oxetane, 3-methyl-3-(3-vinyloxypropyl)oxetane, 3-ethyl-3-(3-vinyloxypropyl)oxetane, 3-propyl ... Vinyl ether compounds containing oxetane, such as 3-methyl-3-(3-ethoxybutyl)oxetane, 3-ethyl-3-(3-ethoxybutyl)oxetane, 3-propyl-3-(3-ethoxybutyl)oxetane, ethylene glycol ((3-ethyl-3-oxetane)methyl)vinyl ether, propylene glycol ((3-ethyl-3-oxetane)methyl)vinyl ether, or 3,3-bis((ethoxybutyl)methyl)oxetane.

[0086] Examples of alkyl methacrylates include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, dibutyl methacrylate, or terbutyl methacrylate.

[0087] Examples of cyclohexyl methacrylates include: cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 2.6]dec-8-yl(meth)acrylate (or dicyclopentyl(meth)acrylate), dicyclopentoxyethyl(meth)acrylate, or isobornyl(meth)acrylate.

[0088] Aryl esters of (meth)acrylates include, for example, phenyl (meth)acrylate or benzyl (meth)acrylate.

[0089] Examples of unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, or diethyl itaconic acid.

[0090] Examples of hydroxyalkyl (meth)acrylates include: 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate.

[0091] Examples of polyethers of (meth)acrylates include polyethylene glycol mono(meth)acrylate or polypropylene glycol mono(meth)acrylate.

[0092] Examples of aromatic ethylene compounds include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, or p-methoxystyrene.

[0093] Other unsaturated compounds besides those mentioned above include, for example: acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, ethyl vinylidene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-succinimino-3-maleimide benzoate, N-succinimino-4-maleimide butyrate, N-succinimino-6-maleimide hexanoate, N-succinimino-3-maleimide propionate, or N-(9-acridyl)maleimide.

[0094] Other unsaturated monomers (a-4) can be used alone or in combination.

[0095] The acid-dissociable resin (A) has a weight-average molecular weight (Mw) of 2,000 to 38,000, preferably 3,000 to 32,000, and more preferably 4,000 to 26,000, as determined by gel permeation chromatography (GPC).

[0096] Based on the total weight of the solid components of the chemically amplified positive photosensitive resin composition, the amount of acid-dissociating resin (A) used is 60% to 95% by weight, preferably 62% to 93% by weight, and more preferably 65% ​​to 90% by weight, on a 100% by weight basis.

[0097] [[] [Photogenic acid production] [dosage] [B] [)] []] Photoacid generating agent (B) includes fluorine-free photoacid generating agent (B-1). Furthermore, provided that the fluorine content of the chemically amplified positive photosensitive resin composition is 500 ppm or less, photoacid generating agent (B) may further include fluorine-containing photoacid generating agent (B-2).

[0098] [Fluorine-free photoacid generator()] [B-1] [)] Fluorine-free photoacid generators (B-1) may include oxime sulfonate compounds (B-1-1) and other photoacid generators (B-1-2).

[0099] [Oxime sulfonate compounds() [B-1-1] [)] The oxime sulfonate compound (B-1-1) has the structure shown in the following formula (b1-1). Equation (b1-1) In formula (b1-1), A1 represents an alkyl or aryl group with 1 to 10 carbon atoms that is substituted or unsubstituted; A2 represents an alkyl group with 1 to 10 carbon atoms, an aryl group with 1 to 10 carbon atoms, or a nitrile group; A3 to A7 independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms that is substituted or unsubstituted with an ether group (-O-) or a thioether group (-S-), or an aryl group.

[0100] The aryl group represented by A1 may be substituted with an alkyl group. Preferably, A1 is an alkyl or phenyl group with 1 to 6 carbon atoms that has been substituted with a substituent.

[0101] A2 is preferably an alkyl, phenyl, or nitrile group (-CN) having 1 to 6 carbon atoms.

[0102] The alkyl groups represented by A3 to A7, having 1 to 10 carbon atoms, may be substituted with an ether group (-O-) or a thioether group (-S-), and the aryl groups represented by A3 to A7 may be substituted with alkyl groups. Preferably, A3 to A7 are alkyl or phenyl groups that independently represent hydrogen atoms, have 1 to 6 carbon atoms, and are substituted or unsubstituted with an ether group (-O-) or a thioether group (-S-), and at least one of A3 to A7 represents an alkyl group substituted with an ether group (-O-) or a thioether group (-S-).

[0103] In formula (b1-1), A1 is preferably an alkyl or phenyl group with 1 to 6 carbon atoms that has been substituted with a substituent; A2 is preferably an alkyl, phenyl, or nitrile group with 1 to 6 carbon atoms; A3 to A7 are preferably alkyl or phenyl groups with 1 to 6 carbon atoms that have been substituted with or unsubstituted with an ether group (-O-) or a thioether group (-S-), and at least one of A3 to A7 represents an alkyl group substituted with an ether group (-O-) or a thioether group (-S-). Under these preferred conditions, the developability and adhesion of the prepared hardened film can be further improved.

[0104] Examples of oxime sulfonate compounds (B-1-1) include the following compounds. Equation (b1-1-1) Equation (b1-1-2) Equation (b1-1-3) Equation (b1-1-4) Equation (b1-1-5) Equation (b1-1-6) Equation (b1-1-7) Equation (b1-1-8) Equation (b1-1-9) Equation (b1-1-10) Equation (b1-1-11) Equation (b1-1-12) Equation (b1-1-13) Equation (b1-1-14) Equation (b1-1-15) Equation (b1-1-16) Equation (b1-1-17) Equation (b1-1-18) Equation (b1-1-19) Equation (b1-1-20)

[0105] Oxime sulfonate compounds (B-1-1) can be used alone or in combination of multiple compounds.

[0106] Based on the total weight of the solid components of the chemically amplified positive photosensitive resin composition, the amount of oxime sulfonate compound (B-1-1) used is 0.3% to 3% by weight, preferably 0.35% to 2.9% by weight, and more preferably 0.4% to 2.8% by weight.

[0107] If the chemically amplified positive photosensitive resin composition of the present invention further includes an oxime sulfonate compound (B-1-1), the storage stability of the chemically amplified positive photosensitive resin composition can be further improved.

