Chemically amplified positive photosensitive resin composition, hardened film and element having hardened

Abstract

The invention discloses a chemically amplified positive photosensitive resin composition, a hardened film and an element with the hardened film. The chemically amplified positive optical rotation-sensitive resin composition contains a resin (A), a photoacid generator (B) and a solvent (C). The resin (A) includes a resin (A-1) containing an acid-dissociable group, and the photoacid generator (B) includes a compound (B-1) containing an oxime sulfonate group. The hardened film prepared by using the chemically amplified positive optical rotation-sensitive resin composition has good high temperature and high humidity reliability and development adherence.

Description

Technical Field

[0001] The present invention relates to a chemically amplified positive photosensitive resin composition, and more particularly to a chemically amplified positive photosensitive resin composition having good high temperature and high humidity reliability and developing adhesion, a hardened film obtained therefrom, and a device containing the hardened film. Background Art

[0002] An electronic device such as a thin film transistor type liquid crystal display device, an organic electroluminescence device (organic EL device), a semiconductor device or a photosensitive device generally includes an interlayer insulating film or a planarizing film, and the interlayer insulating film or the planarizing film is generally formed using a photosensitive composition. In order to meet the requirements of patterning performance, a positive photosensitive resin composition containing an acid generator such as naphthoquinone diazide (refer to Japanese Patent Laid-Open No. 2001-354822) is generally used, but other photosensitive compositions have been proposed in recent years.

[0003] For example, Japanese Patent Laid-Open No. 2004-4669 is about a positive-type chemical amplification material that forms a hardened film for a display element. The positive-type chemical amplification material has a higher sensitivity than the positive-type photosensitive resin composition using an acid generator such as naphthoquinone diazide. The positive-type chemical amplification material contains a crosslinking agent, an acid generator, and an acid-dissociable resin, wherein the acid-dissociable resin has a protective group that can be dissociated by an acid. Although the acid-dissociable resin itself is insoluble or difficult to dissolve in an alkaline aqueous solution, the protective group is dissociated by the action of an acid and becomes soluble in an alkaline aqueous solution. In addition, Japanese Patent Laid-Open No. 2004-264623, Japanese Patent Laid-Open No. 2011-215596, and Japanese Patent Laid-Open No. 2008-304902 also propose positive-type photosensitive compositions containing a resin having an acetal structure and / or a ketal structure and an epoxy group and an acid generator.

[0004] Such photosensitive resin compositions, when used as hardened film materials, must have good adhesion to form an ideal pattern, and must also have good reliability so that the device containing the hardened film also has good reliability. However, hardened films formed by current photosensitive resin compositions still have problems with high temperature and high humidity reliability and poor development adhesion, and are still not accepted by the industry. Summary of the invention

[0005] In view of this, one aspect of the present invention is to provide a chemically amplified positive photosensitive resin composition, which comprises a resin (A), a photoacid generator (B) and a solvent (C). The hardened film prepared by using the chemically amplified positive photosensitive resin composition has good high temperature and high humidity reliability and development adhesion.

[0006] Another aspect of the present invention is to provide a cured film formed by using the chemically amplified positive photosensitive resin composition.

[0007] Another aspect of the present invention is to provide a device, which includes the above-mentioned hardened film.

[0008] According to the above aspect of the present invention, a chemically amplified positive-type photosensitive resin composition is provided, and the chemically amplified positive-type photosensitive resin composition comprises a resin (A), a photoacid generator (B) and a solvent (C), which are described below.

[0009] Resin (A)

[0010] The resin (A) of the present invention comprises a resin (A-1) having an acid-dissociable group and another resin (A-2).

[0011] Resin containing acid dissociable groups (A-1)

[0012] The acid-dissociable group-containing resin (A-1) includes a repeating unit containing an acid-dissociable group and a repeating unit having at least one structure selected from the following formulas (I-1) to (I-4):

[0013]

[0014] In formula (I-1) to formula (I-4), R1, R2, R3, R4, R5 and R6 independently represent a hydrogen atom or a straight-chain or branched alkyl group with a carbon number of 1 to 30, preferably represent a hydrogen atom or a straight-chain or branched alkyl group with a carbon number of 1 to 10, more preferably represent a hydrogen atom or a straight-chain or branched alkyl group with a carbon number of 1 to 5, and particularly preferably represent a methyl group.

[0015] In some embodiments, the resin (A-1) containing an acid-dissociable group of the present invention may selectively contain a repeating unit represented by the following formula (II):

[0016]

[0017] In formula (II), R7 represents a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, a phenyl group which may be substituted with a substituent, a benzyl group, or a cycloalkyl group having 3 to 6 carbon atoms. The substituent may be an alkyl group having 1 to 5 carbon atoms.

[0018] The resin (A-1) containing an acid dissociable group can be formed by copolymerization of the first mixture. The first mixture can include an unsaturated monomer (a-1) containing an acid dissociable group having a structure as shown in the following formula (a1-1) and an unsaturated monomer (a-2) having a structure as shown in the following formula (a2-1) or formula (a2-2) and two alkenyl groups. In addition, the first mixture can selectively include an unsaturated monomer (a-3) containing a maleimide group having a structure as shown in the following formula (a3-1), an unsaturated carboxylic acid monomer (a-4), an unsaturated monomer (a-5) containing a lactone structure, and other unsaturated monomers (a-6).

[0019] Unsaturated monomer containing an acid dissociable group (a-1)

[0020] The unsaturated monomer (a-1) containing an acid-dissociable group of the present invention has a structure represented by the following formula (a1-1):

[0021]

[0022] In formula (a1-1), R8 and R9 independently represent a hydrogen atom, an alkyl group which may be substituted or unsubstituted, an alicyclic hydrocarbon group or an aryl group, and R8 and R9 cannot be hydrogen atoms at the same time; R 10 represents an alkyl group, an alicyclic hydrocarbon group, an aralkyl group or an aryl group which may be substituted or unsubstituted; R8 and R 10 The carbon atom and R bonded to R8 can bond to each other. 10 The bonded oxygen atoms together form a cyclic ether structure; wherein R8, R9 and R 10 The substituent includes a halogen atom, a hydroxyl group or an organic group.

[0023] The acid dissociable group of the unsaturated monomer (a-1) containing an acid dissociable group dissociates by the action of an acid generated from a photoacid generator (B) described later during exposure to generate a polar group, thereby making the resin (A) originally insoluble or poorly soluble in an alkaline aqueous solution soluble in an alkaline aqueous solution.

[0024] The acid-dissociable group-containing unsaturated monomer (a-1) is not particularly limited as long as it has a structure represented by the formula (a1-1). The acid-dissociable group-containing unsaturated monomer (a-1) can be easily dissociated by an acid.

[0025] The alicyclic hydrocarbon group represented by R8 and R9 may be, for example, an alicyclic hydrocarbon group having 3 to 20 carbon atoms. In addition, the alicyclic hydrocarbon group having 3 to 20 carbon atoms may be polycyclic. The alicyclic hydrocarbon group having 3 to 20 carbon atoms may be, for example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bornyl, norbornyl or adamantyl.

[0026] The aryl group represented by R8 and R9 may be, for example, an aryl group having 6 to 14 carbon atoms. The aryl group having 6 to 14 carbon atoms may be a single ring, a structure formed by linking single rings, or a condensed ring. The aryl group having 6 to 14 carbon atoms may be, for example, a phenyl group or a naphthyl group.

[0027] The substituent of the alkyl group, alicyclic hydrocarbon group and aryl group which may be substituted represented by R8 and R9 may be, for example, a halogen atom, a hydroxyl group or an organic group.

