Chemical amplification positive photosensitive resin composition and use thereof

Abstract

The present application provides a kind of chemical amplification positive photosensitive resin composition and its application, the chemical amplification positive photosensitive resin composition includes a first resin (A1), a second resin (A2), a photoacid generator (B), a solvent (C), a compound (D) shown in formula (6) or formula (7) and a hindered amine compound (E) shown in formula (e1), and the protective film prepared has the advantages of good sensitivity and stability over time.The present application is also about the protective film prepared by the chemical amplification positive photosensitive resin composition and the component comprising the protective film.

Description

TECHNICAL FIELD

[0001] The present application relates to a chemically amplified positive photosensitive resin composition and applications thereof, in particular, to a chemically amplified positive photosensitive resin having the advantages of good sensitivity and good stability over time, and a protective film prepared therefrom and a component comprising the same. BACKGROUND

[0002] A display component such as a thin film transistor liquid crystal display component or an organic electroluminescence device (organic EL component) generally includes an insulating film such as an interlayer insulating film or a planarization film, and such an insulating film is generally formed using a radiation-sensitive composition. In order to meet the requirements of patterning performance, a positive photosensitive resin composition including an acid generator such as naphthoquinone diazide (see Japanese Patent Laid-Open No. 2001-354822) can be generally used, but many other photosensitive compositions have been proposed in recent years.

[0003] For example, Japanese Patent Laid-Open No. 2004-4669 relates to a positive chemically amplified material that forms a hardened film for a display component, and the positive chemically amplified material has higher sensitivity than the aforementioned positive photosensitive resin composition using an acid generator such as naphthoquinone diazide. The positive chemically amplified material contains a crosslinking agent, an acid generator, and an acid-dissociable resin having a protective group that can be dissociated by the action of an acid, and although the acid-dissociable resin itself is not soluble or hardly soluble in an alkaline aqueous solution, the protective group is dissociated by the action of an acid to become soluble in an alkaline aqueous solution. In addition, for example, Japanese Patent Laid-Open No. 2004-264623, Japanese Patent Laid-Open No. 2011-215596, and Japanese Patent Laid-Open No. 2008-304902 also propose a positive photosensitive composition containing a resin having an acetal structure and / or a ketal structure and an epoxy group and an acid generator.

[0004] In such a photosensitive resin composition, in addition to having high light sensitivity, it is also required to have storage stability in which the viscosity does not easily change over time, so that the hardened film formed from such a photosensitive resin composition can have resistance to swelling due to a developer or the like. Accordingly, the pattern formed by the hardened film can also be sufficiently adhered to a substrate after development without easily peeling, and the hardened film has sufficient transparency, and even after exposure, the pattern is sufficiently adhered to the substrate without easily peeling.

[0005] However, the current photosensitive resin composition still has the problems of poor sensitivity and poor stability over time, and is still not acceptable in the industry. SUMMARY

[0006] The present application has the advantages of good sensitivity and good stability over time by the special composition and / or ratio of the chemical-amplification positive photosensitive resin composition.

[0007] Therefore, the present application provides a chemical-amplification positive photosensitive resin composition, comprising:

[0008] a first resin (A1) obtained by copolymerization of a first mixture containing an unsaturated carboxylic acid monomer (a1-1), a monomer containing an acid-dissociable group represented by formula (1) (a1-2), and an unsaturated monomer containing a lactone structure (a1-3);

[0009]

[0010] In formula (1), R 11 and R 12 are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, or an aryl group, wherein the hydrogen atoms of the alkyl group, the alicyclic hydrocarbon group, or the aryl group can be partially or entirely substituted, and R 11 and R 12 are not simultaneously hydrogen atoms; R 13 is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group, or an aryl group, wherein the hydrogen atoms of the alkyl group, the alicyclic hydrocarbon group, the aralkyl group, and the aryl group can be partially or entirely substituted; R 11 and R 13 may be mutually bonded to form a cyclic ether structure together with the carbon atom to which R 11 is bonded and the oxygen atom to which R 13 is bonded;

[0011] a second resin (A2) obtained by copolymerization of a second mixture containing an unsaturated carboxylic acid monomer (a2-1) and an unsaturated monomer containing a phenolic hydroxyl group (a2-2);

[0012] a photo-acid generator (B);

[0013] a solvent (C);

[0014] a compound (D) represented by formula (6) or formula (7):

[0015]

[0016] In formula (6), R 1 and R 2 are each independently an alkyl group having a carbon number of 1 to 4; n6 is an integer of 0 to 2; L 1 is a single bond or a divalent linking group; X 1 is -S- or -NH-; R 3 is a monovalent organic group;

[0017]

[0018] in formula (7), R 5 and R 6 each independently is an alkyl group having 1 to 4 carbons; n7 is an integer of 0 to 2; L 2 is a single bond or a divalent linking group; X 2 is -S- or -NH-; A is a heterocycle containing carbon atoms and nitrogen atoms; and

[0019] a hindered amine compound (E) represented by formula (el),

[0020]

[0021] in formula (el), n is an integer of 4 or more; E1 is an n-valent organic group; E2 to E5 each independently is a monovalent organic group having 1 to 12 carbons; and E6 is a hydrogen atom or a monovalent alkyl group having 1 to 12 carbons.

[0022] The present application also provides a protective film formed by applying the aforementioned chemically amplified positive photosensitive resin composition to a substrate, and then performing a pre-baking, exposure, development, and post-baking process.

[0023] The present application further provides an assembly having a protective film, comprising a substrate and the aforementioned protective film attached to the substrate. DETAILED DESCRIPTION

[0024] The present application provides a chemically amplified positive photosensitive resin composition, comprising:

[0025] a first resin (Al) obtained by copolymerization of a first mixture containing an unsaturated carboxylic acid monomer (al-1), a monomer (al-2) containing an acid dissociable group represented by formula (1), and an unsaturated monomer (al-3) containing a lactone structure;

[0026]

[0027] in formula (1), R 11 and R 12 each independently is a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, or an aryl group, wherein the hydrogen atoms of the alkyl group, the alicyclic hydrocarbon group, or the aryl group can be partially or entirely substituted, and R 11 and R 12 are not simultaneously a hydrogen atom; R 13 is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group, or an aryl group, wherein the hydrogen atoms of the alkyl group, the alicyclic hydrocarbon group, the aralkyl group, and the aryl group can be partially or entirely substituted; R 11 and R 13 may be bonded to each other to form a ring with R 11the bonded carbon atoms and R 13 the bonded oxygen atoms form a cyclic ether structure together;

[0028] a second resin (A2) obtained by copolymerization of a second mixture containing an unsaturated carboxylic acid monomer (a2-1) and an unsaturated monomer containing a phenolic hydroxyl group (a2-2);

[0029] a photo acid generator (B);

[0030] a solvent (C);

[0031] a compound (D) represented by formula (6) or formula (7):

[0032]

[0033] in formula (6), R 1 and R 2 each independently is an alkyl group having 1 to 4 carbons; n6 is an integer of 0 to 2; L 1 is a single bond or a divalent linking group; X 1 is -S- or -NH-; R 3 is a monovalent organic group;

[0034]

[0035] in formula (7), R 5 and R 6 each independently is an alkyl group having 1 to 4 carbons; n7 is an integer of 0 to 2; L 2 is a single bond or a divalent linking group; X 2 is -S- or -NH-; A is a heterocycle containing carbon atoms and nitrogen atoms; and

[0036] a hindered amine compound (E) represented by formula (el),

[0037]

[0038] in formula (el), n is an integer of 4 or more; E1 is an n-valent organic group; E2 to E5 each independently is a monovalent organic group having 1 to 12 carbons; and E6 is a hydrogen atom or a monovalent alkyl group having 1 to 12 carbons.

[0039] Each component of the chemically amplified positive photosensitive resin composition used in the present application will be described in detail below.

[0040] The first resin (Al) of the present application can be obtained by copolymerization of a first mixture which can contain an unsaturated carboxylic acid monomer (al-1), a monomer containing an acid dissociation group represented by formula (1) (al-2), and an unsaturated monomer containing a lactone structure (al-3).

[0041] The unsaturated carboxylic acid monomer (a1-1) of the present application refers to a compound containing a carboxylic acid group or a carboxylic anhydride structure and an unsaturated bond for polymerization, and the structure is not particularly limited, which can include but is not limited to unsaturated monocarboxylic acid compounds, unsaturated dicarboxylic acid compounds, unsaturated dicarboxylic anhydride compounds, polycyclic unsaturated carboxylic acid compounds, polycyclic unsaturated dicarboxylic acid compounds, and polycyclic unsaturated dicarboxylic anhydride compounds.

[0042] Specific examples of the aforementioned unsaturated monocarboxylic acid compounds include (meth)acrylic acid, crotonic acid, alpha-chloroacrylic acid, ethyl acrylic acid, cinnamic acid, 2-(meth)acryloyloxyethoxy succinic acid ester, 2-(meth)acryloyloxyethoxy hexahydrophthalic acid ester, 2-(meth)acryloyloxyethoxy phthalic acid ester, and omega-carboxy poly(caprolactone) polyol monoacrylate (trade name: ARONIX M-5300, manufactured by Toagosei).

[0043] Specific examples of the aforementioned unsaturated dicarboxylic acid compounds include maleic acid, fumaric acid, methyl fumaric acid, itaconic acid, citraconic acid, and the like.

[0044] In specific examples of the present application, the unsaturated dicarboxylic anhydride compound is an anhydride compound of the aforementioned unsaturated dicarboxylic acid compound.

[0045] Specific examples of the aforementioned polycyclic unsaturated carboxylic acid compound include 5-carboxy bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methyl bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethyl bicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methyl bicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethyl bicyclo[2.2.1]hept-2-ene.

[0046] Specific examples of the aforementioned polycyclic unsaturated dicarboxylic acid compound include 5,6-dicarboxy bicyclo[2.2.1]hept-2-ene.

[0047] The aforementioned polycyclic unsaturated dicarboxylic anhydride compound is an anhydride compound of the aforementioned polycyclic unsaturated dicarboxylic acid compound.

[0048] Preferred specific examples of the aforementioned unsaturated carboxylic acid monomer (a1-1) are acrylic acid, methacrylic acid, maleic anhydride, 2-methacryloyloxyethoxy succinic acid ester, 2-methacryloyloxyethoxy hexahydrophthalic acid, or a combination thereof.