[0108] [Other photoacids produced] [dosage] [B-1-2] [)] Other photoacid generators (B-1-2) may include compounds containing oxime sulfonates other than the aforementioned oxime sulfonate compounds (B-1-1), N-sulfonoxyimine compounds, onium salts, halogenated compounds, diazomethane compounds, urethane compounds, sulfonate compounds, or carboxylic acid ester compounds.

[0109] Other compounds containing oxime sulfonate groups include, for example, oxime sulfonate compounds having the following formulas (b1-2-1) to (b1-2-3). Equation (b1-2-1) Equation (b1-2-2) Equation (b1-2-3) In formulas (b1-2-1) to (b1-2-3), A8 can represent a substituted or unsubstituted alkyl, alicyclic hydrocarbon, or aryl group with 1 to 20 carbon atoms. In formulas (b1-2-1) and (b1-2-2), A9 can represent an alkyl group with 1 to 12 carbon atoms. In formula (b1-2-3), A10 represents an alkyl, alkoxy, or halogen atom. i is an integer from 0 to 3, and when i is 2 or 3, multiple A10s can be the same or different from each other.

[0110] The alkyl group represented by A 10 is preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by A 10 is preferably a straight-chain or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by A 10 is preferably a chlorine atom.

[0111] Oxime sulfonate compounds as shown in formula (b1-2-3) can be exemplified by compounds shown in formulas (b1-2-4) to (b1-2-8) below. Equation (b1-2-4) Equation (b1-2-5) Equation (b1-2-6) Equation (b1-2-7) Equation (b1-2-8)

[0112] Oxime sulfonate compounds as shown in formula (b1-2-3) include, for example, (5-propylsulfoxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfoxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-camphorsulfoxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfoxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, 2-(octylsulfoxyimino)-2-(4-methoxyphenyl)acetonitrile, 4-methylphenylsulfoxyimino-α-(4-methoxyphenyl)acetonitrile, and commercially available products of the above compounds may be used.

[0113] Examples of N-sulfonoxy acetimine compounds include: N-(camphorsulfonoxy)butadieneimide, N-(4-methylphenylsulfonoxy)butadieneimide, N-(camphorsulfonoxy)phthalimide, N-(camphorsulfonoxy)diphenylcis-butenediimide, (4-methylphenylsulfonoxy)diphenylcis-butenediimide, N-(phenylsulfonoxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxylated acetimine, N-(4- N-(camphorsulfonoxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxylated nimodiamine, N-(camphorsulfonoxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxylated nimodiamine, N-(camphorsulfonoxy)-7-oxabicyclo[2.2.1]hept-5-en-2,3-dicarboxylated nimodiamine, N-(4-methylphenylsulfonoxy) ... N-(camphorsulfonyl)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylated nitroimidide, N-(4-methylphenylsulfonyl)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylated nitroimidide, N-(camphorsulfonyl)naphthalenedimethyl nitroimidide, N-(4-methylphenylsulfonyl)naphthalenedimethyl nitroimidide Nitroimide, N-(phenylsulfonoxy)naphthodimethylimide, N-(ethylsulfonoxy)naphthodimethylimide, N-(propylsulfonoxy)naphthodimethylimide, N-(butylsulfonoxy)naphthodimethylimide, N-(pentylsulfonoxy)naphthodimethylimide, N-(hexylsulfonoxy)naphthodimethylimide, N-(heptylsulfonoxy)naphthodimethylimide, N-(octylsulfonoxy)naphthodimethylimide, or N-(nonylsulfonoxy)naphthodimethylimide, etc.

[0114] Based on the total weight of the solid components of the chemically amplified positive photosensitive resin composition, the amount of fluorine-free photoacid generator (B-1) used is 0.3% to 3% by weight, preferably 0.35% to 2.9% by weight, and more preferably 0.4% to 2.8% by weight, based on 100% by weight.

[0115] [Fluorocyanate-containing photoacid generator() [B-2] [)] Provided that the fluorine content of the chemically amplified positive photosensitive resin composition is less than 500 ppm, the photoacid generator (B) may further include a fluorinated photoacid generator (B-2). As a fluorinated photoacid generator (B-2), other photoacid generators (B-1-2) mentioned above that include fluorine atoms can be listed.

[0116] Examples of fluorinated photoacid generators (B-2) include: compounds in formulas (b1-2-1) and (b1-2-2) where A9 represents a fluoroalkyl group having 1 to 12 carbon atoms; compounds in formula (b1-2-3) where A10 represents a fluorine atom; N-(trifluoromethylsulfonyl)butadieneimide; N-(2-trifluoromethylphenylsulfonyl)butadieneimide; N-(4-fluorophenylsulfonyl)butadieneimide; N-(trifluoromethylsulfonyl)phthalimide; N-(2-trifluoromethylphenylsulfonyl)phthalimide; N-(2-fluorophenylsulfonyl)phthalimide; N-(trifluoromethylsulfonyl)diphenylcis-butenediimide; N-(2-trifluoromethylphenyl)butadi ... N-(4-fluorophenylsulfonyl)diphenylcis-butene diimide, N-(trifluoromethanesulfonyl)bicyclo[2.2.1]hept-5-en-2,3-dicarboxylated diimide, N-(nonafluorobutyroxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxylated diimide, N-(trifluoromethylsulfonyl)-7-oxabicyclo[2.2.1]hept-5-en-2,3-dicarboxylated diimide, N-(2-trifluoromethylphenylsulfonyl) (2.2.1)Hept-5-ene-2,3-dicarboxylated nitroimidine, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]Hept-5-ene-2,3-dicarboxylated nitroimidine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]Hept-5-ene-2,3-dicarboxylated nitroimidine, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]Hept-5-ene-2,3-dicarboxylated nitroimidine, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]Hept-5-ene-2,3-dicarboxylated nitroimidine, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]Hept-5-ene-2,3-dicarboxylated nitroimidine, N-(4-fluoromethyl ... Bicyclic [2.2.1]heptane-5,6-oxy-2,3-dicarboxylated nitroimidine, N-(2-trifluoromethylphenylsulfonyl)oxybicyclic [2.2.1]heptane-5,6-oxy-2,3-dicarboxylated nitroimidine, N-(4-fluorophenylsulfonyl)oxybicyclic [2.2.1]heptane-5,6-oxy-2,3-dicarboxylated nitroimidine, N-(trifluoromethylsulfonyl)oxy)naphthalenedimethylnitroimidine (N-(trifluoromethylsulfonyl)oxy) Naphthalene dicarboximide, N-(2-trifluoromethylphenylsulfonoxy)naphthalene dimethylimide, N-(4-fluorophenylsulfonoxy)naphthalene dimethylimide, N-(pentafluoroethylsulfonoxy)naphthalene dimethylimide, N-(heptafluoropropylsulfonoxy)naphthalene dimethylimide, or N-(nonafluorobutylsulfonoxy)naphthalene dimethylimide, etc.