[0028] The organic group may be, for example, a nitro group, a cyano group, a carboxyl group, a carbonyl group, an alicyclic hydrocarbon group (for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bornyl group, a norbornyl group or an adamantyl group), an aryl group (for example, a phenyl group or a naphthyl group), an alkoxy group (for example, an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a n-butoxy group, a pentyl group, a hexyl group, a heptyl group or an octyl group), an acyl group (for example, an acyl group having 2 to 20 carbon atoms, such as an acetyl group, a propionyl group, a butyryl group or an isobutyryl group), an acyloxy group (for example, an acyloxy group having 2 to 10 carbon atoms, such as an acetyloxy group, a propionyloxy group, a butyryl group, a tert-butyryloxy group or a tert-pentanoyloxy group). The present invention also includes substituents such as alkyl, alkyl, alkylene ...

[0029] R 10 The alkyl group, alicyclic hydrocarbon group and aryl group represented by R8 and R9 may be the same as the alkyl group, alicyclic hydrocarbon group and aryl group represented by R8 and R9. 10 The alkyl group represented is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group, an ethyl group or an n-propyl group. 10 The aralkyl group represented may be, for example, benzyl, phenethyl, naphthylmethyl or naphthylethyl.

[0030] R8 and R 10 The cyclic ether structure formed by mutual bonding is preferably a cyclic ether structure having 3 to 20 ring members, more preferably a cyclic ether structure having 5 to 8 ring members, and most preferably, for example, tetrahydrofuran or tetrahydropyran.

[0031] The structure represented by formula (a1-1) may be, for example, a group as shown below:

[0032]

[0033]

[0034] The unsaturated monomer (a-1) containing an acid-dissociable group may be, 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-tetrahydropyranylmethacrylate, 2-tetrahydrofuranylmethacrylate, 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-ethoxyethoxystyrene or m-1-ethoxyethoxystyrene, p-1-methoxyethoxystyrene or m-1-methoxyethoxystyrene, p-1- n-butoxyethoxystyrene or m-1-n-butoxyethoxystyrene, p-1-isobutoxyethoxystyrene or m-1-isobutoxyethoxystyrene, p-1-(1,1-dimethylethoxy)ethoxystyrene or m-1-(1,1-dimethylethoxy)ethoxystyrene, p-1-(2-chloroethoxy)ethoxystyrene or m-1-(2-chloroethoxy)ethoxystyrene, p-1-(2-ethylhexyloxy)ethoxystyrene or m-1-(2-ethylhexyloxy)ethoxystyrene, p-1-n-propoxyethoxystyrene or m-1-n-propoxyethoxystyrene, p-1-cyclohexylethoxystyrene or m-1-cyclohexylethoxystyrene, p-1-(2-cyclohexylethoxy)ethoxystyrene or m-1-(2-cyclohexylethoxy)ethoxystyrene, p-1-benzyloxyethoxystyrene or m-1-benzyloxyethoxystyrene, and the like.

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

[0036] The above-mentioned acid-dissociable group-containing unsaturated monomer (a-1) may be used alone or in combination of two or more.

[0037] Based on 100 parts by weight of the first mixture, the amount of the unsaturated monomer (a-1) containing an acid-dissociable group is 10 to 60 parts by weight, preferably 12 to 58 parts by weight, and more preferably 15 to 55 parts by weight.

[0038] Unsaturated monomer containing two olefinic groups (a-2)

[0039] The unsaturated monomer (a-2) containing two alkenyl groups may have a structure as shown in the following formula (a2-1) or formula (a2-2):

[0040]

[0041] In formula (a2-1) and formula (a2-2), R1, R2 and R3 are as defined above and are not further described here.

[0042] In some specific examples, the unsaturated monomer containing two olefinic groups (a-2) may include but is not limited to the following compounds:

[0043]

[0044]

[0045] The aforementioned unsaturated monomer containing two ethylenic groups (a-2) may be used alone or in combination of two or more.

[0046] Based on 100 parts by weight of the first mixture, the amount of the unsaturated monomer containing two olefinic groups (a-2) may be 2 to 30 parts by weight, preferably 2.5 to 25 parts by weight, and more preferably 3 to 20 parts by weight.

[0047] If the first mixture of the resin (A-1) containing an acid-dissociable group in the chemically amplified positive optically sensitive resin composition of the present invention does not include the unsaturated monomer (a-2) containing two olefinic groups, the obtained cured film has poor high temperature and high humidity reliability.

[0048] Maleimide group-containing unsaturated monomer (a-3)

[0049] The maleimide group-containing unsaturated monomer (a-3) may have a structure as shown in the following formula (a3-1):

[0050]

[0051] In formula (a3-1), R7 is as defined above and will not be further described here.

[0052] The maleimide-containing unsaturated monomer (a-3) may include, but is not limited to, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-chlorophenyl)maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, Nitrogen substituted or unsubstituted maleimide such as N-phenylmethylmaleimide, N-(2,4,6-tribromophenyl)maleimide, N-[3-(triethoxysilyl)propyl]maleimide, N-octadecenylmaleimide, N-dodecenylmaleimide, N-(2-methoxyphenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, N-(1-hydroxyphenyl)maleimide, etc.

[0053] Among them, the unsaturated monomer (a-3) containing a maleimide group is preferably N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-laurylmaleimide, N-cyclohexylmaleimide, or N-benzylmaleimide, and is more preferably N-phenylmaleimide or N-cyclohexylmaleimide.

[0054] In some specific examples, the maleimide-containing unsaturated monomer (a-3) may include but is not limited to the following compounds:

[0055]

[0056]

[0057] The maleimide group-containing unsaturated monomer (a-3) may be used alone or in combination of two or more.

[0058] Based on 100 parts by weight of the first mixture, the amount of the maleimide group-containing unsaturated monomer (a-3) may be 1 to 24 parts by weight, preferably 2 to 22 parts by weight, and more preferably 3 to 20 parts by weight.

[0059] If the first mixture of the resin (A-1) containing an acid-dissociable group in the chemically amplified positive optically sensitive resin composition of the present invention includes an unsaturated monomer (a-3) containing a maleimide group, the high temperature and high humidity reliability of the obtained cured film can be further improved.

[0060] Unsaturated carboxylic acid monomer (a-4)

[0061] The unsaturated carboxylic acid monomer (a-4) of the present invention refers to a compound comprising a carboxylic acid group or a carboxylic anhydride structure and an unsaturated bond for polymerizing. The structure is not particularly limited, and may include but is not limited to an unsaturated monocarboxylic acid compound, an unsaturated dicarboxylic acid compound, an unsaturated dicarboxylic anhydride compound, a polycyclic unsaturated carboxylic acid compound, a polycyclic unsaturated dicarboxylic acid compound or a polycyclic unsaturated dicarboxylic anhydride compound.

[0062] Specific examples of the unsaturated monocarboxylic acid compound include: (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, ethylacrylic acid, cinnamic acid, 2-(meth)acryloylethoxysuccinate, 2-(meth)acryloylethoxyhexahydrophthalate, 2-(meth)acryloylethoxyphthalate, or ω-carboxy polycaprolactone polyol monoacrylate (trade name ARONIX M-5300, manufactured by Toa Gosei Co., Ltd.).

[0063] Specific examples of the unsaturated dicarboxylic acid compound include maleic acid, fumaric acid, methylfumaric acid, itaconic acid, and citraconic acid.

[0064] In a specific example of the present invention, the unsaturated dicarboxylic acid anhydride compound may be an anhydride compound of the unsaturated dicarboxylic acid compound mentioned above.

[0065] Specific examples of the polycyclic unsaturated carboxylic acid compound include 5-carboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, or 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene.

[0066] A specific example of the polycyclic unsaturated dicarboxylic acid compound is 5,6-dicarboxylic acid bicyclo[2.2.1]hept-2-ene.