[0049] The aforementioned unsaturated carboxylic acid monomer (a1-1) can be used alone or in a mixture. The amount of the unsaturated carboxylic acid monomer (a1-1) used is 3 parts by weight to 30 parts by weight, preferably 4 parts by weight to 28 parts by weight, and more preferably 5 parts by weight to 25 parts by weight, based on 100 parts by weight of the total amount of the first mixture of the first resin (A1).

[0050] The acid-dissociable group-containing monomer (a1-2) of the present application has an acid-dissociable group represented by the following formula (1):

[0051]

[0052] In formula (1), R 11 and R 12 each independently is a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, or an aryl group, wherein the alkyl group, the alicyclic hydrocarbon group, or the aryl group can be partially or entirely substituted with a hydrogen atom, and R 11 and R 12 are not simultaneously a hydrogen atom; R 13 is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group, or an aryl group, wherein the alkyl group, the alicyclic hydrocarbon group, the aralkyl group, and the aryl group can be partially or entirely substituted with a hydrogen atom; R 11 and R 13 may be bonded to each other to form a cyclic ether structure together with the carbon atom to which R 11 is bonded and the oxygen atom to which R 13 is bonded.

[0053] The acid-dissociable group of the acid-dissociable group-containing monomer (a1-2) dissociates by the action of an acid generated from the photo-acid generator (B) described below at the time of exposure, and generates a polar group, and thus a resin (A) that is originally insoluble or hardly soluble in an aqueous alkali solution becomes soluble in the aqueous alkali solution.

[0054] The acid-dissociable group-containing monomer (a1-2) is not particularly limited as long as it contains a structure represented by formula (1). The acid-dissociable group-containing monomer (a1-2) can easily dissociate by means of an acid.

[0055] The alicyclic hydrocarbon group represented by R 11 and R 12 may be exemplified by an alicyclic hydrocarbon group having a carbon number of 3 to 20, and the like. In addition, the alicyclic hydrocarbon group having a carbon number of 3 to 20 can be polycyclic. The alicyclic hydrocarbon group having a carbon number of 3 to 20 may be exemplified by, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bornyl group, a norbornyl group, an adamantyl group, and the like.

[0056] The aryl group represented by R 11 and R 12 may be exemplified by an aryl group having a carbon number of 6 to 14, and the like. The aryl group having a carbon number of 6 to 14 can be monocyclic, can be a structure in which monocyclic rings are linked, or can be a condensed ring. The aryl group having a carbon number of 6 to 14 may be exemplified by, for example, a phenyl group, a naphthyl group, and the like.

[0057] The alicyclic hydrocarbon group represented by R 11 and R 12The substituents of the alkyl group, alicyclic hydrocarbon group and aryl group represented by the above R1may be exemplified by a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, alicyclic hydrocarbon group (e.g., cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, bornyl group, norbornyl group, adamantyl group, etc.), aryl group (e.g., phenyl group, naphthyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, propoxy group, n-butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, etc., alkoxy group having carbon number of 1 to 20, etc.), acyl group (e.g., acetyl group, propionyl group, butyryl group, isobutyryl group, etc., acyl group having carbon number of 2 to 20, etc.), acyloxy group (e.g., acetyloxy group, propionyloxy group, butyryloxy group, tertiary butyryloxy group, tertiary pentoxy group, etc., acyloxy group having carbon number of 2 to 10, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc., alkoxycarbonyl group having carbon number of 2 to 20), halogenated alkyl group (e.g., methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, etc., straight-chain alkyl group; isopropyl group, isobutyl group, tertiary butyl group, neopentyl group, 2-hexyl group, 3-hexyl group, etc., branched-chain alkyl group; alicyclic hydrocarbon group obtained by substituting a part or all of hydrogen atoms of the above-mentioned groups with halogen atom), hydroxyalkyl group (e.g., hydroxymethyl group, etc.), etc.

[0058] The above-mentioned R1 13 The above-mentioned alkyl group, alicyclic hydrocarbon group and aryl group represented by the above R1 11 The above-mentioned R1 12 The above-mentioned R1 13 The aralkyl group represented by the above R1may be exemplified by benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, etc.

[0059] The above-mentioned R1 11 The above-mentioned R1 13 The above-mentioned R1

[0060] The above-mentioned group represented by the formula (1) may be exemplified by a group represented by the following formula, etc.

[0061]

[0062] The monomer (a1-2) having an acid-dissociable group described above can be exemplified by, for example, 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, tetrahydrofurfuryl 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-bis(1-methoxyethoxycarbonyl)-2-norbornene, 5,6-bis(1-(cyclohexyloxy)ethoxycarbonyl)-2-norbornene, 5,6-bis(1-(benzyloxy)ethoxycarbonyl)-2-norbornene, p-1-ethoxyethoxy-styrene or m-1-ethoxyethoxy-styrene, p-1-methoxyethoxy-styrene or m-1-methoxyethoxy-styrene, p-1-n-butoxyethoxy-styrene or m-1-n-butoxyethoxy-styrene, p-1-isobutoxyethoxy-styrene or m-1-isobutoxyethoxy-styrene, p-1-(1,1-dimethylethoxy)ethoxy-styrene or m-1-(1,1-dimethylethoxy)ethoxy-styrene, p-1-(2-chloroethoxy)ethoxy-styrene or m-1-(2-chloroethoxy)ethoxy-styrene, p-1-(2-ethylhexyloxy)ethoxy-styrene or m-1-(2-ethylhexyloxy)ethoxy-styrene, p-1-n-propoxyethoxy-styrene or m-1-n-propoxyethoxy-styrene, p-1-cyclohexyloxyethoxy-styrene or m-1-cyclohexyloxyethoxy-styrene, p-1-(2-cyclohexylethoxy)ethoxy-styrene or m-1-(2-cyclohexylethoxy)ethoxy-styrene, p-1-benzyloxyethoxy-styrene or m-1-benzyloxyethoxy-styrene, and the like.

[0063] The monomer (a1-2) having an acid dissociable group is preferably 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 1-benzyloxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, tetrahydrofurfuryl methacrylate, more preferably 2-tetrahydropyranyl methacrylate and tetrahydrofurfuryl methacrylate.

[0064] The total amount of use of the first mixture of the first resin (A1) is 100 parts by weight, and the amount of use of the monomer (a1-2) having an acid dissociable group is 15 to 70 parts by weight, preferably 17 to 68 parts by weight, more preferably 20 to 65 parts by weight.

[0065] If the monomer (a1-2) having an acid dissociable group is not used in the first mixture of the first resin (A1) used in the chemically amplified positive photosensitive resin composition of the present application, there is a problem that the sensitivity is not good.

[0066] The unsaturated monomer (a1-3) having a lactone structure of the present application is preferably a compound represented by the formula (3):

[0067]

[0068] In the formula (3), R X1 is a hydrogen atom or an alkyl group; R A2 is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group or an acid dissociable group, and when n2 is more than 1, a plurality of R A2 may be the same or different; A 1 is a single bond or a divalent linking group; and Z 2 is a monocyclic or polycyclic structure having -O-C(=O)-; and n2 is an integer of 0 or more.

[0069] The alkyl group of the aforementioned R X1 is preferably a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. The alkyl group can have a substituent, and the substituent is preferably a hydroxyl group or a halogen atom (particularly a fluorine atom).

[0070] The aforementioned R A2 is preferably an alkyl group having 1 to 4 carbon atoms or a cyano group.

[0071] The divalent linking group of the aforementioned A 1 may be exemplified by a linear, branched or cyclic alkylene group, an aralkylene group, a divalent group such as -O-, -COO-, -S-, -NR"- (wherein R" is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom), -CO-, -NR"CO-, -SO2-, or a group having a combination of these groups. Among them, A 1The divalent linking group of the unsaturated monomer (a1-3) is preferably a group containing at least one of -0-, -COO-, -S-, -NH-, and -CO-, or a group in combination with -(CH2) m m is an integer of 1 to 10, preferably an integer of 1 to 6, and more preferably an integer of 1 to 4.

[0072] The aforementioned Z 2 is preferably a monocyclic structure. In the case where Z 2 represents a monocyclic structure, it is preferably a lactone structure forming a 5-membered ring to a 7-membered ring, and more preferably a lactone structure forming a 5-membered ring or a 6-membered ring. In the case where Z 1 represents a polycyclic structure, it is preferably a structure in which other ring structures are annelated to the lactone structure in the form of a bicyclic structure or a spiro structure. The other ring structures can include a cyclic hydrocarbon group having a carbon number of 3 to 20, a heterocyclic group having a carbon number of 3 to 20, and the like. The heterocyclic group is not particularly limited, and can include a heteroatom in one or more of the atoms constituting the ring, or an aromatic heterocyclic group. In addition, the heterocyclic group is preferably a 5-membered ring or a 6-membered ring, and more preferably a 5-membered ring. Specifically, the heterocyclic group is preferably a group containing at least one oxygen atom, and can include, for example, an oxolane ring, an oxane ring, a dioxane ring, and the like.

[0073] The aforementioned n2 is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0. In the case where n2 represents an integer of 2 or more, the plurality of R A2 may be the same or different. In addition, the plurality of R A2 may be bonded to each other to form a ring, but is preferably not bonded to each other to form a ring.

[0074] In addition, the unsaturated monomer (a1-3) containing a lactone structure is preferably represented by the following general formula (3-1):

[0075]

[0076] In formula (3-1), R X2 is a hydrogen atom or an alkyl group; R A3 is an alkyl group having a carbon number of 1 to 8, a cycloalkyl group having a carbon number of 3 to 7, an alkoxy group having a carbon number of 1 to 8, an alkoxycarbonyl group having a carbon number of 2 to 8, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid-decomposable group, and when n3 is greater than 1, the plurality of R A3 may be the same or different; A 2 is a single bond or a divalent linking group; Z 3 is a monocyclic or polycyclic structure containing -0-C(=0)-; n3 is an integer of 0 or more; X 1 is an oxygen atom or -NR"-, and R" is a hydrogen atom or an alkyl group.

[0077] The aforementioned R X2The alkyl group of the group -C(=O)R' is preferably a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. The alkyl group can have a substituent, and the substituent is preferably a hydroxyl group or a halogen atom (particularly a fluorine atom).

[0078] The aforementioned R A3 is preferably an alkyl group having 1 to 4 carbon atoms or a cyano group.