[0117] In addition, compounds described in Japanese Patent Application Publication No. 2011-232632 may be used as onium salts, halogenated compounds, diazomethane compounds, sulfonate compounds, and carboxylic acid ester compounds. For example, benzyl(4-hydroxyphenyl)methylthioonium hexafluoroantimonate.

[0118] Based on the total weight of the solid components of the chemically amplified positive photosensitive resin composition, the amount of photoacid generator (B) used is 0.3% to 3.5% by weight, preferably 0.35% to 3.3% by weight, and more preferably 0.4% to 3% by weight.

[0119] The fluorine content of the chemically amplified positive photosensitive resin composition of the present invention is 500 ppm or less, preferably 300 ppm or less, and more preferably 100 ppm or less. Furthermore, the fluorine content of the chemically amplified positive photosensitive resin composition of the present invention is preferably 0 ppm or more.

[0120] If the chemically amplified positive photosensitive resin composition of the present invention contains a fluorinated photoacid generator (B-2) resulting in a fluorine content exceeding 500 ppm, the storage stability of the chemically amplified positive photosensitive resin composition is poor and it is environmentally unfriendly.

[0121] [[] [solvent() [C] [)] []] Solvents (C) include, for example, compounds containing alcoholic hydroxyl groups or cyclic compounds containing carbonyl groups.

[0122] Compounds containing an alcoholic hydroxyl group include, for example: acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (also known as diacetone alcohol; DAA), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether (PGEE), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol mono-n-propyl ether, and propylene glycol mono-n-butyl ether. The compounds containing an alcoholic hydroxyl group are preferred to be diacetone alcohol, ethyl lactate, propylene glycol mono-t-butyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, or combinations thereof. The compounds containing an alcoholic hydroxyl group may be used alone or in combination.

[0123] Examples of carbonyl-containing cyclic compounds include: γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methyl pyrrolidone, cyclohexanone, or cycloheptanone. Preferred carbonyl-containing cyclic compounds are γ-butyrolactone, N-methyl pyrrolidone, cyclohexanone, or combinations thereof. Carbonyl-containing cyclic compounds can be used alone or in combination.

[0124] Compounds containing hydroxyl groups can be used in combination with cyclic compounds containing carbonyl groups, and there are no particular restrictions on their weight ratio. The preferred weight ratio of the hydroxyl-containing compound to the cyclic compound containing carbonyl groups is 99 / 1 to 50 / 50, more preferably 95 / 5 to 60 / 40.

[0125] Without impairing the effects of the present invention, the solvent (C) may also include other solvents. Other solvents may include, for example: (1) esters: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate or 3-methyl-3-methoxy-1-butyl acetate, etc.; (2) ketones: methyl isobutyl ketone, diisopropyl ketone or diisobutyl ketone, etc.; or (3) ethers: diethyl ether, diisopropyl ether, di-n-butyl ether or diphenyl ether, etc.

[0126] Solvent (C) can be used alone or in combination of multiple solvents.

[0127] Based on the total weight of the chemically amplified positive photosensitive resin composition, the amount of solvent (C) used is 15% to 60% by weight, preferably 17% to 58% by weight, and more preferably 20% to 55% by weight, with a total weight of 100% by weight.

[0128] [[] [resin()] [D] [)] []] Resin (D) is formed by copolymerization of monomer mixture 2. Monomer mixture 2 includes unsaturated monomers (d-1) having alkoxysilyl groups. In addition, monomer mixture 1 may also include other unsaturated monomers (d-2).

[0129] [Unsaturated monomers with alkoxysilane groups] [d-1] [)] The unsaturated monomer (d-1) with an alkoxysilyl group has a structure as shown in the following formula (d1-1): Equation (d1-1) In formula (d1-1), R61, R62 and R63 are independently hydrogen atoms, halogen atoms, hydroxyl groups, alkoxy groups with 1 to 6 carbon atoms, alkyl groups with 1 to 10 carbon atoms or phenyl groups, respectively; wherein one or more of R61, R62 and R63 are alkoxy groups with 1 to 6 carbon atoms; "*" indicates a bond.

[0130] The group represented by formula (d1-1) is preferably bonded to a benzene ring, a naphthalene ring, or an alkyl chain. Specifically, the structural unit derived from the unsaturated monomer (d-1) having an alkoxysilyl group is preferably a structural unit having at least one of the groups selected from the group consisting of the group represented by formula (d1-2), the group represented by formula (d1-3), and the group represented by formula (d1-4). Equation (d1-2) Equation (d1-3) Equation (d1-4)

[0131] In formulas (d1-2), (d1-3), and (d1-4), A11 and A12 are independently halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, or alkoxy groups with 1 to 6 carbon atoms, respectively; n1 is an integer from 0 to 4; n2 is an integer from 0 to 6; wherein, when n1 is 2 or more, multiple A11s are the same or different from each other; when n2 is 2 or more, multiple A12s are the same or different from each other; R64 is an alkyldiyl group; R61, R62, and R63 have the same meaning as in formula (d1-1); "*" indicates a bond.

[0132] In formulas (d1-2) and (d1-3), examples of alkoxy groups having 1 to 6 carbon atoms in A11 and A12, and alkyl groups having 1 to 6 carbon atoms, can be given as the same groups exemplified as R61 to R63 in formula (d1-1). The bonding position of "-SiR61R62R63" in the benzene ring or naphthalene ring can be arbitrary. For example, in the case of formula (d1-2), the bonding position of "-SiR61R62R63" relative to the bond indicated by "*" can be any of the ortho, meta, or para positions, preferably para. n1 is preferably 0 or 1, more preferably 0. n2 is preferably 0 to 2, more preferably 0. Furthermore, formula (d1-3) does not limit the bonding positions of "-SiR61R62R63" and A12 in the naphthalene ring and can be arbitrary.