[0067] The polycyclic unsaturated dicarboxylic acid anhydride compound is an anhydride compound of the above-mentioned polycyclic unsaturated dicarboxylic acid compound.

[0068] Preferred specific examples of the unsaturated carboxylic acid monomer (a-4) include acrylic acid, methacrylic acid, maleic anhydride, 2-methacryloylethoxysuccinate, or 2-methacryloylethoxyhexahydrophthalic acid.

[0069] The unsaturated carboxylic acid monomers (a-4) mentioned above may be used alone or in combination of two or more.

[0070] Based on 100 parts by weight of the first mixture, the unsaturated carboxylic acid monomer (a-4) is used in an amount of 2 to 30 parts by weight, preferably 2.5 to 28 parts by weight, and more preferably 3 to 25 parts by weight.

[0071] Unsaturated monomer containing lactone structure (a-5)

[0072] The unsaturated monomer (a-5) containing a lactone structure may be a compound represented by the following formula (a5):

[0073]

[0074] In formula (a5), R 11 represents a hydrogen atom or an alkyl group; R 12 represents 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-decomposable group; R 14 Represents a single bond or a divalent linking group; R 13 Represents b1 represents an integer greater than 0. When b1 is greater than 1, multiple R 12 Can be the same or different.

[0075] R 11 The alkyl group represented is preferably a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. The alkyl group may have a substituent, and the substituent is preferably a hydroxyl group or a halogen atom (especially a fluorine atom).

[0076] R 12 Preferred is an alkyl group having 1 to 4 carbon atoms or a cyano group.

[0077] R 14 The divalent linking group may be, for example, a linear alkylene group, a branched alkylene group, a cyclic alkylene group, an arylene group, -O-, -COO-, -S-, -NR"-, -CO-, -NR"CO- or -SO2- divalent linking group, or a group containing a combination of the aforementioned functional groups, wherein R" may be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom. R 14 The divalent linking group preferably contains at least one of -O-, -COO-, -S-, -NH- and -CO-, or these groups and -(CH2) d -, wherein d represents an integer of 1 to 10, preferably an integer of 1 to 6, and more preferably an integer of 1 to 4.

[0078] R13 Preferably it is a monocyclic structure. 13 When R represents a monocyclic structure, it preferably forms a lactone structure having 5 to 7 members, and more preferably forms a lactone structure having 5 or 6 members. 13 When a polycyclic structure is represented, it is preferably other ring structures, and a condensed ring in the form of a bicyclic structure or a spirocyclic structure is formed on the lactone structure. Other ring structures may be, for example, a cyclic hydrocarbon group having 3 to 20 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms. The heterocyclic group is not particularly limited, and it can be enumerated in which one or more of the atoms constituting the ring are heteroatoms, or an aromatic heterocyclic group. In addition, the heterocyclic group is preferably a 5-membered ring or a 6-membered ring, and is particularly preferably a 5-membered ring. Specifically, the heterocyclic group preferably contains at least one oxygen atom, and for example, oxacyclopentane ring, oxane ring, dioxane ring, etc. can be enumerated.

[0079] b1 is preferably an integer from 0 to 4, more preferably an integer from 0 to 2, and most preferably 0. When b1 represents an integer greater than 2, a plurality of R 12 Can be the same or different. 12 They may bond to each other to form a ring, but preferably they do not bond to each other to form a ring.

[0080] The unsaturated monomer (a-5) containing a lactone structure is preferably a compound represented by the following formula (a5-1):

[0081]

[0082] In formula (a5-1), R 11 ' is a hydrogen atom or an alkyl group; R 12 ' 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-decomposable group; b2 represents an integer greater than 0. When b2 is greater than 1, multiple R 12 ' can be the same or different; R 14 ' is a single bond or a divalent linking group; R 13 ' is the The monocyclic or polycyclic structure of R 15 ' is an oxygen atom or -NR"-, and R" is a hydrogen atom or an alkyl group.

[0083] R 11 The alkyl group represented by ' may preferably be a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. The alkyl group may have a substituent, and the substituent is preferably a hydroxyl group or a halogen atom, more preferably a fluorine atom.

[0084] R 12 ' is preferably an alkyl group having 1 to 4 carbon atoms or a cyano group.

[0085] R 14The divalent linking group of ' can be, for example, a straight-chain alkylene group, a branched alkylene group, a cyclic alkylene group, an arylene group, a divalent group such as -O-, -COO-, -S-, -NR"-, -CO-, -NR"CO-, -SO2-, or a combination of the aforementioned functional groups, wherein R" can be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom. R 14 The divalent linking group of ' preferably contains at least one of -COO- and -CO-, or these groups and -(CH2) d -, d represents an integer from 1 to 10, preferably an integer from 1 to 6, and more preferably an integer from 1 to 4. 14 ' is particularly preferably a single bond.

[0086] R 13 ' is preferably a monocyclic structure. 13 When R represents a monocyclic structure, it preferably forms a lactone structure having 5 to 7 members, and more preferably forms a lactone structure having 5 or 6 members. 13 When ' represents a polycyclic structure, it is preferably other ring structures, and forms a condensed ring in the form of a bicyclic structure or a spirocyclic structure on the lactone structure. Other ring structures can include cyclic hydrocarbon groups with 3 to 20 carbon atoms, or heterocyclic groups with 3 to 20 carbon atoms. The heterocyclic group is not particularly limited, and it can include one or more heteroatoms in 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 is particularly preferably a 5-membered ring. Specifically, the heterocyclic group preferably contains at least one oxygen atom, for example, oxacyclopentane ring, oxane ring, dioxane ring, etc.

[0087] b2 is preferably an integer from 0 to 4, more preferably an integer from 0 to 2, and most preferably 0. When b2 represents an integer greater than 2, a plurality of R 12 ' can be the same or different. In addition, multiple R 12 ' may be bonded to each other to form a ring, but preferably they are not bonded to each other to form a ring.

[0088] R 15 ' is preferably an oxygen atom. 15 ' is -NR"-, R" may be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom.

[0089] The compound represented by formula (a5) preferably contains a structure represented by any one of the following formulas (a5-2-1) to (a5-2-21):

[0090]

[0091]

[0092] In formula (a5-2-1) to formula (a5-2-21), R 16 represents 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-decomposable group. When s is greater than 1, multiple R 16 Can be the same or different.

[0093] The structures represented by formula (a5-2-1) to formula (a5-2-21) may or may not have R 16 , and preferably does not have R 16 (i.e. s is 0). 16 Preferably it represents an alkyl group having 1 to 4 carbon atoms or a cyano group.

[0094] s is preferably an integer from 0 to 4, more preferably an integer from 0 to 2, and more preferably 0. When s represents an integer greater than 2, a plurality of R 16 Can be the same or different. 16 They may be bonded to each other to form a ring, but preferably they are not bonded to each other to form a ring.

[0095] The compound shown in formula (a5) preferably contains the structure shown in formula (a5-2-1), formula (a5-2-4), formula (a5-2-5), formula (a5-2-6), formula (a5-2-13), formula (a5-2-14) or formula (a5-2-17), and more preferably contains the structure shown in formula (a5-2-1), formula (a5-2-4) or formula (a5-2-17).

[0096] Specific examples of the compound represented by formula (a5) include compounds represented by the following formulas (a5-3-1) to (a5-3-21):

[0097]

[0098]

[0099]

[0100]

[0101] In formula (a5-3-1) to formula (a5-3-2), R 17 The definition of R is the same as above 11 The definitions of ' are the same and are not repeated here. In formula (a5-3-18), Me represents a methyl group.

[0102] Specific examples of the unsaturated monomer (a-5) containing a lactone structure include compounds represented by the following formulas (a5-4-1) to (a5-4-11), and preferably compounds represented by the following formulas (a5-4-1) to (a5-4-11):

[0103]

[0104]

[0105]

[0106] The aforementioned lactone structure-containing unsaturated monomer (a-5) may be used alone or in combination of two or more.