[0079] The aforementioned A 2 The divalent linking group of the group -A-R" can be exemplified by a linear, branched or cyclic alkylene group, an arylene group, -O-, -COO-, -S-, -NR"-, -CO-, -NR"CO-, -SO2-, or the like divalent group, or a group containing a combination of these groups, R" being a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. Among them, the divalent linking group of the group -A-R" 2 is preferably a group containing at least one of -COO-, -CO-, or a combination of these groups and -(CH2) m , m being an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4. The group -A-R 2 is particularly preferably a single bond.

[0080] The aforementioned Z 3 is preferably a monocyclic structure. In the case where Z 3 represents a monocyclic structure, it is preferably a lactone structure forming a 5- to 7-membered ring, more preferably a lactone structure forming a 5- or 6-membered ring. In the case where Z 1 represents a polycyclic structure, it is preferably a structure in which another ring structure is annelated to the lactone structure in the form of a bicyclic structure or a spiro structure. The other ring structure can be exemplified by a cyclic hydrocarbon group having 3 to 20 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, or the like. The heterocyclic group is not particularly limited, and can be exemplified by a structure in which one or more of the atoms constituting the ring is a heteroatom, or an aromatic heterocyclic group. In addition, the heterocyclic group is preferably a 5- or 6-membered ring, more preferably a 5-membered ring. Specifically, the heterocyclic group is preferably a structure containing at least one oxygen atom, and can be exemplified by an oxolane ring, an oxane ring, a dioxane ring, or the like.

[0081] The aforementioned n3 is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0. In the case where n3 represents an integer of 2 or more, the plurality of R A3 may be the same or different. In addition, the plurality of R A3 may also be bonded to each other to form a ring, but is preferably not bonded to each other to form a ring.

[0082] The aforementioned X 1 is preferably an oxygen atom. In the case where X 1 is -NR"-, R" can be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom.

[0083] The structure represented by formula (3) is preferably a structure represented by any one of the following formulae (LC1-1) to (LC1-21):

[0084]

[0085] In formulae (LC1-1) to (LC1-21), Rb2is an alkyl group having 1 to 8 carbons, a cycloalkyl group having 3 to 7 carbons, an alkoxy group having 1 to 8 carbons, an alkoxycarbonyl group having 2 to 8 carbons, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid-decomposable group, and when n4is an integer of 2 or more, a plurality of Rb2may be the same or different.

[0086] The structure represented by the aforementioned formulae (LC1-1) to (LC1-21) can have or can not have Rb2; preferably, it does not have Rb2, that is, n4is 0. The aforementioned Rb2is preferably an alkyl group having 1 to 4 carbons or a cyano group.

[0087] The aforementioned n4is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and further more preferably 0. When n4represents an integer of 2 or more, a plurality of Rb2may be the same or different. In addition, a plurality of Rb2may be bonded to each other to form a ring, but preferably, they are not bonded to each other to form a ring.

[0088] Among them, the structure represented by formula (3) is preferably a structure represented by formula (LC1-1), formula (LC1-4), formula (LC1-5), formula (LC1-6), formula (LC1-13), formula (LC1-14), or formula (LC1-17), and more preferably a structure represented by formula (LC1-1), formula (LC1-4), or formula (LC1-17).

[0089] The following formulae (3-3) to (3-23) are specific examples of the lactone structure-containing unsaturated monomer (a1-3) of the present application, but the present application is not limited thereto:

[0090]

[0091]

[0092] R 8e in formulae (3-23) to (3-23) is the same as the definition of R X2 in the aforementioned formula (3).

[0093] Preferably, the lactone structure-containing unsaturated monomer (a1-3) is a structure represented by the following formulae (3-24) to (3-34), and preferably a structure represented by formulae (3-24) to (3-29).

[0094]

[0095]

[0096] The amount of the unsaturated monomer (a1-3) having a lactone structure used is 1 to 15 parts by weight, preferably 1 to 14 parts by weight, and more preferably 2 to 13 parts by weight, based on 100 parts by weight of the total amount of the first mixture of the first resin (A1). If the unsaturated monomer (a1-3) having a lactone structure is not used in the first mixture of the first resin (A1) used in the chemically amplified positive photosensitive resin composition of the present application, there is a problem that the sensitivity is not good.

[0097] The first mixture of the first resin (A1) can further include other unsaturated monomers (a1-4). The other unsaturated monomers (a1-4) of the present application are unsaturated monomers other than the aforementioned unsaturated carboxylic acid monomers (a1-1), the monomers (a1-2) having an acid dissociable group, and the unsaturated monomers (a1-3) having a lactone structure. In some embodiments, the other unsaturated monomers (a1-4) include unsaturated monomers having an epoxy group, alkyl (meth)acrylate, alicyclic (meth)acrylate, aryl (meth)acrylate, unsaturated dicarboxylic acid diester, hydroxyalkyl (meth)acrylate, polyether (meth)acrylate, aromatic vinyl compound, and other unsaturated compounds other than the aforementioned.

[0098] The unsaturated monomers having an epoxy group can include, but are not limited to, epoxy group-containing (meth)acrylate compounds, epoxy group-containing α-alkyl acrylate compounds, glycidyl ether compounds, ethylenically unsaturated monomers having an oxetanyl group as represented by Formula (9), and any combination thereof:

[0099]

[0100] In Formula (9), R 8 is a hydrogen atom or an alkyl group having a carbon number of 1 to 4; R 9 is a hydrogen atom or an alkyl group having a carbon number of 1 to 4; R 10 , R 11 , R 12 , and R 13 are each independently a hydrogen atom, a fluorine atom, a phenyl group, an alkyl group having a carbon number of 1 to 4, or a perfluoroalkyl group having a carbon number of 1 to 4; and a is an integer of 1 to 6.

[0101] Specific examples of the aforementioned epoxy group-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, and 3,4-epoxycyclohexylmethyl (meth)acrylate.

[0102] Specific examples of the aforementioned epoxy group-containing α-alkyl acrylate compounds include α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, and α-ethyl glycidyl 6,7-epoxyheptanoate.

[0103] Specific examples of the aforementioned glycidyl ether compounds include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

[0104] Specific examples of the aforementioned ethylenically unsaturated monomers having an oxetanyl group represented by Formula (9) can include, but are not limited to, methacrylate compounds, acrylate compounds, or unsaturated monomers having structures represented by Formulas (9-1) to (9-4) below:

[0105]

[0106]

[0107] The aforementioned methacrylate compounds can include, but are not limited to, compounds of 3-(methacryloyloxymethyl)oxetane [OXMA], 3-(methacryloyloxymethyl)-3-ethyloxetane [EOXMA], 3-(methacryloyloxymethyl)-3-methyloxetane [MOXMA], 3-(methacryloyloxymethyl)-2-methyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(methacryloyloxymethyl)-2,2-difluoroxetane, 3-(methacryloyloxymethyl)-2,2,4-trifluoroxetane, 3-(methacryloyloxymethyl)-2,2,4,4-tetrafluoroxetane, 3-(methacryloyloxyethyl)oxetane, 3-(methacryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-(methacryloyloxyethyl)oxetane, 3-(methacryloyloxyethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxyethyl)-2-phenyloxetane, 2,2-difluoro-3-(methacryloyloxyethyl)oxetane, 3-(methacryloyloxyethyl)-2,2,4-trifluoroxetane, or 3-(methacryloyloxyethyl)-2,2,4,4-tetrafluoroxetane, and the like.

[0108] The above-mentioned acrylate compounds can include, but are not limited to, 3- (acryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3-(acryloyloxymethyl)- 3-methyloxetane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-2- trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-pentafluoroethyloxetane, 3- (acryloyloxymethyl)-2-phenyloxetane, 3-(acryloyloxymethyl)-2,2-difluoroxetane, 3- (acryloyloxymethyl)-2,2,4-trifluoroxetane, 3-(acryloyloxymethyl)-2,2,4,4- tetrafluoroxetane, 3-(acryloyloxyethyl)oxetane, 3-(acryloyloxyethyl)-3- ethyloxetane, 2-ethyl-3-(acryloyloxyethyl)oxetane, 3-(acryloyloxyethyl)-2- trifluoromethyloxetane, 3-(acryloyloxyethyl)-2-pentafluoroethyloxetane, 3- (acryloyloxyethyl)-2-phenyloxetane, 2,2-difluoro-3-(acryloyloxyethyl)oxetane, 3- (acryloyloxyethyl)-2,2,4-trifluoroxetane, or 3-(acryloyloxyethyl)-2,2,4,4- tetrafluoroxetane, and the like.

[0109] In some embodiments, the epoxy-containing unsaturated monomer can further include other ethylenically unsaturated monomers having an oxetanyl group, 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-3-(3- vinyloxypropyl)oxetane, 3-methyl-3-(3-vinyloxybutyl)oxetane, 3-ethyl-3-(3- vinyloxybutyl)oxetane, 3-propyl-3-(3-vinyloxybutyl)oxetane, ethylene glycol [(3-ethyl-3- oxetanyl)methyl] vinyl ether, propylene glycol [(3-ethyl-3-oxetanyl)methyl] vinyl ether, or 3,3-bis[(vinyloxy)methyl]oxetane, and the like vinyl ether compounds having an oxetanyl group.

[0110] Specific examples of the aforementioned alkyl methacrylates include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, dibutyl methacrylate, and tributyl methacrylate.

[0111] Specific examples of the aforementioned cyclohexyl (meth)acrylates include: cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and tricyclo[5.2.1.0] 2，6 Decyl-8-yl(meth)acrylate (or dicyclopentyl(meth)acrylate), dicyclopentoxyethyl(meth)acrylate, isobornyl(meth)acrylate, tetrahydrofuran(meth)acrylate.

[0112] Specific examples of the aforementioned aryl methacrylates include: phenyl methacrylate and benzyl methacrylate.

[0113] Specific examples of the aforementioned unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, and diethyl itaconic acid.

[0114] Specific examples of the aforementioned hydroxyalkyl methacrylates include: 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0115] Specific examples of the aforementioned (meth)acrylate polyethers include: polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate.

[0116] Specific examples of the aforementioned aromatic ethylene compounds include: styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene.

[0117] Other unsaturated compounds not mentioned above include, for example: acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, ethylene ethyl ester, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylidenemaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N-succinimide-6-maleimide hexanoate, N-succinimide-3-maleimide propionate, and N-(9-acridyl)maleimide.