[0133] The structural unit derived from the unsaturated monomer having an alkoxysilyl group (d-1) is preferably a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond. Specifically, it is preferably at least one selected from the group consisting of structural units represented by the structural units represented by the following formulas (d1-5) and (d1-6). Equation (d1-5) Equation (d1-6) In formulas (d1-5) and (d1-6), R 67 is a hydrogen atom, methyl, hydroxymethyl, cyano or trifluoromethyl; R 65 and R 66 are independently divalent aromatic cyclic groups or chain hydrocarbon groups; R 61, R 62 and R 63 have the same meaning as in formula (d1-1).

[0134] In formulas (d1-5) and (d1-6), the divalent aromatic cyclic groups of R 65 and R 66 are preferably substituted or unsubstituted pentenyl or substituted or unsubstituted pentenylnaphthyl. The divalent chain hydrocarbon group is preferably an alkyldiyl having 1 to 6 carbons, more preferably an alkyldiyl having 1 to 4 carbons, and even more preferably a straight-chain alkyldiyl having 1 to 4 carbons.

[0135] As specific examples of the structural unit represented by equation (d1-5), structural units represented by equations (d1-5-1) and (d1-5-2) can be listed below. As specific examples of the structural unit represented by equation (d1-6), structural units represented by equations (d1-6-1) and (d1-6-2) can be listed below. Equation (d1-5-1) Equation (d1-5-2) Equation (d1-6-1) Equation (d1-6-2) In formulas (d1-5-1), (d1-5-2), (d1-6-1), and (d1-6-2), R71 and R72 are each independently an alkyl group having 1 to 4 carbon atoms; R73 is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group having 1 to 4 carbon atoms; n3 is an integer from 1 to 4; A11, A12, n1, and n2 have the same meaning as in formulas (d1-2) and (d1-3); R67 has the same meaning as in formulas (d1-5) and (d1-6).

[0136] Specific examples of unsaturated monomers (d-1) with alkoxysilyl groups include: Examples of compounds having the groups represented by formulas (d1-2) include styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethoxydimethoxysilane, (meth)acryloxyphenylethyldiethoxysilane, etc. Examples of compounds having the groups represented by formulas (d1-3) include trimethoxy(4-vinylnaphthyl)silane, triethoxy(4-vinylnaphthyl)silane, methyldimethoxy(4-vinylnaphthyl)silane, ethyldiethoxy(4-vinylnaphthyl)silane, and (meth)acryloxynaphthyltrimethoxysilane. Examples of compounds having the groups represented by formulas (d1-4) include 3-(meth)propenyloxypropyltrimethoxysilane, 3-(meth)propenyloxypropyltriethoxysilane, 3-(meth)propenyloxypropylmethyldimethoxysilane, 3-(meth)propenyloxypropylmethyldiethoxysilane, and 4-(meth)propenyloxybutyltrimethoxysilane.

[0137] Based on the total weight of monomer mixture 2 being 100 parts by weight, the amount of the unsaturated monomer (d-1) having an alkoxysilyl group used is 6 to 50 parts by weight, preferably 8 to 45 parts by weight, and more preferably 10 to 40 parts by weight.

[0138] [Other unsaturated monomers()] [d-2] [)] As for other unsaturated monomers (d-2), the same monomers as those for other unsaturated monomers (a-4) mentioned above can be used, and will not be described again here.

[0139] The resin (D) has a weight-average molecular weight (Mw) of 6,000 to 15,000, preferably 6,500 to 14,000, and more preferably 7,000 to 13,000, as determined by colloidal permeation chromatography.

[0140] Based on the total weight of the solid components of the chemically amplified positive photosensitive resin composition, the amount of resin (D) used is 4% to 39% by weight, preferably 5% to 37% by weight, and more preferably 6% to 35% by weight, based on 100% by weight of the total solid components.

[0141] If the chemically amplified positive photosensitive resin composition of the present invention further includes resin (D), the coating uniformity of the chemically amplified positive photosensitive resin composition can be further improved.

[0142] [[] [add] [Additives()] [E] [)] []] Without affecting the effectiveness of the present invention, the chemically amplified positive photosensitive resin composition of the present invention may selectively include additives (E). Examples of additives (E) include: adhesion auxiliary agents, surfactants, solubility promoters, defoamers, or combinations thereof.

[0143] Adhesion aids include, for example, melamine compounds and silane compounds.

[0144] Examples of melamine include commercially available products manufactured by Mitsui Chemicals and marketed under the names Cymel-300 or Cymel-303; or commercially available products manufactured by Sanwa Chemicals and marketed under the names MW-30MH, MW-30, MS-11, MS-001, MX-750, or MX-706.

[0145] When melamine compounds are used as adhesion promoters, the amount of acid-dissociative resin (A) used is 100 parts by weight, and the amount of melamine compound used is 0 to 20 parts by weight, preferably 0.5 to 18 parts by weight, and more preferably 1.0 to 15 parts by weight.

[0146] Examples of silane compounds include: vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-epoxypropoxysilane. Propyltrimethoxysilane, 3-epoxypropoxypropyldimethylmethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, or commercially available products manufactured by Shin-Etsu Chemical Co., Ltd. (trade names such as KBM403), etc.

[0147] When a silane compound is used as an adhesion promoter, the amount of acid-dissociable resin (A) used is 100 parts by weight, and the amount of silane compound used is 0 to 2 parts by weight, preferably 0.05 to 1 part by weight, and more preferably 0.1 to 0.8 parts by weight.

[0148] Examples of surfactants include: anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane surfactants, fluorinated surfactants, or combinations thereof.

[0149] Surfactants can be listed as follows: (1) Polyoxyethylene alkyl ethers: polyoxyethylene dodecyl ether, etc.; (2) Polyoxyethylene alkylphenyl ethers: polyoxyethylene octylphenyl ether, or polyoxyethylene nonylphenyl ether, etc.; (3) Polyethylene glycol diesters: such as polyethylene glycol dilaurate or polyethylene glycol distearate; (4) Sorbitan fatty acid esters; (5) Fatty acid modified polyesters; and (6) Tertiary amine modified polyurethanes, etc.