[0107] Based on 100 parts by weight of the first mixture, the amount of the unsaturated monomer (a-5) containing a lactone structure is 1 to 15 parts by weight, preferably 1.5 to 14 parts by weight, and more preferably 2 to 13 parts by weight.

[0108] Other unsaturated monomers (a-6)

[0109] Other unsaturated monomers (a-6) may include epoxy-containing unsaturated monomers, alkyl (meth)acrylates, alicyclic (meth)acrylates, aryl (meth)acrylates, unsaturated dicarboxylic acid diesters, hydroxyalkyl (meth)acrylates, polyethers of (meth)acrylates, aromatic vinyl compounds and other unsaturated monomers other than the aforementioned compounds.

[0110] The epoxy-containing unsaturated monomer may include, but is not limited to, epoxy-containing (meth)acrylate compounds, epoxy-containing α-alkylacrylate compounds, glycidyl ether compounds, ethylenically unsaturated monomers having an oxetane group as shown in formula (a6), and any combination of the above monomers:

[0111]

[0112] In formula (a6), R 51 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 52 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 53 , R 54 , R 55 and R 56 Each independently represents a hydrogen atom, a fluorine atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, or a perfluoroalkyl group having 1 to 4 carbon atoms; and a is an integer of 1 to 6.

[0113] Specific examples of the epoxy-containing (meth)acrylate compound may be: glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate.

[0114] Specific examples of the epoxy group-containing α-alkyl acrylate compound include α-ethyl acrylate glycidyl ester, α-n-propyl acrylate glycidyl ester, α-n-butyl acrylate glycidyl ester, or α-ethyl acrylate 6,7-epoxyheptyl ester.

[0115] Specific examples of the glycidyl ether compound include o-vinylbenzylglycidyl ether (o-vinylbenzylglycidyl ether), m-vinylbenzylglycidyl ether (m-vinylbenzylglycidyl ether), and p-vinylbenzylglycidyl ether (p-vinylbenzylglycidyl ether).

[0116] Specific examples of the ethylenically unsaturated monomer having an oxetane group as represented by formula (a6) may include, but are not limited to, methacrylate compounds, acrylate compounds, or unsaturated monomers represented by the following formulas (a6-1) to (a6-4):

[0117]

[0118] Methacrylate compounds may include, but are not limited to, 3-(methacryloyloxymethyl)oxetane (3-(methacryloyloxymethyl)oxetane; OXMA), 3-(methacryloyloxymethyl)-3-ethyloxetane (3-(methacryloyloxymethyl)-3-ethyloxetane; EOXMA), 3-(methacryloyloxymethyl)-3-methyloxetane (3-(methacryloyloxymethyl)-3-methyloxetane; MOXMA), 3-(methacryloyloxymethyl)-2-methyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane oxetane, 3-(methacryloyloxymethyl)-2,2-difluorooxetane, 3-(methacryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(methacryloyloxyethyl)oxetane, 3-(methacryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-(methacryloyloxyethyl)oxetane, 3-(methacryloyloxyethyl)-2,2,4,4-tetrafluorooxetane The invention also includes compounds such as 2-(methacryloyloxyethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxyethyl)-2-phenyloxetane, 2,2-difluoro-3-(methacryloyloxyethyl)oxetane, 3-(methacryloyloxyethyl)-2,2,4-trifluorooxetane or 3-(methacryloyloxyethyl)-2,2,4,4-tetrafluorooxetane.

[0119] Acrylate compounds may 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-difluorooxetane, 3-(acryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(acryloyloxymethyl)- Compounds such as 2,2,4,4-tetrafluorooxetane, 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-trifluorooxetane or 3-(acryloyloxyethyl)-2,2,4,4-tetrafluorooxetane.

[0120] In some embodiments, the epoxy-containing unsaturated monomer may further include other ethylenically unsaturated monomers having an oxetane group, such as: 3-methyl-3-(vinyloxymethyl)oxetane (3-methyl-3-(vinyloxymethyl)oxetane; MOXV), 3-ethyl-3-(vinyloxymethyl)oxetane (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 A vinyl ether compound having an oxetane group such as 3-methyl-3-(3-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-oxetane)methyl)vinyl ether, propylene glycol ((3-ethyl-3-oxetane)methyl)vinyl ether or 3,3-bis((vinyloxy)methyl)oxetane.

[0121] Specific examples of the alkyl (meth)acrylate may include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate or tertiary butyl (meth)acrylate.

[0122] Specific examples of alicyclic (meth)acrylates include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2.6 ]Decan-8-yl (meth)acrylate (or known as dicyclopentyl (meth)acrylate), dicyclopentyloxyethyl (meth)acrylate or isobornyl (meth)acrylate.

[0123] Specific examples of the aryl (meth)acrylate include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0124] Specific examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, or diethyl itaconate.

[0125] Specific examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0126] Specific examples of the polyether of (meth)acrylate include polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate.

[0127] Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene or p-methoxystyrene.

[0128] Specific examples of other unsaturated compounds other than the aforementioned compounds may include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl 1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate or N-(9-acridinyl)maleimide.

[0129] The above-mentioned other unsaturated monomers (a-6) may be used alone or in combination of two or more.

[0130] Based on 100 parts by weight of the first mixture, the amount of the other unsaturated monomer (a-6) is 5 to 87 parts by weight, preferably 10 to 85 parts by weight, and more preferably 15 to 80 parts by weight.

[0131] Based on 100 parts by weight of the resin (A), the amount of the resin (A-1) containing an acid-dissociable group may be 30 to 100 parts by weight, preferably 50 to 100 parts by weight, and more preferably 70 to 100 parts by weight.

[0132] If the resin (A) of the chemically amplified positive optically sensitive resin composition of the present invention does not include the resin (A-1) containing an acid dissociable group, the obtained cured film has poor high temperature and high humidity reliability.

[0133] Other resins (A-2)

[0134] The other resin (A-2) of the present invention is not particularly limited, and it only needs to contain an acid-dissociable group and be different from the aforementioned resin (A-1) containing an acid-dissociable group. For example, the other resin (A-2) can be a copolymer formed by copolymerizing the second mixture. The difference between the second mixture and the aforementioned first mixture is that the second mixture does not contain the aforementioned unsaturated monomer (a-2) containing two olefinic groups.

[0135] In addition, in the preparation process of other resin (A-2), specific examples of unsaturated monomers containing acid-dissociable groups, unsaturated monomers containing maleimide groups, unsaturated carboxylic acid monomers, unsaturated monomers containing lactone structures and other unsaturated monomers used may be the same as the specific examples of unsaturated monomers containing acid-dissociable groups (a-1), unsaturated monomers containing maleimide groups (a-3), unsaturated carboxylic acid monomers (a-4), unsaturated monomers containing lactone structures (a-5) and other unsaturated monomers (a-6) used in the preparation process of resin (A-1) containing acid-dissociable groups, and therefore they are not further described herein.

[0136] Synthesis method of resin (A-1) containing acid dissociable groups and other resins (A-2)

[0137] The synthesis method of the resin (A-1) or other resin (A-2) containing acid dissociable groups can be, for example, by using a free radical polymerization initiator to polymerize the monomers in the first mixture or the second mixture in an appropriate solvent to obtain the resin (A-1) or other resin (A-2) containing acid dissociable groups. For example, it is preferably synthesized by the following method: a solution containing monomers and a free radical polymerization initiator is added dropwise to a solution containing a reaction solvent or a monomer to carry out a polymerization reaction; a solution containing a monomer and a solution containing a free radical polymerization initiator are added dropwise to a solution containing a reaction solvent or a monomer to carry out a polymerization reaction; or a plurality of solutions containing each monomer and a solution containing a free radical polymerization initiator are added dropwise to a solution containing a reaction solvent or a monomer to carry out a polymerization reaction.