[0118] The other unsaturated monomer (a1-4) described above can be used alone or in a mixture of a plurality of kinds. The amount of use of the other unsaturated monomer (a1-4) is 5 parts by weight to 95 parts by weight, preferably 10 parts by weight to 90 parts by weight, and more preferably 15 parts by weight to 80 parts by weight, based on 100 parts by weight of the total amount of use of the first mixture of the first resin (A1).

[0119] The second resin (A2) of the present application can be obtained by copolymerization of a second mixture which can contain an unsaturated carboxylic acid monomer (a2-1) and an unsaturated monomer containing a phenolic hydroxyl group (a2-2).

[0120] The definition, specific examples and preferable specific examples of the unsaturated carboxylic acid monomer (a2-1) of the present application can be the same as those of the aforementioned unsaturated carboxylic acid monomer (a1-1), and thus will not be described here. In addition, the unsaturated carboxylic acid monomer (a1-1) used in the first mixture of the first resin (A1) can be the same as or different from the unsaturated carboxylic acid monomer (a2-1) used in the second mixture of the second resin (A2).

[0121] The unsaturated carboxylic acid monomer (a2-1) described above can be used alone or in a mixture of a plurality of kinds. The amount of use of the unsaturated carboxylic acid monomer (a2-1) is 1 part by weight to 20 parts by weight, preferably 1 part by weight to 18 parts by weight, and more preferably 2 parts by weight to 15 parts by weight, based on 100 parts by weight of the total amount of use of the second mixture of the second resin (A2).

[0122] The unsaturated monomer containing a phenolic hydroxyl group (a2-2) of the present application is preferably a compound represented by formula (4):

[0123]

[0124] In formula (4), R 220 is a hydrogen atom or a methyl group; R 221 is a single bond or a divalent linking group; R 222 is a halogen atom or a linear or branched alkyl group having a carbon number of 1 to 5, and when b is greater than 1, a plurality of R 222 may be the same or different; b is an integer of 0 to 4, c is an integer of 1 to 5, and b + c is 5 or less.

[0125] The aforementioned R 220 is preferably a methyl group.

[0126] The divalent linking group of R 221 may be, for example, an alkylene group, and specific examples of the alkylene group can include a methylene group, an ethylene group, a propylene group, an isopropylene group, a n-propylene group, an isobutylene group, a t-butylene group, a pentylene group, an isopentylene group, a neopentylene group, a hexylene group, and the like. Among these, R 221The divalent linking group is preferably a single bond, methylene, or ethylene. The divalent linking group can also have a substituent, which can be exemplified by a halogen atom, a hydroxyl group, an alkoxy group, and the like.

[0127] With respect to the hydroxyl group on the benzene ring, when the carbon atom to which the hydroxyl group is bonded is taken as a reference (1-position), the hydroxyl group is preferably bonded to the 4-position. Furthermore, in view of the effects of the present application and the ease of production, a is preferably 1 or 2, more preferably 1. 221

[0128] R 222 Specific examples of R

[0129] Specific examples of the unsaturated monomer (a2-2) having a phenolic hydroxyl group can be the following formulas (4-1) to (4-8), of which formulas (4-1) to (4-5) are preferred, although the present application is not limited thereto.

[0130]

[0131] The total amount of the second mixture of the second resin (A2) is 100 parts by weight, and the amount of the unsaturated monomer (a2-2) having a phenolic hydroxyl group used is 5 to 50 parts by weight, preferably 7 to 45 parts by weight, more preferably 10 to 40 parts by weight. If the unsaturated monomer (a2-2) having a phenolic hydroxyl group is not used in the second mixture of the second resin (A2) used in the chemically amplified positive photosensitive resin composition of the present application, there is a problem that the stability over time is poor.

[0132] The second mixture used to copolymerize the second resin (A2) of the present application can further include a monomer (a2-3) having an acid dissociable group. The monomer (a2-3) having an acid dissociable group of the present application has an acid dissociable group represented by the following formula (2):

[0133]

[0134] In formula (2), R 21 and R 22 are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, or an aryl group, wherein the alkyl group, the alicyclic hydrocarbon group, or the aryl group can have some or all of the hydrogen atoms thereof substituted, and R 21 and R 22 are not simultaneously a hydrogen atom; R 23 is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group, or an aryl group, wherein the alkyl group, the alicyclic hydrocarbon group, the aralkyl group, and the aryl group can have some or all of the hydrogen atoms thereof substituted; R 21 and R​23 may be mutually bonded to form a ring structure. 21 the bonded carbon atoms and R 23 the bonded oxygen atoms together form a cyclic ether structure.

[0135] The acid-dissociable group of the acid-dissociable group-containing monomer (a2-3) dissociates by the action of an acid generated from a photo-acid generator (B) described later at the time of exposure, and a polar group is generated, and thus a resin (A) that is originally insoluble or hardly soluble in an aqueous alkali solution becomes soluble in an aqueous alkali solution.

[0136] The acid-dissociable group-containing monomer (a2-3) is not particularly limited as long as it contains a structure of formula (2). This acid-dissociable group-containing monomer (a2-3) is easily dissociated by an acid.

[0137] In the acid-dissociable group-containing monomer (a2-3) of the present application, R 21 , R 22 , and R 23 are defined, specific examples, and preferable specific examples can be the same as those of R 11 , R 12 , and R 13 in the aforementioned acid-dissociable group-containing monomer (a1-2), and thus will not be described here. In addition, the acid-dissociable group-containing monomer (a1-2) used in the first mixture of the first resin (A1) can be the same as or different from the acid-dissociable group-containing monomer (a2-3) used in the second mixture of the second resin (A2).

[0138] The acid-dissociable group-containing monomer (a2-3) is used in an amount of 0 parts by weight to 70 parts by weight, preferably 0 parts by weight to 65 parts by weight, and more preferably 5 parts by weight to 60 parts by weight, based on 100 parts by weight of the total amount of the second mixture of the second resin (A2).

[0139] If the acid-dissociable group-containing monomer (a2-3) is included in the second mixture of the second resin (A2) used in the chemically amplified positive photosensitive resin composition of the present application, the sensitivity can be further improved.

[0140] The second mixture used to copolymerize the second resin (A2) of the present application can further include another unsaturated monomer (a2-4). The other unsaturated monomer (a2-4) of the present application is an unsaturated monomer other than the aforementioned unsaturated carboxylic acid monomer (a2-1), the phenolic hydroxyl group-containing unsaturated monomer (a2-2), and the acid-dissociable group-containing monomer (a2-3).

[0141] The definition, specific examples, and preferable examples of the other unsaturated monomer (a2-4) of the present application can be the same as those of the aforementioned other unsaturated monomer (a1-4), and thus will not be described here. In addition, the other unsaturated monomer (a1-4) used in the first mixture of the first resin (A1) can be the same as or different from the other unsaturated monomer (a2-4) used in the second mixture of the second resin (A2).

[0142] The aforementioned other unsaturated monomer (a2-4) can be used alone or in a mixture of a plurality of kinds. The amount of the other unsaturated monomer (a2-4) used is 5 parts by weight to 95 parts by weight, preferably 10 parts by weight to 85 parts by weight, and more preferably 15 parts by weight to 80 parts by weight, based on 100 parts by weight of the total amount of the second mixture of the second resin (A2).

[0143] The polymerization of the first resin (A1) can be performed, for example, by using a radical polymerization initiator, so as to polymerize the monomers in the first mixture in an appropriate solvent, to produce the first resin (A1). For example, it is preferable to synthesize by a method in which a solution containing monomers and a radical polymerization initiator is added dropwise to a solution containing a reaction solvent or monomers to perform a polymerization reaction; a solution containing monomers, and a solution containing a radical polymerization initiator, are separately added dropwise to a solution containing a reaction solvent or monomers to perform a polymerization reaction; a plurality of solutions containing respective monomers, and a solution containing a radical polymerization initiator, are separately added dropwise to a solution containing a reaction solvent or monomers to perform a polymerization reaction; or the like.

[0144] The solvent used in the polymerization reaction of the first resin (A1) can be exemplified by the same solvent as that described later for the solvent (C), or the like.

[0145] A common radical polymerization initiator can be used as the polymerization initiator for the polymerization reaction, and can be exemplified by azo compounds such as 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionamide) methyl ester, and the like; organic peroxides such as benzoyl peroxide, lauroyl peroxide, tertiary butyl peroxymethyl acetate, 1,1'-bis-(tertiary butylperoxy)cyclohexane, and the like; hydrogen peroxide, and the like.

[0146] In the polymerization reaction of the first resin (A1), a molecular weight adjusting agent can be appropriately used in order to adjust the molecular weight, and can be exemplified by chloroform, carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolic acid, 3-mercaptopropionic acid, and the like.

[0147] The polystyrene-conversion weight average molecular weight (Mw) of the first resin (Al) obtained by gel penetration chromatography (GPC) is 4,000 to 38,000, preferably 5,000 to 28,000, and more preferably 6,000 to 18,000.

[0148] Similarly, the polymerization of the second resin (A2) can be the same as the polymerization of the aforementioned first resin (Al), except that the second mixture is used for the polymerization, and thus will not be described here. The polystyrene-conversion weight average molecular weight (Mw) of the second resin (A2) obtained by gel penetration chromatography (GPC) is 2,000 to 32,000, preferably 3,000 to 22,000, and more preferably 4,000 to 12,000.

[0149] Based on the total amount of the first resin (Al) and the second resin (A2) being 100 parts by weight, the amount of the first resin (Al) used is 40 parts by weight to 90 parts by weight, preferably 45 parts by weight to 85 parts by weight, and more preferably 50 parts by weight to 80 parts by weight; and the amount of the second resin (A2) used is 10 parts by weight to 60 parts by weight, preferably 15 parts by weight to 55 parts by weight, and more preferably 20 parts by weight to 50 parts by weight.

[0150] If the first resin (Al) is not used in the chemically amplified positive photosensitive resin composition of the present application, there is a problem of poor sensitivity. If the second resin (A2) is not used in the chemically amplified positive photosensitive resin composition of the present application, there is a problem of poor stability over time.