[0150] Commercially available surfactants include, for example: KP (manufactured by Shin-Etsu Chemical Industry), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow (manufactured by Kyoeisha Oil & Fat Chemical Industry), F-Top (manufactured by Tochem Products Co., Ltd.), Megaface (manufactured by Dai Nippon Ink Chemical Industry (DIC), Fluorade (manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Asahi Glass), SINOPOL E8008 (manufactured by Chunghwa Synthetic Chemicals), F-475 (manufactured by Dai Nippon Ink Chemical Industry (DIC)), F-563 (manufactured by Dai Nippon Ink Chemical Industry (DIC)), or any combination of the above compounds.

[0151] The amount of acid-dissociable resin (A) used is 100 parts by weight, and the amount of surfactant used is 0.5 parts by weight to 50 parts by weight, preferably 1 part by weight to 40 parts by weight, and more preferably 3 parts by weight to 30 parts by weight.

[0152] Examples of solubility promoters include N-hydroxydicarboxylic imide or compounds containing phenolic hydroxyl groups.

[0153] Based on the amount of acid-dissociable resin (A) used being 100 parts by weight, the amount of dissolution accelerator used being 1 to 20 parts by weight, preferably 2 to 15 parts by weight, and more preferably 3 to 10 parts by weight.

[0154] Examples of defoamers include: Surfynol MD-20, Surfynol MD-30, EnviroGem AD01, EnviroGem AE01, EnviroGem AE02, Surfynol DF110D, Surfynol 104E, Surfynol 420, Surfynol DF37, Surfynol DF58, Surfynol DF66, Surfynol DF70, and Surfynol DF210 (manufactured by Air Products and Chemicals, Inc.).

[0155] Adhesion additives, surfactants, solubilizers and defoamers can be used individually or in combination.

[0156] [<] [Method for manufacturing chemically amplified positive photosensitive resin composition] [>] The chemically amplified positive photosensitive resin composition of the present invention can be prepared by the following method: acid-dissociating resin (A), photoacid generator (B) and solvent (C) are placed in a stirrer and stirred to mix them uniformly into a solution state. If necessary, resin (D) and additives (E) can be added.

[0157] [<] [Manufacturing methods for hardened films and components] [>] The present invention also provides a curing film, which is formed by coating a chemically amplified positive photosensitive resin composition as described above onto a substrate, followed by pre-baking, exposure, development, and post-baking.

[0158] The present invention also provides an element having a hardened film, comprising a substrate and a hardened film as described above disposed on the substrate.

[0159] The chemically amplified positive photosensitive resin composition of the present invention can be used as a forming material for a curing film of a display element. Furthermore, the present invention also includes a curing film suitable for display elements formed from the chemically amplified positive photosensitive resin composition.

[0160] The method for forming the hardened film includes the following steps: The step of forming a coating on a substrate using a chemically amplified positive photosensitive resin composition (hereinafter referred to as step (1)); The step of irradiating at least a portion of the above coating with radiation (hereinafter referred to as step (2)); The step of developing the above-mentioned coating after irradiation (hereinafter referred to as step (3)); and The step of heating the developed coating (hereinafter referred to as step (4)).

[0161] According to this formation method, a curing film for display devices with excellent surface hardness, solvent resistance, heat resistance, and voltage retention can be formed. Furthermore, by using a chemically amplified positive photosensitive resin composition with good high-temperature and high-humidity reliability and development adhesion, a curing film for display devices with fine and intricate patterns can be easily formed. Therefore, the formed curing film for display devices is suitable for display devices such as liquid crystal display devices or organic EL display devices.

[0162] Step (1): In this step, a chemically amplified positive photosensitive resin composition is coated onto a substrate to form a coating film. Preferably, the solvent is removed by pre-baking the coating film. The substrate may be, for example, glass, quartz, silicon substrate, or resin. The resin may be, for example, polyethylene terephthalate, polybutylene terephthalate, polyether ether, polycarbonate, polyimide, ring-opening polymers of cyclic olefins, and their hydrides. The pre-baking conditions vary depending on the type and mixing ratio of each component, and may be set to 70°C to 120°C for 1 to 10 minutes.

[0163] Step (2): In this step, at least a portion of the coating film formed above is exposed to radiation. Exposure is typically performed through a photomask with a predetermined pattern. The radiation used for exposure is preferably in the wavelength range of 190 nm to 450 nm, and more preferably includes ultraviolet radiation at 365 nm. The exposure dose is obtained by measuring the intensity of the 365 nm wavelength radiation using a lux meter (manufactured by OAI Optical Associates, model OAI 356), preferably 500 J / m² to 6,000 J / m², more preferably 1,500 J / m² to 1,800 J / m².

[0164] Step (3): In this step, the above-mentioned coating after irradiation is developed. By developing the exposed coating, unwanted parts (the irradiated parts) are removed to form a predetermined pattern. The developing solution used in the developing step is preferably an alkaline aqueous solution. The alkali can be, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, or amines; or quaternary ammonium salts such as tetramethylammonium hydroxide or tetraethylammonium hydroxide.

[0165] In alkaline aqueous solutions, appropriate amounts of water-soluble organic solvents such as methanol and ethanol, or surfactants, can be added. From the viewpoint of obtaining suitable developability, the concentration of alkali in the alkaline aqueous solution is preferably 0.1% to 5% by mass. Developing methods include, for example, the puddle method, immersion method, agitated immersion method, or spray method. The developing time varies depending on the composition of the chemically amplified positive photosensitive resin, and can be, for example, 1 second to 180 seconds. After developing, the coating is rinsed, for example, with running water for 30 to 90 seconds, and then air-dried using, for example, compressed air or compressed nitrogen, to form the desired pattern.

[0166] Step (4): In this step, the developed coating is heated. During heating, the patterned film is heated using a heating device such as a heating plate or an oven to promote the curing reaction of the resin (A) and obtain a cured product. The heating temperature is, for example, 120°C to 250°C. The heating time varies depending on the type of heating machine, for example, 5 minutes to 30 minutes on a heating plate and 30 minutes to 90 minutes in an oven. Alternatively, a staged baking method that involves two or more heating steps can be used. In this way, a patterned film corresponding to the hardened film for the target display element can be formed on the surface of the substrate. Furthermore, the use of the hardened film is not limited to hardened films for display elements; it can also be used as a spacer or an interlayer insulating film.