[0138] The solvent used for the polymerization reaction of the acid-dissociable group-containing resin (A-1) and the other resin (A-2) may be, for example, the same solvent as that described below as the solvent (C).

[0139] Common free radical polymerization initiators can be used as polymerization initiators for polymerization reactions, for example, 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(methyl 2-methylpropionate); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxytrimethylacetate, 1,1′-bis-(t-butylperoxy)cyclohexane; or hydrogen peroxide, etc.

[0140] In the polymerization reaction of the resin (A-1) containing an acid-dissociable group and other resins (A-2), a molecular weight regulator may be used in an appropriate amount to adjust the molecular weight. The molecular weight regulator may be, for example, chloroform, carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolic acid, 3-mercaptopropionic acid, etc.

[0141] The weight average molecular weight (Mw) of the resin (A-1) containing an acid dissociable group and the other resin (A-2) obtained by colloid permeation chromatography (GPC) using polystyrene conversion is independently 2,000 to 38,000, preferably 3,000 to 28,000, and more preferably 4,000 to 18,000.

[0142] Photoacid generator (B)

[0143] The photoacid generator (B) of the present invention may include a compound having an oxime sulfonate group (B-1) and other photoacid generating compounds (B-2).

[0144] Oxime sulfonate group compound (B-1)

[0145] The oxime sulfonate group compound (B-1) has a structure as shown in the following formula (b-1):

[0146]

[0147] In formula (b-1), A1 represents an alkyl group or aryl group with a carbon number of 1 to 10 which may be substituted or unsubstituted by a substituent; A2 represents an alkyl group with a carbon number of 1 to 10, an aryl group with a carbon number of 1 to 10, or a nitrile group; and A3 to A7 independently represent a hydrogen atom, an alkyl group or an aryl group with a carbon number of 1 to 10, wherein the alkyl group with a carbon number of 1 to 10 may be substituted or unsubstituted by an ether group (-O-) or a thioether group (-S-).

[0148] The alkyl group having 1 to 10 carbon atoms represented by A1 may be substituted by a fluorine atom, and the aryl group represented by A1 may be substituted by an alkyl group. Preferably, A1 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group substituted by a substituent.

[0149] Preferably, A2 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group or a nitrile group (-CN).

[0150] The alkyl group having 1 to 10 carbon atoms represented by A3 to A7 may be substituted by an ether group (—O—) or a thioether group (—S—), and the aryl group represented by A3 to A7 may be substituted by an alkyl group. Preferably, A3 to A7 may independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and being substituted or not substituted by an ether group (—O—) or a thioether group (—S—), or a phenyl group, and at least one of A3 to A7 represents an alkyl group substituted by an ether group (—O—) or a thioether group (—S—).

[0151] Preferably, in formula (b-1), A1 represents an alkyl group or phenyl group having 1 to 6 carbon atoms substituted by a substituent; A2 represents an alkyl group, phenyl group or nitrile group having 1 to 6 carbon atoms; A3 to A7 can independently represent a hydrogen atom, an alkyl group or phenyl group having 1 to 6 carbon atoms and substituted or not substituted by an ether group (-O-) or a thioether group (-S-), and at least one of A3 to A7 represents an alkyl group substituted by an ether group (-O-) or a thioether group (-S-). Under this preferred condition, the development adhesion of the obtained hardened film can be further improved.

[0152] In some specific examples, the oxime sulfonate group compound (B-1) may include but is not limited to the following compounds:

[0153]

[0154]

[0155]

[0156]

[0157] The above-mentioned oxime sulfonate group-containing compound (B-1) may be used alone or in combination of two or more.

[0158] Based on 100 parts by weight of the resin (A), the amount of the oxime sulfonate group compound (B-1) may be 0.3 to 15 parts by weight, preferably 0.4 to 13 parts by weight, and more preferably 0.5 to 12 parts by weight.

[0159] If the chemically amplified positive-type photosensitive resin composition of the present invention does not include the compound (B-1) having an oxime sulfonate group, the development adhesion of the obtained cured film is poor.

[0160] Other photoacid generating compounds (B-2)

[0161] Other photoacid generating compounds (B-2) may include other oxime sulfonate group-containing compounds other than the aforementioned oxime sulfonate group-containing compound (B-1), N-sulfonyloxyimide compounds, onium salts, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, or carboxylate compounds.

[0162] Other oxime sulfonate group-containing compounds may include oxime sulfonate compounds represented by the following formulas (b-2-1) to (b-2-3):

[0163]

[0164] In formula (b-2-1) to formula (b-2-3), A8 may represent a substituted or unsubstituted alkyl group, alicyclic hydrocarbon group or aryl group having 1 to 20 carbon atoms. In formula (b-2-1) and formula (b-2-2), A9 may represent an alkyl group having 1 to 12 carbon atoms or a fluoroalkyl group having 1 to 12 carbon atoms. In formula (b-2-3), A 10 represents an alkyl group, an alkoxy group or a halogen atom. i is an integer from 0 to 3, and when i is 2 or 3, multiple A 10 Can be the same as or different from each other.

[0165] A 10 The alkyl group represented may preferably be a linear or branched alkyl group having 1 to 4 carbon atoms. 10 The alkoxy group represented is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. 10 The halogen atom represented is preferably a chlorine atom or a fluorine atom.

[0166] The oxime sulfonate compound represented by formula (b-2-3) may be, for example, a compound represented by the following formula (b-2-4) to formula (b-2-8), etc.:

[0167]

[0168] The oxime sulfonate compound shown in formula (b-2-3) may be, for example, (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, 4-methylphenylsulfonyloxyimino-αt-(4-methoxyphenyl)acetonitrile, and commercially available products of the above compounds may be used.

[0169] The N-sulfonyloxy imide compound may be, for example, 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)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(4-fluorophenylsulfonyloxy)phthalimide, 2-(trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic imide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic imide, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic imide, N-(nonafluorobutanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic imide, N-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic imide imide, N-(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide -5-ene-2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxyl-2,3-dicarboximide, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxyl-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxyl-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)naphthalene dicarboximide, N-(camphorsulfonyloxy)naphthalene dicarboximide, N-(4-methylphenylsulfonyloxy)naphthalene dicarboximide, N-(phenylsulfonyloxy)naphthalene dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)naphthalene dicarboximide, N-(4-fluorophenylsulfonyloxy)naphthalene dicarboximide, N-(pentafluoroethylsulfonyloxy)naphthalene dicarboximide, N-(heptafluoropropylsulfonyloxy)naphthalene dicarboximide, N- (Nonafluorobutylsulfonyloxy)naphthalene dicarboximide, N-(ethylsulfonyloxy)naphthalene dicarboximide, N-(propylsulfonyloxy)naphthalene dicarboximide, N-(butylsulfonyloxy)naphthalene dicarboximide, N-(pentylsulfonyloxy)naphthalene dicarboximide, N-(hexylsulfonyloxy)naphthalene dicarboximide, N-(heptylsulfonyloxy)naphthalene dicarboximide, N-(octylsulfonyloxy)naphthalene dicarboximide or N-(nonylsulfonyloxy)naphthalene dicarboximide, etc.

[0170] As the onium salt, halogen-containing compound, diazomethane compound, sulfone compound, sulfonate compound, carboxylate compound, etc., compounds described in Japanese Patent Application Laid-Open No. 2011-232632 can be used, for example, benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate.

[0171] The photoacid generator (B) mentioned above may be used alone or in combination of two or more.