[0151] The photoacid generator (B) of the present application is a compound that generates an acid by irradiation of a radiation ray, and can be, for example, at least one of an oxime sulfonate group-containing compound of the following formula (8), and an N-sulfonyloxy imide compound. The radiation ray can be, for example, visible light, ultraviolet light, far ultraviolet light, an electron beam, X-rays, or the like. Since the chemically amplified positive photosensitive resin composition of the present application contains the photoacid generator (B), the chemically amplified positive photosensitive resin composition can exhibit a radiation ray-sensing (or light-sensing) property, and can have good radiation ray sensitivity. As the photoacid generator (B) in the chemically amplified positive photosensitive resin composition, it can be in the form of a compound as described later, it can be incorporated into the first resin (Al) or the second resin (A2) as part of the polymer constituting the first resin (Al) or the second resin (A2), or it can be a combination of both. Such photoacid generators (B) can be used alone or in combination of two or more.

[0152] The photoacid generator (B) can contain, in addition to the oxime sulfonate compound containing an oxime sulfonate group, an onium salt, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonate compound, a carboxylate compound, and the like.

[0153] The oxime sulfonate compound is a compound containing an oxime sulfonate group of the following formula (8):

[0154]

[0155] In formula (8), R 16 is an alkyl group, an alicyclic hydrocarbon group, or an aryl group having a carbon number of 1 to 20, in which the hydrogen atoms of the alkyl group, the alicyclic hydrocarbon group, or the aryl group can be partially or entirely substituted; and * is a bond.

[0156] R 16 preferably represents an alkyl group having a carbon number of 1 to 12.

[0157] R 16 preferably represents a monovalent alicyclic hydrocarbon group having a carbon number of 4 to 12.

[0158] R 16 preferably represents an aryl group having a carbon number of 6 to 20, more preferably a phenyl group, a naphthyl group, a tolyl group, a xylyl group.

[0159] The substituent group can be exemplified by an alkyl group, an alkoxy group, an oxo group, a halogen atom, and the like, each having a carbon number of 1 to 5.

[0160] The compound containing the oxime sulfonate group represented by formula (8) can be exemplified by oxime sulfonate compounds represented by the following formulas (8-1) to (8-3):

[0161]

[0162] In formulas (8-1) to (8-3), R 26 have the same meanings as R 16 of structural formula (3). In formulas (8-1) and (8-2), R 27 is an alkyl group having a carbon number of 1 to 12 or a fluoroalkyl group having a carbon number of 1 to 12. In formula (8-3), X is an alkyl group, an alkoxy group, or a halogen atom. i is an integer of 0 to 3, and in the case where i is 2 or 3, the plurality of X can be the same as or different from each other.

[0163] The alkyl group represented by X preferably is a straight-chain or branched alkyl group having a carbon number of 1 to 4. The alkoxy group represented by X preferably is a straight-chain or branched alkoxy group having a carbon number of 1 to 4. The halogen atom represented by X preferably is a chlorine atom or a fluorine atom.

[0164] The oxime sulfonate compound represented by the formula (8-3) can include, for example, a compound represented by the following formula (8-4) to formula (8-8) and the like:

[0165]

[0166] The compounds represented by the formula (8-4) to formula (8-8) are (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, 4-methylphenylsulfonyloxyimino-α-(4-methoxyphenyl)acetonitrile, and the like. The above compounds can be commercially available.

[0167] The above-mentioned N-sulfonyloxy imide compounds can be exemplified by N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenyl maleimide, N- (camphorsulfonyloxy) diphenyl maleimide, (4-methylphenylsulfonyloxy) diphenyl maleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenyl maleimide, N- (4-fluorophenylsulfonyloxy) diphenyl maleimide, N- (phenylsulfonyloxy) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N- (nonafluorobutylsulfonyloxy) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N- (camphorsulfonyloxy) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N- (camphorsulfonyloxy) -7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (camphorsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (phenylsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (camphorsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (nonafluorobutylsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (camphorsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (nonafluorobutylsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (camphorsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (nonafluorobutylsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (camphorsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (nonafluorobutylsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (camphorsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (nonafluorobutylsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (camphorsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (nonafluorobutylsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (camphorsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (nonafluorobutylsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (camphorsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N- (nonafluorobutylsulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide,1] heptane-5, 6-oxyl-2, 3-dicarboxylic imide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5, 6-oxyl-2, 3-dicarboxylic imide, N- (trifluoromethylsulfonyloxy) naphthalene dicarboxylic imide, N- (camphorsulfonyloxy) naphthalene dicarboxylic imide, N- (4-methylphenylsulfonyloxy) naphthalene dicarboxylic imide, N- (phenylsulfonyloxy) naphthalene dicarboxylic imide, N- (2-trifluoromethylphenylsulfonyloxy) naphthalene dicarboxylic imide, N- (4-fluorophenylsulfonyloxy) naphthalene dicarboxylic imide, N- (pentafluoroethylsulfonyloxy) naphthalene dicarboxylic imide, N- (heptafluoropropylsulfonyloxy) naphthalene dicarboxylic imide, N- (nonafluorobutylsulfonyloxy) naphthalene dicarboxylic imide, N- (ethylsulfonyloxy) naphthalene dicarboxylic imide, N- (propylsulfonyloxy) naphthalene dicarboxylic imide, N- (butylsulfonyloxy) naphthalene dicarboxylic imide, N- (pentylsulfonyloxy) naphthalene dicarboxylic imide, N- (hexylsulfonyloxy) naphthalene dicarboxylic imide, N- (heptylsulfonyloxy) naphthalene dicarboxylic imide, N- (octylsulfonyloxy) naphthalene dicarboxylic imide, N- (nonylsulfonyloxy) naphthalene dicarboxylic imide, and the like.

[0168] The onium salt, the halogen-containing compound, the diazomethane compound, the sulfone compound, the sulfonate compound, the carboxylate compound, and the like can use the compounds described in Japanese Patent Kokai No. 2011-232632. For example, benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate.

[0169] The photoacid generator (B) is preferably the compound represented by the formula (8-4) to the formula (8-8) among the compounds containing the oxime sulfonate of the formula (8). In addition, preferably, the photoacid generator (B) also contains an N-sulfonyloxy imide compound.

[0170] The amount of use of the photoacid generator (B) is 0.3 parts by weight to 5 parts by weight, preferably 0.4 parts by weight to 4.5 parts by weight, and more preferably 0.5 parts by weight to 4 parts by weight, based on 100 parts by weight of the total amount of use of the first resin (Al) and the second resin (A2).

[0171] The kind of the solvent (C) of the present application is not particularly limited. Specific examples of the solvent (C) are a compound containing an alcoholic hydroxy or a cyclic compound containing a carbonyl group, and the like.

[0172] Specific examples of the compound containing an alcoholic hydroxyl group are 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, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, or a combination thereof. Notably, the compound containing an alcoholic hydroxyl group is preferably acetol, ethyl lactate, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, or a combination thereof. The compound containing an alcoholic hydroxyl group can be used alone or in combination with multiple compounds.

[0173] Specific examples of the cyclic compound containing a carbonyl group are γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methyl pyrrolidone, cyclohexanone, or cycloheptanone, and the like. Notably, the cyclic compound containing a carbonyl group is preferably γ-butyrolactone, N-methyl pyrrolidone, cyclohexanone, or a combination thereof. The cyclic compound containing a carbonyl group can be used alone or in combination with a plurality of compounds.

[0174] The compound containing an alcoholic hydroxyl group can be used in combination with the cyclic compound containing a carbonyl group, and the weight ratio thereof is not particularly limited. The weight ratio of the compound containing an alcoholic hydroxyl group to the cyclic compound containing a carbonyl group is preferably 99 / 1 to 50 / 50; more preferably 95 / 5 to 60 / 40.

[0175] Other solvents can also be contained within a range that does not impair the effects of the present application. Specific examples of the other solvents are: (1) esters: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol methyl ether acetate, 3-methoxy-l-butyl acetate, or 3-methyl-3-methoxy-l-butyl acetate, and the like; (2) ketones: methyl isobutyl ketone, diisopropyl ketone, or diisobutyl ketone, and the like; or (3) ethers: diethyl ether, diisopropyl ether, di-n-butyl ether, or diphenyl ether, and the like.

[0176] The solvent (C) is used in an amount of 150 parts by weight to 1200 parts by weight, preferably 170 parts by weight to 1100 parts by weight, more preferably 200 parts by weight to 1000 parts by weight, based on 100 parts by weight of the total amount of use of the first resin (Al) and the second resin (A2).

[0177] The chemically amplified positive photosensitive resin composition of the present application can further preferably contain a compound (D) represented by Formula (6) or Formula (7):

[0178]

[0179] In Formula (6), R 1 and R 2 each independently is an alkyl group having a carbon number of 1 to 4; n6 is an integer of 0 to 2; L 1 is a single bond or a divalent linking group; X 1 is -S- or -NH-; R 3 is a monovalent organic group.

[0180] R 1 and R 2Preferably, it is an alkyl group having 1 to 3 carbon atoms, more preferably methyl or ethyl. 1 and R 2 It is preferable to represent the same group.

[0181] n6 is preferably an integer of 0 or 1, and more preferably 0.

[0182] L 1 Preferably, it is a divalent linker, such as alkyl or aryl groups, with alkyl being more preferred.

[0183] L 1 The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 2 to 8 carbon atoms, and even more preferably an alkyl group having 3 to 5 carbon atoms. The alkyl group may have substituents, but is preferably unsubstituted. Specific examples of alkyl groups include: methylene, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, etc.

[0184] L 1 The aryl group is preferably an aryl group with 6 to 20 carbon atoms, and more preferably an aryl group with 6 to 10 carbon atoms. Specifically, examples include: arylphenyl, arylnaphthyl, etc.

[0185] It can also make L 1 The alkyl and aryl groups contain ether oxygen atoms and thus become alkoxy and aryloxy groups.

[0186] X 1 -NH- is preferred.

[0187] R 3 Examples of monovalent organic groups include alkyl, aryl, alkoxy, aryloxy, acyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, etc., with alkyl and aryl being preferred.

[0188] R 3 The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Specifically, examples include: methyl, ethyl, propyl, isopropyl, butyl, tributyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, etc.

[0189] R 3 The aryl group is preferably an aryl group with 6 to 20 carbon atoms, and more preferably an aryl group with 6 to 10 carbon atoms. Specifically, examples include phenyl, naphthyl, anthracene, etc.

[0190] R 3 The alkoxy group is preferably an alkoxy group with 1 to 10 carbon atoms, and more preferably an alkoxy group with 1 to 6 carbon atoms. Specifically, examples include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, tributoxy, pentoxy, etc.

[0191] R 3R7is an alkoxy group having 1 to 30 carbon atoms, preferably an alkoxy group having 1 to 10 carbon atoms. Specifically, mention can be made of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, 2-ethylhexyloxy, and the like.