[0167] The thickness of the hardened film for the formed display element is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and even more preferably 0.1 μm to 4 μm.

[0168] The present invention will be further described with reference to the following embodiments, but it should be understood that these embodiments are for illustrative purposes only and should not be construed as limiting the implementation of the present invention. [<] [Example] [>]

[0169] [[] [Acid dissociation] [Sexual resin()] [A] Example of synthesis of [)] []] The following is an example of the synthesis of acid-dissociable resin (A):

[0170] Synthesis Example A-1 A nitrogen inlet, stirrer, heater, condenser, and thermometer were installed on a 1000 mL four-necked conical flask. After introducing nitrogen, 15 parts by weight of 2-tetrahydrofuranyl methacrylate (hereinafter referred to as a11), 20 parts by weight of the compound shown in formula (a2-2-1) (hereinafter referred to as a21), 11 parts by weight of the compound shown in formula (a3-1-3) (hereinafter referred to as a32), 8 parts by weight of methacrylic acid (hereinafter referred to as a41), 16 parts by weight of glycidyl methacrylate (hereinafter referred to as a42), 10 parts by weight of the compound shown in formula (a4-5-2) (hereinafter referred to as a44), 20 parts by weight of methyl methacrylate (hereinafter referred to as a45), 10 parts by weight of 2,2'-azobis(2,4-dimethylpentanonitrile) (hereinafter referred to as ADVN) and 200 parts by weight of diethylene glycol dimethyl ether (hereinafter referred to as Diglyme) were added. Next, the above components were slowly stirred to raise the solution temperature to 70°C, and polymerization was carried out at this temperature for 6 hours. Then, after the solvent was evaporated, the acid-dissociative resin (A) of Synthesis Example A-1 was obtained.

[0171] Synthesis Examples A-2 to A-5 The acid-dissociating resins (A) of Synthetic Examples A-2 to A-5 were prepared using the same steps as those of Synthetic Example A-1, except that the types and amounts of components in monomer mixture 1 were changed. The formulation is shown in Table 1 and will not be described again here.

[0172] In addition, the compounds corresponding to the abbreviations in Table 1 are shown below. Abbreviation compound a11 2-Tetrahydrofuranyl methacrylate a12 2-Tetrahydropyranyl methacrylate a13 1-Ethoxyethyl methacrylate a21 Unsaturated monomers having the structure shown in formula (a2-1-1) a22 Unsaturated monomers having the structure shown in formula (a2-2-1) a23 Unsaturated monomers having the structure shown in formula (a2-1-2) a24 Unsaturated monomers having the structure shown in formula (a2-2-2) a31 Unsaturated monomers having the structure shown in formula (a3-1-2) a32 Unsaturated monomers having the structure shown in formula (a3-1-3) a33 Unsaturated monomers having the structure shown in formula (a3-1-4) a34 Unsaturated monomers having the structure shown in formula (a3-1-5) a41 methacrylic acid a42 Glycidyl methacrylate a43 3-(methacryloxy)oxetane a44 Unsaturated monomers having the structure shown in formula (a4-5-2) a45 Methyl methacrylate Diglyme Diethylene glycol dimethyl ether PGMEA Propylene glycol methyl ether acetate AMBN 2,2'-Azobis-2-methylbutyronitrile ADVN 2,2'-Azobis(2,4-dimethylpentanonitrile)

[0173] [Table 1] Synthesis example A-1 A-2 A-3 A-4 A-5 Monomer Mixture 1 (parts by weight) Unsaturated monomers with acid-dissociable groups (a-1) a11 15 - - 29 - a12 - 36 - - - a13 - - 50 - 35 Unsaturated monomer (a-2) a21 - - - 8 6 a22 20 - - - - a23 - 12 - - - a24 - - 4 - - Unsaturated monomers with maleic imine groups (a-3) a31 - - - 5 4 a32 11 - - - - a33 - 6 - - - a34 - - 2 - - Other unsaturated monomers (a-4) a41 8 16 - 5 20 a42 16 - 5 29 15 a43 - 10 5 5 - a44 10 - 4 5 - a45 20 20 30 14 20 solvent Diglyme 200 - 250 200 600 PGMEA - 50 - 200 - catalyst AMBN - 12 12 - - ADVN 10 - - 10 10 Reaction temperature (°C) 70 70 70 75 80 Aggregation time (hours) 6 6 5 6 6

[0174] [[] [resin()] [D] Example of synthesis of [)] []] The following is an example of the synthesis of resin (D):

[0175] Synthetic Example D-1 A nitrogen inlet, stirrer, heater, condenser, and thermometer were installed on a 1000 mL four-necked conical flask. After introducing nitrogen, 20 parts by weight of methacryloxypropyltriethoxysilane (hereinafter referred to as d11), 7 parts by weight of methacrylic acid (hereinafter referred to as d21), 24 parts by weight of glycidyl methacrylate (hereinafter referred to as d22), 11 parts by weight of 3-(methacryloxymethoxy)oxetane (hereinafter referred to as d23), 19 parts by weight of methyl methacrylate (hereinafter referred to as d24), 19 parts by weight of styrene (hereinafter referred to as d25), 10 parts by weight of 2,2'-azobis(2,4-dimethylpentanonitrile) (hereinafter referred to as ADVN), and 200 parts by weight of diethylene glycol dimethyl ether (hereinafter referred to as Diglyme) were added. The above components were then slowly stirred to raise the solution temperature to 70°C, and polymerization was carried out at this temperature for 6 hours. Then, after the solvent is evaporated, the acid-dissociative resin (D) of Synthetic Example D-1 can be obtained.

[0176] Synthesis Examples D-2 to D-5 The resin (D) of Synthetic Examples D-2 to D-5 was prepared using the same steps as that of Synthetic Example D-1, except that the types and amounts of components in monomer mixture 2 were changed. The formulation is shown in Table 2 and will not be described again here.