[0172] Based on 100 parts by weight of the resin (A), the photoacid generator (B) may be used in an amount of 0.3 to 20 parts by weight, preferably 0.4 to 19 parts by weight, and more preferably 0.5 to 18 parts by weight.

[0173] Solvent (C)

[0174] The solvent (C) of the present invention is not particularly limited. Specific examples of the solvent (C) include compounds containing alcoholic hydroxyl groups or cyclic compounds containing carbonyl groups.

[0175] Specific examples of the compound containing an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (also called 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 (PGEE), propylene glycol mono-n-propyl ether (PGEE), ...butyl ether (PGEE), propylene glycol mono-n-propyl ether (PGEE), propylene glycol mono-n-butyl ether (PGEE), propylene glycol mono-n-butyl ether (PGEE), propylene glycol mono-n-butyl ether (PGEE), propylene glycol mono-n-butyl ether (PGEE), propylene glycol mono-methyl ether acetate (PGMEA), propylene glycol mono-n-propyl ether (PGEE), propylene glycol mono-n-butyl ether (PGEE), propylene glycol mono-n- 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. Preferably, the compound containing an alcoholic hydroxyl group may be diacetone alcohol, ethyl lactate, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate or a combination thereof. The aforementioned compounds containing an alcoholic hydroxyl group may be used alone or in combination of multiple types.

[0176] Specific examples of carbonyl-containing cyclic compounds are γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methyl pyrrolidone, cyclohexanone or cycloheptanone. Preferably, the carbonyl-containing cyclic compound may be γ-butyrolactone, N-methyl pyrrolidone, cyclohexanone or a combination thereof. The aforementioned carbonyl-containing cyclic compounds may be used alone or in combination.

[0177] The alcoholic hydroxyl group-containing compound can be used in combination with the carbonyl group-containing cyclic compound, and the weight ratio thereof is not particularly limited. The weight ratio of the alcoholic hydroxyl group-containing compound to the carbonyl group-containing cyclic compound is preferably 99 / 1 to 50 / 50, and more preferably 95 / 5 to 60 / 40.

[0178] The solvent (C) may also include other solvents within the scope that does not impair the effects of the present invention. Specific examples of the other solvents may include: (1) esters: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate or 3-methyl-3-methoxy-1-butyl acetate, etc.; (2) ketones: methyl isobutyl ketone, diisopropyl ketone or diisobutyl ketone, etc.; or (3) ethers: diethyl ether, diisopropyl ether, di-n-butyl ether or diphenyl ether, etc.

[0179] The aforementioned solvent (C) may be used alone or in combination of two or more.

[0180] Based on 100 parts by weight of the resin (A), the amount of the solvent (C) may be 50 parts by weight to 1500 parts by weight, preferably 80 parts by weight to 1400 parts by weight, and more preferably 100 parts by weight to 1300 parts by weight.

[0181] Sensitizer (D)

[0182] The chemically amplified positive-type photosensitive resin composition of the present invention may selectively include a sensitizer (D) represented by the following formula (d-1):

[0183]

[0184] In formula (d-1), X1 and X2 independently represent an alkyl group, an aralkyl group, an alkoxyalkyl group, an aryloxyalkyl group or a glycidyl group; X3 and X4 independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group or a halogen atom; r1 and r2 independently represent an integer from 0 to 2, and the sum of r1 and r2 is 0 to 2, wherein multiple X3 and X4 are the same or different.

[0185] In formula (d-1), specific examples of the alkyl represented by X1 and X2 may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-decyl or n-dodecyl. Specific examples of the aralkyl represented by X1 and X2 may include benzyl or phenethyl. Specific examples of the alkoxyalkyl represented by X1 and X2 may include 2-methoxyethyl or 2-ethoxyethyl. Specific examples of the aryloxyalkyl represented by X1 and X2 may include 2-phenoxyethyl or 2-naphthyloxyethyl. Specific examples of the glycidyl represented by X1 and X2 may include glycidyl or 2-methylglycidyl.

[0186] In formula (d-1), specific examples of the alkyl represented by X3 and X4 may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl or 4-methylpentyl. Specific examples of the alkoxy represented by X3 and X4 may include methoxy, ethoxy, propoxy or butoxy. Specific examples of the aryloxy represented by X3 and X4 may include phenoxy. Specific examples of the halogen atom represented by X3 and X4 may include chlorine atom, bromine atom or iodine atom.

[0187] Specific examples of the sensitizer (D) represented by formula (d-1) include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-di(n-propoxy)anthracene, 9,10-di(isopropoxy)anthracene, 9,10-di(n-butoxy)anthracene, 9,10-di(isobutoxy)anthracene, 9,10-di(n-pentyloxy)anthracene, 9,10-di(n-hexyloxy)anthracene, 9,10-di(2-ethylhexyloxy)anthracene, 9,10-di(dodecyloxy)anthracene, 9,10-di(allyloxy)anthracene, 9,10-di(2-methylallyloxy)anthracene, 9,10-di(benzyloxy)anthracene, 9,10-di(phenethyloxy)anthracene, 9,10-bis(2-phenoxyethoxy)anthracene, 9,10-diglycidyloxy anthracene, 2-methyl-9,10-dimethoxyanthracene, 2-methyl-9,10-diethoxyanthracene, 2-methyl-9,10-di(n-propoxy)anthracene, 2-methyl-9,10-di(isopropoxy)anthracene, 2-methyl-9,10-di(n-butoxy)anthracene, 2-methyl-9,10-di(isobutoxy)anthracene, 2-methyl-9,10-di(n-pentyloxy)anthracene, 2-methyl-9,10-di(n-hexyloxy)anthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-ethyl-9,10-di(n-propoxy)anthracene, 2-ethyl-9,10-di(isopropoxy)anthracene, 2-ethyl-9,10-di(n-butoxy)anthracene, 2-ethyl-9,10-di 2-tert-butyl-9,10-di(n-pentyloxy)anthracene, 2-tert-butyl-9,10-di(n-hexyloxy)anthracene, 2-tert-butyl-9,10-dimethoxyanthracene, 2-tert-butyl-9,10-diethoxyanthracene, 2-tert-butyl-9,10-di(n-propoxy)anthracene, 2-tert-butyl-9,10-di(isopropoxy)anthracene, 2-tert-butyl-9,10-di(n-butoxy)anthracene, 2-tert-butyl-9,10-di(isobutoxy)anthracene, 2-tert-butyl-9,10-di(n-pentyloxy)anthracene, 2-tert-butyl-9,10-di(n-hexyloxy)anthracene, 2-(4-methylpentyl)-9,10-dimethoxyanthracene, 2-(4-methylpentyl)-9,10-diethoxyanthracene, 2-(4 2-(4-methylpentyl)-9,10-di(n-propoxy)anthracene, 2-tert-butyl-9,10-di(isopropoxy)anthracene, 2-(4-methylpentyl)-9,10-di(n-butoxy)anthracene, 2-(4-methylpentyl)-9,10-di(isobutoxy)anthracene, 2-(4-methylpentyl)-9,10-di(n-pentyloxy)anthracene, 2-(4-methylpentyl)-9,10-di(n-hexyloxy)anthracene, 2-chloro-9,10-dimethoxyanthracene, 2-chloro-9,10-diethoxyanthracene, 2-chloro-9,10-di(n-propoxy)anthracene, 2-chloro-9,10-di(isopropoxy)anthracene, 2-chloro-9,10-di(n-butoxy)anthracene, 2-chloro-9,10-di(isobutoxy)anthracene, 2-chloro-9,10-di(n-butoxy)anthracene,10-di(n-pentyloxy)anthracene, 2-chloro-9,10-di(n-hexyloxy)anthracene, 2-phenoxy-9,10-dimethoxyanthracene, 2-phenoxy-9,10-diethoxyanthracene, 2-phenoxy-9,10-di(n-propoxy)anthracene, 2-phenoxy-9,10-di(isopropoxy)anthracene, 2-phenoxy-9,10-di(n-butoxy)anthracene, 2-phenoxy-9,10-di(isobutoxy)anthracene, 2-phenoxy-9,10-di(n-pentyloxy)anthracene, 2-phenoxy-9,10-di( 2,3-dimethyl-9,10-di(n-hexyloxy)anthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-diethoxyanthracene, 2,3-dimethyl-9,10-di(n-propoxy)anthracene, 2,3-dimethyl-9,10-di(isopropoxy)anthracene, 2,3-dimethyl-9,10-di(n-butoxy)anthracene, 2,3-dimethyl-9,10-di(isobutoxy)anthracene, 2,3-dimethyl-9,10-di(n-pentyloxy)anthracene or 2,3-dimethyl-9,10-di(n-hexyloxy)anthracene, etc.