[0192] R 3 R7is an acyloxy group having 1 to 30 carbon atoms, preferably a formyloxy group, an alkylcarbonyloxy group having 2 to 30 carbon atoms, or an arylcarbonyloxy group having 6 to 30 carbon atoms. Specifically, mention can be made of acetyloxy, trimethylacetyloxy, pivaloyloxy, phenylcarbonyloxy, p-methoxyphenylcarbonyloxy, and the like.

[0193] R 3 R7is an alkoxycarbonyloxy group having 1 to 30 carbon atoms, preferably an alkoxycarbonyloxy group having 2 to 30 carbon atoms. Specifically, mention can be made of methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy, and the like.

[0194] R 3 R7is an aryloxycarbonyloxy group having 1 to 30 carbon atoms, preferably an aryloxycarbonyloxy group having 7 to 30 carbon atoms. Specifically, mention can be made of phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, p-n-hexadecyloxyphenoxycarbonyloxy, and the like.

[0195] R 3 The monovalent organic group can have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a linear, branched, or cyclic alkyl group (e.g., methyl group, ethyl group, propyl group, and the like), an alkenyl group, an alkynyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a cyano group, a carboxyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a heterocyclic oxy group, an acyloxy group, an amino group, a nitro group, a hydrazine group, a heterocyclic group, and the like. In addition, the group can be further substituted.

[0196] R 3 Preferably, R7is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, which further improves the development adhesion of the chemically amplified positive photosensitive resin composition of the present application.

[0197] The compound (D) represented by formula (7) is as follows:

[0198]

[0199] In formula (7), R 5 and R 6 are each independently an alkyl group having 1 to 4 carbon atoms; n7is an integer of 0 to 2; L 2 is a single bond or a divalent linking group; X 2 is -S- or -NH-; and A is a heterocyclic ring including carbon atoms and nitrogen atoms.

[0200] R 5 and R 6 are the same as R1 and R 2 have the same meaning, and the preferable range is also the same.

[0201] n7has the same meaning as n6in General Formula (6), and the preferable range is also the same.

[0202] L 2 has the same meaning as L 1 in General Formula (6), and the preferable range is also the same.

[0203] X 2 has the same meaning as X 1 in General Formula (6), and the preferable range is also the same.

[0204] The heterocycle containing a carbon atom and a nitrogen atom represented by A can be aromatic or non-aromatic, and is usually an aromatic heterocycle. The heterocycle containing a carbon atom and a nitrogen atom can further contain a heteroatom such as an oxygen atom, a nitrogen atom, a sulfur atom, in addition to the nitrogen atom. Furthermore, the heterocycle can be either a monocyclic ring or a condensed ring, but is preferably a monocyclic ring. The heterocycle is preferably a 3- to 7-membered ring, and more preferably a 5- or 6-membered ring.

[0205] The heterocycle containing a carbon atom and a nitrogen atom represented by A can be specifically exemplified by a pyridyl group, a thiazolyl group, a 2-furyl group, a thienyl group, a pyrimidinyl group, a benzothiazolyl group, a morpholinyl group, a pyrrolyl group, an indolyl group, a carbazolyl group, a furan group, a thiophene group, and the like.

[0206] The heterocycle containing a carbon atom and a nitrogen atom represented by A can have a substituent. The substituent can have the same meaning as R 3 in General Formula (6).

[0207] The following Formulae (S-1) to (S-24) represent the compounds (D) used in the present application, but the present application is of course not limited to these compounds:

[0208] (S-1)

[0209]

[0210] (S-2)

[0211]

[0212] (S-3)

[0213]

[0214] (S-4)

[0215]

[0216] (S-5)

[0217]

[0218] (S-6)

[0219]

[0220] (S-7)

[0221]

[0222] (S-8)

[0223]

[0224] (S-9)

[0225]

[0226] (S-110)

[0227]

[0228] (S-11)

[0229]

[0230] (S-12)

[0231]

[0232] (S-13)

[0233]

[0234] (S-14)

[0235]

[0236] (S-15)

[0237]

[0238] (S-16)

[0239]

[0240] (S-17)

[0241]

[0242] (S-18)

[0243]

[0244] (S-119)

[0245]

[0246] (S-20)

[0247]

[0248] (S-21)

[0249]

[0250] (S-22)

[0251]

[0252] (S-23)

[0253]

[0254] (S-24)

[0255]

[0256] In formulae (S-1) to (S-24), Me represents a methyl group, and Et represents an ethyl group.

[0257] In formulae (S-1) to (S-24), preferably, formulae (S-1) to (S-24), more preferably, formula (S-1) to (S-8), and particularly preferably, formula (S-1) to (S-2).

[0258] In the compound (D) represented by formula (6) and formula (7), preferably, the compound (D) represented by formula (7).

[0259] The molecular weight of the compound (D) represented by formula (6) and formula (7) is preferably 1,000 or less, more preferably 500 or less, and particularly preferably 400 or less. There is no particular limitation on the lower limit, and it can be, for example, 100 or more. By setting the molecular weight of the compound (D) represented by formula (6) and formula (7) to the range described above, the present application can achieve a preferable effect.

[0260] The compound (D) is used in an amount of 0.05 parts by weight to 0.8 parts by weight, preferably 0.06 parts by weight to 0.75 parts by weight, and more preferably 0.07 parts by weight to 0.7 parts by weight, based on 100 parts by weight of the total amount of use of the first resin (A1) and the second resin (A2). The compound (D) can be used alone or in combination of two or more. In the case where the components of the compound (D) are two or more, preferably, the total amount thereof is in the range described above. If the chemically amplified positive photosensitive resin composition of the present application does not use the compound (D), there is a problem that the sensitivity is poor.

[0261] The hindered amine compound (E) of the present application can be represented by the following formula (el):

[0262]

[0263] In formula (el), n is an integer of 4 or more, for example, an integer of 4 to 12, or an integer of 4 to 8. Preferably, n is an integer of 5 or more.

[0264] In formula (el), E1is an n-valent organic group. The organic group can include, for example, an aliphatic hydroxyl group, an aromatic hydroxyl group, a heterocyclic group, or a group formed by one or two or more combinations of a nitrogen atom, an oxygen atom, -C(=O)-, and -NH-. The molecular weight of E1may be 50 to 5,000, preferably 200 to 4,000.

[0265] In formula (el), E2to E5are each independently a monovalent organic group having a carbon number of 1 to 12. The monovalent organic group having a carbon number of 1 to 12 can include, for example, an alkyl group having a carbon number of 1 to 12 or an alkoxy group having a carbon number of 1 to 12. Such an organic group can further have a substituent, but is preferably unsubstituted. Preferably, E2to E5are an alkyl group having a carbon number of 1 to 6, more preferably an alkyl group having a carbon number of 1 to 3, and even more preferably a methyl group.

[0266] In formula (el), E6is a hydrogen atom or a monovalent alkyl group having a carbon number of 1 to 12, and is preferably a monovalent alkyl group having a carbon number of 1 to 12. Preferably, E6is an alkyl group having a carbon number of 1 to 6, more preferably an alkyl group having a carbon number of 1 to 3, and even more preferably a methyl group.

[0267] Examples of the hindered amine compound (E) can include compounds represented by formula (el l) to formula (el4):

[0268]

[0269]

[0270] In formula (el3), BTC is a structure represented by the following formula (el5):

[0271]

[0272] Further, examples of the hindered amine compound (E) can include, for example, a linear or cyclic condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine (CHIMASSORB 944); a linear or cyclic condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine (CYASORB UV-3346); a condensation reaction product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; a methylation reaction product of a polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine and morpholine-2,4,6-trichloro-1,3,5-triazine (CYASORB UV 3529); a polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine, reacted with N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine reaction product (CHIMASSORB 2020); a polymer of N,N'1,2-ethanediylbis-1,3-propanediamine and 2,4,6-trichloro-1,3,5-triazine, reacted with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine reaction product (UVASORB HA 88); a reaction product of 1,2,3,4-butanetetracarboxylic acid and a copolymer of β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol and 2,2,6,6-pentamethyl-4-piperidyl ester (ADK STAB LA 68). The amount of use of the hindered amine compound (E) is 0.02 parts by weight to 0.2 parts by weight, preferably 0.02 parts by weight to 0.19 parts by weight, and more preferably 0.03 parts by weight to 0.18 parts by weight, based on 100 parts by weight of the total amount of use of the first resin (A1) and the second resin (A2).

[0273] If the chemical amplification positive photosensitive resin composition of the present application does not use the hindered amine compound (E), there is a problem that the stability over time is poor.

[0274] If the amount of use of the hindered amine compound (E) used in the chemical amplification positive photosensitive resin composition of the present application falls within the above range, the stability over time is better.

[0275] In the hindered amine compound (E) used in the chemical amplification positive photosensitive resin composition of the present application, if n of formula (e1) is an integer of 5 or more and E6 is a monovalent alkyl group having 1 to 12 carbon atoms, the time stability of the chemical amplification positive photosensitive resin composition of the present application can be further improved.

[0276] When the weight ratio (D) / (E) of the compound (D) and the hindered amine compound (E) used is 0.5 to 10, the sensitivity and the time stability can be further simultaneously improved.

[0277] The chemical amplification positive photosensitive resin composition of the present application can further include an additive (F). Specifically, specific examples of the additive (F) are a sensitizer, an adhesion auxiliary agent, a surfactant, a solubility promoter, a defoamer, or a combination thereof.

[0278] The kind of the sensitizer is not particularly limited. The sensitizer is preferably a compound containing phenolic hydroxy group, and specific examples thereof include: (1) a trisphenol type compound such as tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, or bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane, etc.; (2) a bisphenol type compound such as bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(3-fluoro-4-hydroxyphenyl)-2-(3'-fluoro-4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, or 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxy-3',5'-dimethylphenyl)propane, etc.;(3) Polynuclear branched compound: such as 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1, 1-bis (4-hydroxyphenyl) ethyl] benzene or 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1, 1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene, etc.; (4) Condensation type phenol compound: such as 1, 1-bis (4-hydroxyphenyl) cyclohexane, etc.; (5) Polyhydroxybenzophenone: such as 2, 3, 4-trihydroxybenzophenone, 2, 4, 4'-trihydroxybenzophenone, 2, 4, 6-trihydroxybenzophenone, 2, 3, 4-trihydroxy-2'-methylbenzophenone, 2, 3, 4, 4'-tetrahydroxybenzophenone, 2, 4, 2', 4'-tetrahydroxybenzophenone, 2, 4, 6, 3', 4'-pentahydroxybenzophenone, 2, 3, 4, 2', 4'-pentahydroxybenzophenone, 2, 3, 4, 2', 5'-pentahydroxybenzophenone, 2, 4, 6, 3', 4', 5'-hexahydroxybenzophenone, or 2, 3, 4, 3', 4', 5'-hexahydroxybenzophenone, etc.; or (6) combination of the above various types of compounds containing phenolic hydroxyl groups.