[0177] In addition, the compounds corresponding to the abbreviations in Table 2 are shown below. Abbreviation compound d11 Methacryloyloxypropyltriethoxysilane d12 Acryloxypropyltriethoxysilane d13 Methoxypropyltrimethoxysilane d14 Styrene triethoxysilane d15 Trimethoxy(4-vinylnaphthalene)silane d21 methacrylic acid d22 Glycidyl methacrylate d23 3-(methacryloxy)oxetane d24 Methyl methacrylate d25 styrene Diglyme Diethylene glycol dimethyl ether PGMEA Propylene glycol methyl ether acetate AMBN 2,2'-Azobis-2-methylbutyronitrile ADVN 2,2'-Azobis(2,4-dimethylpentanonitrile)

[0178] [Table 2] Synthesis example D-1 D-2 D-3 D-4 D-5 Monomer Mixture 2 (parts by weight) Unsaturated monomers with alkoxysilyl groups (d-1) d11 20 - - - - d12 - 10 - - - d13 - - 40 - - d14 - - - 15 - d15 - - - - 25 Other unsaturated monomers (d-2) d21 7 13 25 10 26 d22 twenty four 32 - 20 10 d23 11 - 20 - 10 d24 19 15 15 30 - d25 19 30 - 25 29 solvent Diglyme 200 - 250 200 200 PGMEA - 50 - 200 300 catalyst AMBN - 12 - - 12 ADVN 10 - 10 10 - Reaction temperature (°C) 70 70 80 75 70 Aggregation time (hours) 6 6 5 6 5

[0179] [[] [Examples of chemical amplitude positive photosensitive resin compositions] []] The following are examples of chemical amplitude positive photosensitive resin compositions:

[0180] Example 1 99.2 parts by weight of the acid-dissociative resin (A) of Synthetic Example A-1 (hereinafter referred to as A-1) and 0.8 parts by weight of the compound shown in formula (b1-1-11) (hereinafter referred to as B-11) were added to 40 parts by weight of diethylene glycol dimethyl ether (hereinafter referred to as C-1), and stirred evenly with a shaking stirrer to obtain the chemically amplified positive photosensitive resin composition of Example 1. The chemically amplified positive photosensitive resin composition of Example 1 was evaluated using the evaluation method described below, and the results are shown in Table 3.

[0181] Examples 2 to 7 and Comparative Examples 1 to 2 The chemically amplified positive photosensitive resin compositions of Examples 2 to 7 and Comparative Examples 1 to 2 were prepared using the same steps as in Example 1, except that the types and amounts of components of the chemically amplified positive photosensitive resin compositions were changed. The formulations and evaluation results are shown in Table 3, and will not be repeated here.

[0182] In addition, the compounds corresponding to the abbreviations in Table 3 are shown below. Abbreviation compound A-1 Acid-dissociative resin (A) of Synthetic Example A-1 A-2 Acid-dissociative resin (A) of Synthetic Example A-2 A-3 Acid-dissociative resin (A) of Synthetic Example A-3 A-4 Acid-dissociative resin (A) of Synthetic Example A-4 A-5 Acid-dissociable resin (A) of Synthetic Example A-5 B-11 Oxime sulfonate compounds having the structure shown in formula (b1-1-11) B-12 Oxime sulfonate compounds having the structure shown in formula (b1-1-12) B-13 Oxime sulfonate compounds having the structure shown in formula (b1-1-13) B-14 Oxime sulfonate compounds having the structure shown in formula (b1-1-14) B-15 Oxime sulfonate compounds having the structure shown in formula (b1-1-15) B-16 (5-p-Toluenesulfonyloxyimino)-5h-thiophene-2-yl)-(2-methylphenyl)acetonitrile B-21 N-(trifluoromethylsulfonyl)naphthalenedimethylimide B-22 N-(trifluoromethylsulfonyl)butadiene C-1 Diethylene glycol dimethyl ether C-2 Propylene glycol methyl ether acetate D-1 The resin (D) of Synthetic Example D-1 D-2 The resin (D) of Synthetic Example D-2 D-3 Resin (D) of Synthetic Example D-3 D-4 The resin (D) of Synthetic Example D-4 D-5 The resin (D) of Synthetic Example D-5 E-1 Surfactant SF-8427 (manufactured by Dow Corning Toray Polysiloxane Co., Ltd.) E-2 Surfactant F-563 (manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.)

[0183] [Table 3] Ingredients (parts by weight) Example Comparative example 1 2 3 4 5 6 7 1 2 Acid-dissociable resin (A) A-1 99.2 - - - - 86.7 98.5 99.2 98.7 A-2 - 93.5 - - - - - - - A-3 - - 81.2 - - - - - - A-4 - - - 73.8 - - - - - A-5 - - - - 64.4 - - - - Photoacid Generator (B) Fluorine-free light-sensitive acid Producing agent (B-1) B-11 0.8 - - - - - - - - B-12 - 0.4 - - - - - - - B-13 - - 2.8 - - - - - - B-14 - - - 2.2 - - - - - B-15 - - - - 0.6 - - - - B-16 - - - - - 1.2 1.4 - - Fluorinated photonic acid Generator (B-2) B-21 - - - - - - - 0.8 - B-22 - - - - - - - - 1.6 Solvent (C) C-1 40 - 20 - 110 - 20 55 - C-2 - 65 - 100 - 45 10 - 45 Resin (D) D-1 - 6.0 - - - - - - - D-2 - - 16.0 - - - - - - D-3 - - - 24.0 - - - - - D-4 - - - - 35.0 - - - - D-5 - - - - - 12.0 - - - Additive (E) E-1 - 0.05 - - - 0.10 - - - E-2 - - - - - - 0.06 - - Fluorine content (ppm) 5 10 5 15 15 10 260 520 950 Storage stability assessment ◎ ◎ ◎ ◎ ◎ ○ ○ X X Evaluation of coating uniformity ○ ◎ ◎ ◎ ◎ ◎ ○ ○ ○ [[] [Evaluation Method] []]

[0184] [Fluoride content] The chemically amplified positive photosensitive resin composition of the examples and comparative examples was combusted and decomposed in the combustion tube of the analytical apparatus. The generated gas was absorbed into the absorbent, and then a portion of the absorbent was analyzed by ion chromatography to determine the fluorine content.