[0188] The sensitizer (D) as shown in the formula (d-1) mentioned above is preferably 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-di(n-propoxy)anthracene, 9,10-di(n-butoxy)anthracene, 2-methyl-9,10-di(n-butoxy)anthracene, 2-phenoxy-9,10-diethoxyanthracene, 2-chloro-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-dimethoxyanthracene or 9,10-diglycidyloxyanthracene.

[0189] The aforementioned sensitizer (D) may be used alone or in combination of two or more.

[0190] Based on 100 parts by weight of the resin (A), the amount of the sensitizer (D) may be 0.01 to 0.75 parts by weight, preferably 0.03 to 0.7 parts by weight, and more preferably 0.05 to 0.6 parts by weight.

[0191] If the chemically amplified positive-type photosensitive resin composition of the present invention contains a sensitizer (D), the development adhesion of the obtained cured film can be further improved.

[0192] Additives (E)

[0193] The chemically amplified positive photosensitive resin composition of the present invention may selectively include an additive (E) within the scope of not affecting the efficacy of the present invention. Specific examples of the additive (E) include, for example, an adhesion auxiliary agent, a surfactant, a solubility promoter, a defoamer, or a combination thereof.

[0194] Specific examples of the adhesion aid include melamine compounds and silane compounds.

[0195] Specific examples of melamine include commercial products manufactured by Mitsui Chemicals and sold under the trade names of Cymel-300, Cymel-303, etc., or commercial products manufactured by Sanwa Chemicals and sold under the trade names of MW-30MH, MW-30, MS-11, MS-001, MX-750, or MX-706, etc.

[0196] When the melamine compound is used as the adhesion aid, based on 100 parts by weight of the resin (A), the amount of the melamine compound is 0 to 20 parts by weight, preferably 0.5 to 18 parts by weight, and more preferably 1.0 to 15 parts by weight.

[0197] Specific examples of silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, nitrogen-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, or commercially available products manufactured by Shin-Etsu Chemical Co., Ltd. (trade name such as KBM403), etc.

[0198] When a silane compound is used as an adhesion promoter, based on 100 parts by weight of the resin (A), the amount of the silane compound used is 0 to 2 parts by weight, preferably 0.05 to 1 part by weight, and more preferably 0.1 to 0.8 parts by weight.

[0199] Specific examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane surfactants, fluorine surfactants, or a combination thereof.

[0200] Specific examples of surfactants include (1) polyethylene oxide alkyl ethers: polyethylene oxide dodecyl ether, etc.; (2) polyethylene oxide alkyl phenyl ethers: polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether, etc.; (3) polyethylene glycol diesters: polyethylene glycol dilaurate, polyethylene glycol distearate, etc.; (4) sorbitan fatty acid esters; (5) fatty acid modified polyesters; and (6) tertiary amine modified polyurethanes, etc. Specific examples of commercially available products of surfactants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow (manufactured by Kyoeisha Oil Chemical Industry), F-Top (manufactured by Tochem Products Co., Ltd.), Megaface (manufactured by Dainippon Ink Chemicals (DIC)), Fluorade (manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Asahi Glass), SINOPOL E8008 (manufactured by Chu-Nippon Synthetic Chemical), F-475 (manufactured by Dainippon Ink Chemicals), or any combination of the above compounds.

[0201] Based on 100 parts by weight of the resin (A), the amount of the surfactant is 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, and more preferably 3 to 30 parts by weight.

[0202] Specific examples of the dissolution accelerator may include N-hydroxydicarboxylic imide compounds or phenolic hydroxyl group-containing compounds.

[0203] Based on 100 parts by weight of the resin (A), 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.

[0204] Specific examples of the defoaming agent may include Surfynol MD-20, Surfynol MD-30, EnviroGem AD01, EnviroGem AE01, EnviroGem AE02, Surfynol DF 110D, Surfynol 104E, Surfynol 420, Surfynol DF37, Surfynol DF58, Surfynol DF66, Surfynol DF70, and Surfynol DF210 (manufactured by Air Products and Chemicals, Inc.), and the like.

[0205] The aforementioned adhesion promoter, surfactant, dissolution promoter and defoaming agent may be used alone or in combination.

[0206] Method for producing chemically amplified positive photosensitive resin composition

[0207] The chemically amplified positive photosensitive resin composition of the present invention can be prepared by the following method: resin (A), photoacid generator (B) and solvent (C) are placed in a stirrer and stirred to uniformly mix them into a solution state. If necessary, a sensitizer (D) and / or an additive (E) can be added.

[0208] Preparation method of hardened film and component

[0209] The present invention also provides a hardened film, which is formed by coating the chemically amplified positive photosensitive resin composition on a substrate, and then performing pre-baking, exposure, development and post-baking treatments.

[0210] The present invention further provides a device with a hardened film. The device comprises a substrate and the hardened film, and the hardened film is attached to the substrate.

[0211] In some embodiments, the chemically amplified positive photosensitive resin composition of the present invention can be used as a material for forming a hardened film of a display device. In addition, the present invention also includes a hardened film for a display device formed from the chemically amplified positive photosensitive resin composition.

[0212] The method for forming a cured film comprises the following steps: a step of forming a coating film on a substrate using a chemically amplified positive photosensitive resin composition (hereinafter referred to as step (1)); a step of irradiating at least a portion of the coating film with radiation (hereinafter referred to as step (2)); a step of developing the coating film after irradiation with radiation (hereinafter referred to as step (3)); and a step of heating the developed coating film (hereinafter referred to as step (4)).

[0213] According to this formation method, a hardened film for display elements having excellent surface hardness, solvent resistance, heat resistance, and voltage holding rate can be formed. In addition, by using a chemically amplified positive photosensitive resin composition having good high temperature and high humidity reliability and development adhesion, a hardened film for display elements having fine and delicate patterns can be easily formed. Therefore, the formed hardened film for display elements is suitable for display elements such as liquid crystal display elements or organic EL display elements.

[0214] Step (1): In this step, a chemically amplified positive photosensitive resin composition is coated on a substrate to form a coating film. Preferably, the coating film is pre-baked to remove the solvent. The substrate may be, for example, glass, quartz, a silicon substrate or a resin. The resin may be, for example, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, a ring-opening polymer of a cyclic olefin and a hydride thereof. The pre-baking conditions also vary depending on the type of each component, the blending ratio, etc., and can be set to 70°C to 120°C and performed for 1 minute to 10 minutes.

[0215] Step (2): In this step, at least a portion of the coating film formed above is exposed by irradiating radiation. During exposure, exposure is usually performed through a photomask having a predetermined pattern. The radiation used for exposure is preferably radiation with a wavelength in the range of 190nm to 450nm, and more preferably radiation containing 365nm ultraviolet rays. The exposure amount is a value obtained by measuring the intensity of radiation with a wavelength of 365nm using an illuminometer (manufactured by OAI Optical Associates, and the model is OAI model 356), and is preferably 500J / m 2 Up to 6,000J / m 2 , and more preferably 1,500 J / m 2 Up to 1,800 J / m 2 .