[0279] The amount of the sensitizer used is 5 parts by weight to 50 parts by weight, preferably 8 parts by weight to 40 parts by weight, and more preferably 10 parts by weight to 35 parts by weight, based on 100 parts by weight of the total amount of the first resin (A1) and the second resin (A2).

[0280] Specific examples of the adhesion aid include melamine compounds and silane compounds.

[0281] Specific examples of commercially available products of melamine include those manufactured by Mitsui Chemicals, Inc. under the trade names of Cymel-300 or Cymel-303, etc.; or those manufactured by Sanwa Chemical Co., Ltd. under the trade names of MW-30MH, MW-30, MS-11, MS-001, MX-750, or MX-706, etc.

[0282] When a melamine compound is used as the adhesion aid, the amount of the melamine compound used is 0 parts by weight to 20 parts by weight, preferably 0.5 parts by weight to 18 parts by weight, and more preferably 1.0 parts by weight to 15 parts by weight, based on 100 parts by weight of the total amount of the first resin (A1) and the second resin (A2).

[0283] Specific examples of the silane-based compound are vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, or a commercially available product manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: KBM403), and the like.

[0284] When the silane-based compound is used as the adhesion aid, the amount of the silane-based compound used is 0 to 2 parts by weight, preferably 0.05 to 1 parts by weight, and more preferably 0.1 to 0.8 parts by weight, based on 100 parts by weight of the total amount of the first resin (A1) and the second resin (A2).

[0285] Specific examples of the surfactant are anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane-based surfactants, fluorine-based surfactants, or combinations thereof.

[0286] Examples of the surfactant include (1) polyoxyethylene alkyl ethers: polyoxyethylene dodecyl ether, etc.; (2) polyoxyethylene phenyl ethers: polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc.; (3) polyethylene glycol diesters: polyethylene glycol dilaurate, polyethylene glycol dihardened acid ester, etc.; (4) sorbitan fatty acid esters; and (5) fatty acid modified polyesters; and (6) tertiary amine modified polyurethanes, etc. Specific examples of commercially available products of the surfactant are KP (manufactured by Shin-Etsu Chemical), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow (manufactured by Sanyu Chemical Industries), F-Top (manufactured by Tochem Products Co., Ltd.), Megaface (manufactured by DIC), Fluorade (manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Asahi Glass), SINOPOL E8008 (manufactured by Nippon Soda), F-475 (manufactured by DIC), or a combination thereof.

[0287] The surfactant is used in an amount of 0.5 parts by weight to 50 parts by weight, preferably 1 part by weight to 40 parts by weight, and more preferably 3 to 30 parts by weight, based on 100 parts by weight of the total amount of use of the first resin (A1) and the second resin (A2).

[0288] Examples of the defoaming agent 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), etc.

[0289] The antifoaming agent is used in an amount of 1 to 10 parts by weight, preferably 2 to 9 parts by weight, and more preferably 3 to 8 parts by weight, based on 100 parts by weight of the total amount of the first resin (Al) and the second resin (A2).

[0290] Examples of the dissolution promoter include N-hydroxydicarboxylic imide compounds and compounds containing phenolic hydroxyl groups.

[0291] The dissolution promoter is used in an amount of 1 to 20 parts by weight, preferably 2 to 15 parts by weight, and more preferably 3 to 10 parts by weight, based on 100 parts by weight of the total amount of the first resin (Al) and the second resin (A2).

[0292] The chemically amplified positive photosensitive resin composition of the present application is prepared in the following manner: the first resin (Al), the second resin (A2), the photoacid generator (B), the solvent (C), the compound (D), and the hindered amine compound (E) are placed in a stirrer and stirred to uniformly mix them into a solution state, and if necessary, the additive (E) can be added.

[0293] The present application also provides a protective film formed by applying the aforementioned chemically amplified positive photosensitive resin composition to a substrate, and then performing a pre-baking, exposure, development, and post-baking process.

[0294] The present application also provides an assembly having a protective film, comprising a substrate and the aforementioned protective film attached to the substrate.

[0295] In some embodiments, the chemically amplified positive photosensitive resin composition of the present application can be used as a material for forming a protective film for a display assembly. In addition, the present application also includes a protective film for a display assembly formed from a chemically amplified positive photosensitive resin composition.

[0296] The method for forming the protective film includes the following steps: a step of forming a coating film on a substrate using a chemically amplified positive photosensitive resin composition (hereinafter also referred to as "step (1)"); a step of irradiating at least a portion of the coating film with radiation (hereinafter also referred to as "step (2)"); a step of developing the coating film after irradiation with radiation (hereinafter also referred to as "step (3)"); and a step of heating the coating film after development (hereinafter also referred to as "step (4)").

[0297] According to this formation method, a protective film for a display component having excellent surface hardness, solvent resistance, heat resistance, and voltage holding ratio can be formed. In addition, by using a chemically amplified positive photosensitive resin composition having good sensitivity, a protective film for a display component having a fine and delicate pattern can be easily formed. Therefore, the formed protective film for a display component is suitable for a display component such as a liquid crystal display component, an organic EL display component, and the like.

[0298] Step (1): In this step, a chemically amplified positive photosensitive resin composition is applied to a substrate to form a coating film. Preferably, the coating surface is pre-baked to remove the solvent. The substrate can be exemplified by, for example, glass, quartz, a silicon substrate, a resin, and the like. The resin can be exemplified by, for example, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof, and the like. The conditions of pre-baking also vary depending on the kind of each component, the blending ratio, and the like, and can be set to 70°C to 120°C for about 1 minute to 10 minutes.

[0299] Step (2): In this step, at least a part of the above-mentioned coating film formed is exposed to radiation. At the time of exposure, exposure is usually performed through a mask having a predetermined pattern. The radiation used for exposure is preferably radiation having a wavelength in the range of 190 nm to 450 nm, and more preferably radiation including ultraviolet rays of 365 nm. The exposure dose is a value obtained by measuring the intensity of radiation at a wavelength of 365 nm using an illuminometer (OAI model 356, manufactured by OAIOptical Associates). The exposure dose is preferably 500 J / m 2 to 6,000 J / m 2 , more preferably 1,500 J / m 2 to 1,800 J / m 2 .

[0300] Step (3): In this step, the above-mentioned coating film after radiation is developed. By developing the coating film after exposure, the unnecessary part (the radiation-irradiated part) is removed to form a predetermined pattern. The developing solution used in the developing step is preferably an aqueous alkali solution. The alkali can be exemplified by, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, an amine, and the like, inorganic bases; tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like, quaternary ammonium salts; and the like.

[0301] In the aqueous alkali solution, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added. The concentration of the alkali in the aqueous alkali solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining appropriate developability. The developing method can be exemplified by a puddle method, an immersion method, a swing immersion method, a spray method, and the like. The developing time varies depending on the composition of the chemically amplified positive photosensitive resin composition and is about 10 seconds to 180 seconds. After the developing treatment, the coated film is air-dried by using, for example, compressed air or compressed nitrogen after water washing for 30 seconds to 90 seconds, for example, to form a desired pattern.

[0302] Step (4): In this step, the above developed coated film is heated. At the time of heating, the patterned film is heated by using a heating device such as a hot plate or an oven to promote the hardening reaction of the resin (A) and to obtain a hardened product. The heating temperature is, for example, about 120°C to 250°C. The heating time varies depending on the type of the heating machine and is, for example, about 5 minutes to 30 minutes on a hot plate and about 30 minutes to 90 minutes in an oven. Alternatively, a stage baking method in which the heating step is performed two or more times, or the like can be used. In this way, a patterned film corresponding to a protective film for a display component targeted is formed on the surface of the substrate. Furthermore, the use of the above hardened film is not limited to a protective film for a display component and can be utilized as a spacer or an interlayer insulating film.

[0303] The film thickness of the formed protective film for a display component is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and still more preferably 0.1 μm to 4 μm.

[0304] The present application is described in detail below using the following examples, which are not intended to limit the present application to the contents disclosed in the examples.

[0305] Preparation of the first resin (Al)

[0306] Preparation Example Al-1

[0307] Into a 1000ml four-necked flask equipped with a nitrogen inlet, a stirrer, a heater, a condenser and a thermometer, 3 parts by weight of methacrylic acid (hereinafter referred to as MAA), 20 parts by weight of 1-ethoxyethyl methacrylate (hereinafter referred to as MAEVE), 1 part by weight of the compound of formula (3-24) (hereinafter referred to as a131), 40 parts by weight of dicyclopentyl methacrylate (hereinafter referred to as FA-513M), 20 parts by weight of glycidyl methacrylate (hereinafter referred to as GMA), 6 parts by weight of 3-(methacryloyloxymethoxy)oxetane (hereinafter referred to as GXMA), 10 parts by weight of styrene (hereinafter referred to as SM), 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) (hereinafter referred to as ADVN) and 200 parts by weight of diglyme solvent were introduced under nitrogen. Then, the above ingredients were slowly stirred to warm the solution to 70°C, and the polymerization was carried out at this temperature for 6 hours. Then, the solvent was distilled off to obtain the first resin (A1-1).

[0308] Preparation Examples A1-2 to A1-10 and Preparation Comparative Examples A1'-1 to A1'-2

[0309] The first resins (A1-2) to (A1-10) and the preparation comparative examples (A1'-1) to (A1'-2) were prepared in the same manner as in the preparation example of the first resin (A1-1) described above, except that the types and amounts of the monomers used were as shown in Table 1. The amounts of the solvent and the catalyst used, the reaction temperature and the polymerization time were different from those of the resin (A1-1) described above, and are shown in Table 1-1 and Table 1-2.