[0185] [Combustion and Absorption Conditions] System: AQF-2100H, GA-210 (Made by Mitsubishi Chemical) Electric furnace temperature: Inlet 900℃, Outlet 1000℃ Gases: Ar / O₂ 200 mL / min, O₂ 400 mL / min Absorbent: H₂O₂ 0.1% by mass Absorption liquid volume: 5 mL

[0186] [Ion Chromatography - Anion Analysis Conditions] System: ICS1600 (DIONEX) Mobile phase: 2.7 mmol / L Na₂CO₃, 0.3 mmol / L NaHCO₃ Flow rate: 1.50 mL / min Detector: Conductivity detector Injection volume: 100mL

[0187] [Maintain stability] After coating the chemically amplified positive photosensitive resin composition of the examples and comparative examples onto a glass substrate (100mm × 100mm), it was pre-baked at 110°C for 120 seconds to form a coating with a thickness of 3μm. Next, exposure was performed using an i-line exposure apparatus (apparatus name: FX-702J, Nikon, NA=0.14) with a photomask containing a 10μm via hole. Following this, development was performed for 70 seconds using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 23°C, followed by rinsing with pure water for 15 seconds and spin drying. The exposure amount sufficient to produce a 10μm via photoresist pattern was defined as the original sensitivity (Eop).

[0188] The prepared chemically amplified positive photosensitive resin composition was placed in a light-proof, sealed container. After being placed at 25°C for 7 days, the container was opened and the sensitivity (Eop') after 7 days was measured as described above. The exposure growth rate ΔEop = (Eop' - Eop) / Eop was calculated and evaluated using the following criteria. ◎:△Eop<5% 〇:5%≦△Eop<10% △:10%≦△Eop<20% ╳:△Eop≧20%

[0189] [Uniform coating] [sex] After the chemically amplified positive photosensitive resin composition of the examples and comparative examples was coated on a glass substrate (100mm×100mm), it was pre-baked at 110°C for 120 seconds to form a coating film with a thickness of 3μm. Then, the coating film was irradiated with a sodium lamp, and the unevenness of the coating surface was visually observed to see if there was any inhomogeneity (mura), and the following criteria were used for evaluation. ◎: No unevenness 〇: Only slightly uneven at the edges △: There are a few obvious uneven areas. ╳: There is a large amount of obvious unevenness

[0190] [<] [Evaluation Results] [>] As shown in Table 3, compared with the chemically amplified positive photosensitive resin compositions (Examples 1-7) that include a specific fluorine-free photoacid generator (B-1) and control the fluorine content to below 500 ppm, the chemically amplified positive photosensitive resin compositions of Comparative Examples 1 and 2 have a fluorine content exceeding 500 ppm due to the use of a fluorine-containing photoacid generator (B-2). Therefore, their storage stability evaluation is poor and they are not environmentally friendly.

[0191] Furthermore, when the fluorine-free photoacid generator (B-1) includes an oxime sulfonate compound (B-1-1) (Examples 1-5), the storage stability of the chemically amplified positive photosensitive resin composition is better.

[0192] Furthermore, when the chemically amplified positive photosensitive resin composition further includes resin (D) (Examples 2-6), the coating uniformity of the chemically amplified positive photosensitive resin composition can be further improved.

[0193] In summary, the chemically amplified positive photosensitive resin composition of the present invention includes a specific fluorine-free photoacid generator (B-1) and controls the fluorine content to below 500 ppm, thus obtaining a chemically amplified positive photosensitive resin composition with good coating uniformity, storage stability and environmental friendliness.

[0194] Although the present invention has been disclosed above by way of embodiments, it is not intended to limit the present invention. Anyone skilled in the art can make some modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A chemically amplified positive photosensitive resin composition, comprising: An acid-dissociative resin (A); a photoacid generator (B); and a solvent (C), wherein the acid-dissociative resin (A) is formed by copolymerization of a monomer mixture 1, the monomer mixture 1 comprising an unsaturated monomer (a-1) having an acid-dissociative group, an unsaturated monomer (a-2) having a structure as shown in formula (a2-1) or formula (a2-2) below, and an unsaturated monomer (a-3) having a maleimide group; the photoacid generator (B) comprises a fluorine-free photoacid generator (B-1), the fluorine-free photoacid generator (B-1) having a structure as shown in formula (b1-1) below; the fluorine content of the chemically amplified positive photosensitive resin composition is less than 500 ppm; in formula (a2-1) or formula (a2-2), R1, R2, and R3 independently represent hydrogen atoms or straight-chain alkyl or branched alkyl groups having 1 to 30 carbon atoms; in formula (b1-1) In formula (b1-1), A1 represents an alkyl or aryl group with 1 to 10 carbon atoms that is substituted or unsubstituted; A2 represents an alkyl group with 1 to 10 carbon atoms, an aryl group with 1 to 10 carbon atoms, or a nitrile group; A3 to A7 independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms that is substituted or unsubstituted with an ether group (-O-) or a thioether group (-S-), or an aryl group.

2. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein, The fluorine content of the chemically amplified positive photosensitive resin composition is below 300 ppm.

3. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein, The fluorine content of the chemically amplified positive photosensitive resin composition is less than 100 ppm.

4. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein, The fluorine content of the chemically amplified positive photosensitive resin composition is above 0 ppm.

5. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein, Based on the total weight of the solid components of the chemically amplified positive photosensitive resin composition (100% by weight), the amount of acid-dissociating resin (A) used is 60% to 95% by weight, the amount of photoacid generator (B) used is 0.3% to 3% by weight, and based on the total weight of the chemically amplified positive photosensitive resin composition (100% by weight), the amount of solvent (C) used is 15% to 60% by weight.

6. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein, Based on the total weight of the solid components of the chemically amplified positive photosensitive resin composition being 100% by weight, the amount of photoacid generator (B-1) used is 0.3% to 3% by weight.

7. The chemically amplified positive photosensitive resin composition as claimed in claim 1, further comprising resin (D), said resin (D) being formed by copolymerization of monomer mixture 2, said monomer mixture 2 comprising unsaturated monomers (d-1) having alkoxysilicone groups.

8. The chemically amplified positive photosensitive resin composition as described in claim 7, wherein, Based on the total weight of the solid components of the chemically amplified positive photosensitive resin composition being 100% by weight, the amount of resin (D) used is 4% to 39% by weight.

9. A curing film formed by coating a chemically amplified positive photosensitive resin composition as described in any one of claims 1 to 8 onto a substrate, followed by pre-baking, exposure, development, and post-baking.

10. An element having a hardened film, comprising: Substrate; And a hardened film as described in claim 9, disposed on the substrate.