[0310] Table 1-1:

[0311]

[0312] Table 1-2:

[0313]

[0314] In Table 1-1, Table 1-2:

[0315]

[0316] Preparation of the second resin (A2)

[0317] Preparation Examples A2-1 to A2-10 and Preparation Comparative Example A2'-1

[0318] The second resins (A2-1) to (A2-10) and the preparation of Comparative Example (A2'-1) were prepared in the same manner as in the aforementioned preparation example of the first resin (Al-1), except that the kinds and amounts of the monomers were as shown in Table 1. The amounts of the solvent and the catalyst used, the reaction temperature, and the reaction time of the polycondensation were different from those of the aforementioned resin (Al-1), and are shown in Table 2-1 and Table 2-2.

[0319] Table 2-1:

[0320]

[0321] Table 2-2:

[0322]

[0323] In Table 2-1 and Table 2-2:

[0324]

[0325] Example 1

[0326] Example 1 was prepared by adding 90 parts by weight of the first resin (Al-1), 10 parts by weight of the second resin (A2-1), 0.3 parts by weight of N-(4-methylphenylsulfonyloxy)succinimide (B-1), 0.25 parts by weight of the compound (D-1) represented by the formula (S-23), and 0.02 parts by weight of the compound (E-1) represented by the formula (el l) to 300 parts by weight of propylene glycol methyl ether acetate (C-1), and stirring the mixture with a shaking type stirrer until the mixture was uniform.

[0327] The specific conditions and the evaluation results of Example 1 are shown in Table 3-1.

[0328] Examples 2 to 12 and Comparative Examples 1 to 7

[0329] The chemical amplification positive photosensitive resin compositions and the protective films of Examples 2 to 12 and Comparative Examples 1 to 7 were prepared in the same manner as in Example 1. The only difference was that the conditions such as the composition and the amount used were changed in Examples 2 to 12 and Comparative Examples 1 to 7. The specific conditions and the evaluation results of Examples 2 to 12 and Comparative Examples 1 to 7 are shown in Table 3-1, Table 3-2, and Table 4.

[0330] Table 3-1:

[0331]

[0332] Table 3-2:

[0333]

[0334] Table 4:

[0335]

[0336] Evaluation method

[0337] 1. Sensitivity

[0338] After the chemically amplified positive photosensitive resin composition of the Examples and Comparative Examples was coated on a glass substrate (100 mm x 100 mm), preheating was performed by proximity heating with a gap of about 1 mm at a heating condition of 110°C for 120 seconds to form a resist film having a film thickness of 3 μm. Next, selective exposure was performed using an i-line exposure device (device name: FX-702J, manufactured by Nikon Corporation, NA = 0.14) using a test chart mask (scale line) capable of simultaneously drawing a resist pattern of 2.0 μm L&S (line and space) and a resist pattern of 3.0 μm L&S. Next, after development treatment was performed using a 23°C, 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution for 70 seconds, rinsing was performed using pure water for 15 seconds, and spin drying was performed. The exposure amount (Eop, unit: mJ) at which a resist pattern of 2.0 μm L&S could be faithfully reproduced was used as an index for evaluating sensitivity, and the evaluation criteria were as follows:

[0339] ◎: Exposure amount < 60 mJ;

[0340] O: 60 mJ ≦ exposure amount < 150 mJ;

[0341] Δ: 150 mJ ≦ exposure amount < 300 mJ;

[0342] X: Exposure amount ≧ 300 mJ.

[0343] 2. Long-term stability

[0344] The viscosity of the chemically amplified positive photosensitive resin composition of the Examples and Comparative Examples was measured using a viscometer RE85L manufactured by Tokimec, Inc. at 25°C, and the result was η1. Next, after being left under conditions of a temperature of 32°C and a humidity of 55% for a certain period of time, viscosity measurement was performed again at 25°C, and the result was η2. The time interval in which the change in |η2- η1| / η1 was within ±8% was calculated, and the longer the interval, the better the storage stability.

[0345] ◎: 4 weeks or more;

[0346] O: 3 weeks or more and less than 4 weeks;

[0347] Δ: 2 weeks or more and less than 3 weeks;

[0348] X: Less than 2 weeks.

Claims

1. A chemically amplified positive photosensitive resin composition, comprising: A first resin (A1) is obtained by copolymerization of a first mixture comprising an unsaturated carboxylic acid monomer (a1-1), a monomer containing an acid-dissociable group as shown in structural formula (1) (a1-2), and an unsaturated monomer containing a lactone structure (a1-3). In equation (1), R 11 and R 12 Each is independently a hydrogen atom, alkyl, alicyclic hydrocarbon group, or aryl group, wherein the hydrogen atoms of the alkyl, alicyclic hydrocarbon group, or aryl group may be partially or completely substituted, and R 11 and R 12 Not both are hydrogen atoms; R 13 It is an alkyl, alicyclic hydrocarbon, aralkyl, or aryl group, wherein the hydrogen atoms of the alkyl, alicyclic hydrocarbon, aralkyl, and aryl groups may be partially or completely substituted; R 11 With R 13 They can be mutually bonded and with R 11 The bonded carbon atoms and R 13 The bonded oxygen atoms together form a cyclic ether structure; A second resin (A2) is obtained by copolymerization of a second mixture comprising an unsaturated carboxylic acid monomer (a2-1) and an unsaturated monomer (a2-2) containing phenolic hydroxyl groups; Acid generator (B); One solvent (C); Compound (D) represented by formula (6) or formula (7): In equation (6), R 1 and R 2 Each is an alkyl group having 1 to 4 carbon atoms; n6 is an integer from 0 to 2; L 1 It is a single-bonded or divalent linker; X 1 For -S- or -NH-; R 3 It is a monovalent organic group; In equation (7), R 5 and R 6 Each is an alkyl group having 1 to 4 carbon atoms; n7 is an integer from 0 to 2; L 2 It is a single-bonded or divalent linker; X 2 -S- or -NH-; A is a heterocycle containing carbon and nitrogen atoms; and A hindered amine compound (E) is selected from the group consisting of: Compounds of formulas (e11) to (e14); linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine; linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine; N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine and morpholino-2,4,6-trichloro-1,3, Methylation products of polymers of 5-triazine; polymers of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine, reacted with N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinylamine; and products of the reaction of 1,2,3,4-butanetetracarboxylic acid copolymer with β,β,β',β'-tetramethyl-2,4,8,10-tetraoxazolo[5.5]undecane-3,9-diethanol copolymer with 2,2,6,6-tetramethyl-4-piperidinyl ester; In equation (e13), BTC has the structure of equation (e15):

2. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein, The unsaturated monomer (a1-3) containing the lactone structure is the compound shown in formula (3): In equation (3), R X1 R is a hydrogen atom or an alkyl group; A2 It can be an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid-decomposing group. When n2 is greater than 1, multiple R groups are allowed. A2 Same or different; A 1 It is a single-bonded or divalent linker; Z 2 It is a single-ring or multi-ring structure containing -OC (=O)-; n2 is an integer greater than or equal to 0.

3. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein, The unsaturated monomer (a2-2) containing phenolic hydroxyl groups is the compound shown in formula (4): In equation (4), R 220 It is a hydrogen atom or a methyl group; R 221 It is a single-bonded or divalent linker; R 222 It is a halogen atom or a straight-chain or branched alkyl group having 1 to 5 carbon atoms; when b is greater than 1, multiple R 222 Same or different; b is an integer from 0 to 4, c is an integer from 1 to 5, and b+c is less than 5.

4. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein, The second mixture further comprises monomers (a2-3) containing acid-dissociable groups as shown in structural formula (2); In equation (2), R 21 and R 22 Each is independently a hydrogen atom, alkyl, alicyclic hydrocarbon group, or aryl group, wherein the hydrogen atoms of the alkyl, alicyclic hydrocarbon group, or aryl group may be partially or completely substituted, and R 21 and R 22 Not both are hydrogen atoms; R 23 It is an alkyl, alicyclic hydrocarbon, aralkyl, or aryl group, wherein the hydrogen atoms of the alkyl, alicyclic hydrocarbon, aralkyl, and aryl groups may be partially or completely substituted; R 21 With R 23 They can be mutually bonded and with R 21 The bonded carbon atoms and R 23 The bonded oxygen atoms together form a cyclic ether structure.

5. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein, The photoacid generator (B) is a compound containing an oxime sulfonate group of formula (8): In equation (8), R 16 It is an alkyl, alicyclic hydrocarbon, or aryl group having 1 to 20 carbon atoms, wherein the hydrogen atoms of the alkyl, alicyclic hydrocarbon, or aryl group may be partially or completely substituted; * indicates a bond.

6. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein, Based on a total usage of 100 parts by weight for the first resin (A1) and the second resin (A2), the usage of the first resin (A1) is 40 to 90 parts by weight, the usage of the second resin (A2) is 10 to 60 parts by weight, the usage of the photoacid generator (B) is 0.3 to 5 parts by weight, the usage of the solvent (C) is 150 to 1200 parts by weight, the usage of the compound (D) is 0.05 to 0.8 parts by weight, and the usage of the hindered amine compound (E) is 0.02 to 0.2 parts by weight.

7. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein, The total amount of the first mixture based on the first resin (A1) is 100 parts by weight, the amount of the unsaturated carboxylic acid monomer (a1-1) is 3 to 30 parts by weight, the amount of the monomer (a1-2) containing the acid dissociative group shown in structural formula (1) is 15 to 75 parts by weight, and the amount of the unsaturated monomer (a1-3) containing the lactone structure is 1 to 15 parts by weight.

8. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein, The total amount of the second mixture based on the second resin (A2) is 100 parts by weight, the amount of the unsaturated carboxylic acid monomer (a2-1) is 1 to 20 parts by weight, and the amount of the unsaturated monomer (a2-2) containing phenolic hydroxyl groups is 5 to 50 parts by weight.

9. The chemically amplified positive photosensitive resin composition as described in claim 4, wherein, The total amount of the second mixture based on the second resin (A2) is 100 parts by weight, and the amount of the monomer (a2-3) containing the acid-dissociable group shown in structural formula (2) is 0 to 70 parts by weight.

10. The chemically amplified positive photosensitive resin composition according to claim 1, wherein, The weight ratio of the compound (D) to the hindered amine compound (E) is 0.5 to 10.

11. A protective film is formed by coating a substrate with a chemically amplified positive photosensitive resin composition as described in any one of claims 1 to 10, followed by pre-baking, exposure, development, and post-baking treatments.

12. An assembly having a protective film, comprising a substrate and the protective film as claimed in claim 11, the protective film being attached to the substrate.

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