[0216] Step (3): In this step, the coating film irradiated with radiation is developed. By developing the exposed coating film, unnecessary parts (irradiated parts of radiation) are removed to form a predetermined pattern. The developer used in the development step is preferably an alkaline aqueous solution. The alkali can be, for example, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate or amine; a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide.

[0217] A water-soluble organic solvent or a surfactant such as methanol or ethanol may be added in an appropriate amount to the alkaline aqueous solution. From the viewpoint of obtaining appropriate developability, the concentration of the alkali in the alkaline aqueous solution is preferably not less than 0.1% by mass and not more than 5% by mass. The developing method may be, for example, a puddle method, an immersion method, a shaking immersion method or a spray method. The developing time varies depending on the composition of the chemically amplified positive photosensitive resin composition, and the developing time may be, for example, 1 second to 180 seconds. After the developing treatment, for example, running water washing is performed for 30 seconds to 90 seconds, and then the coating is air-dried using, for example, compressed air or compressed nitrogen to form the desired pattern.

[0218] Step (4): In this step, the developed coating film is heated. During heating, the patterned film is heated by using a heating device such as a heating plate or an oven to promote the curing reaction of the resin (A) and obtain a cured product. The heating temperature is, for example, 120°C to 250°C. The heating time varies depending on the type of heating machine, for example, 5 minutes to 30 minutes on a heating plate and 30 minutes to 90 minutes in an oven. In addition, a staged baking method that performs more than two heating steps can also be used. In this way, a patterned film corresponding to the target display element cured film can be formed on the surface of the substrate. In addition, the use of the above-mentioned cured film is not limited to the cured film for display elements, and can also be used as a spacer or an interlayer insulating film.

[0219] The film thickness of the formed cured film for display elements is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and even more preferably 0.1 μm to 4 μm.

[0220] The following embodiments are used to illustrate the application of the present invention, but they are not used to limit the present invention. Anyone skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. DETAILED DESCRIPTION

[0221] Preparation of resin (A)

[0222] Preparation Example A-1-1

[0223] A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were set on a 1000 ml four-necked conical flask. After the nitrogen was introduced, 10 parts by weight of 1-ethoxyethyl methacrylate (hereinafter referred to as MAEVE), 20 parts by weight of the compound (a211) represented by the formula (a2-1-1), 10 parts by weight of the compound (a311) represented by the formula (a3-1-2), 18 parts by weight of methacrylic acid (hereinafter referred to as MAA), 2 parts by weight of the compound (a5-4-1) represented by the formula (a511), 15 parts by weight of glycidyl methacrylate (hereinafter referred to as GMA), 25 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 diethylene glycol dimethyl ether (hereinafter referred to as Diglyme) were added. Then, the above components were slowly stirred to raise the temperature of the solution to 70° C. and polymerized at this temperature for 6 hours. Then, the solvent is devolatilized to obtain the resin (A-1-1) of Preparation Example A-1-1.

[0224] Preparation Examples A-1-2 to A-1-10, Preparation Examples A-2-1 and A-2-2

[0225] Preparation Examples A-1-2 to A-1-10, A-2-1 and A-2-2 use the same preparation method as the preparation method of the resin (A-1-1) of Preparation Example A-1-1, the difference being that the types and amounts of raw materials in the resin are changed in Preparation Examples A-1-2 to A-1-10, A-2-1 and A-2-2. The formulas are shown in Table 1 and are not described in detail here.

[0226]

[0227] Preparation of chemically amplified positive photosensitive resin composition

[0228] Example 1

[0229] 100 parts by weight of the resin (A-1-1) prepared in Preparation Example A-1-1, 0.3 parts by weight of the compound (B-1-1) represented by formula (b-1-1), and 0.01 parts by weight of 9,10-dimethoxyanthracene (D-1) were added to 50 parts by weight of propylene glycol methyl ether acetate (C-1), and stirred evenly with a shaking type stirrer to obtain the chemically amplified positive photosensitive resin composition of Example 1. The obtained chemically amplified positive photosensitive resin composition was evaluated by the following evaluation method, and the results are shown in Table 2, wherein the detection methods of high temperature and high humidity reliability and development adhesion will be described later.

[0230] Examples 2 to 16 and Comparative Examples 1 to 6

[0231] Examples 2 to 16 and Comparative Examples 1 to 6 use the same preparation method as that of the chemically amplified positive photosensitive resin composition of Example 1, the difference is that Examples 2 to 16 and Comparative Examples 1 to 6 change the types and usage amounts of raw materials in the chemically amplified positive photosensitive resin composition. The formulations and evaluation results are shown in Table 2, which are not further described here.

[0232] Evaluation method

[0233] High temperature and high humidity reliability

[0234] The chemically amplified positive photosensitive resin compositions prepared in Examples 1 to 16 and Comparative Examples 1 to 6 were applied to a glass substrate (100 mm×100 mm) by spin coating. Then, the coating was pre-baked at 110°C for 2 minutes with a gap of about 1 mm to form a coating film with a thickness of 3 μm. Then, the coating film was irradiated with a mercury lamp at 200 mJ / cm 2 Thereafter, the film was heated in an oven at 230°C for 30 minutes to form a cured film.

[0235] The above-mentioned cured film was placed in an oven at a temperature of 85°C, a pressure of 2 atm, and a relative humidity of 85%. After 24 hours, the cured film was cut into 100 base plates with a knife. After sticking with tape and then tearing it off, observe the remaining base plates, and evaluate the high temperature and high humidity reliability of the cured film according to the following criteria. Among them, the less base plates fall off, the better the high temperature and high humidity reliability of the cured film.

[0236] ◎: No base plate fell off.

[0237] ○: 0%<the number of base disc meshes that fall off ≤5%.

[0238] △: 5%<the number of base disc meshes that fall off≤35%.

[0239] ×: 35%<the number of base disc meshes that have fallen off≤100%.

[0240] Development Adhesion

[0241] The chemically amplified positive photosensitive resin compositions prepared in Examples 1 to 16 and Comparative Examples 1 to 6 were applied onto a glass substrate (100 mm×100 mm) by spin coating. Then, the compositions were pre-baked at 110° C. for 2 minutes with a gap of about 1 mm to form a coating film with a thickness of 3 μm.

[0242] Next, the coating film was irradiated with 50 mJ / cm2 using a mercury lamp through a pattern mask having a line and space pattern with a width of 1 μm to 10 μm. 2 After that, a 20-second development treatment was performed using a 23°C 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution. After removing the exposed part, it was rinsed with pure water for 15 seconds, and the developable line width of the developed pattern on the glass substrate was recorded. The development adhesion of the cured film was evaluated according to the following criteria. Among them, the smaller the developable line width, the better the adhesion during development.

[0243] ◎: Developable line width ≤ 5 μm.

[0244] ○: 5 μm<developable line width ≤ 10 μm.

[0245] △: 10μm<developable line width ≤ 20μm.

[0246] ×: Developable line width > 20 μm.

[0247] Table 2

[0248]

[0249] B-1-1 Compound represented by formula (b-1-11)

[0250] B-1-2 Compound represented by formula (b-1-12)

[0251] B-1-3 Compound represented by formula (b-1-13)

[0252] B-1-4 Compound represented by formula (b-1-14)

[0253] B-1-5 Compound represented by formula (b-1-15)

[0254] B-1-6 Compound represented by formula (b-1-16)

[0255] B-1-7 Compound represented by formula (b-1-1)

[0256] B-1-8 Compound represented by formula (b-1-4)

[0257] B-2-1 N-(Trifluoromethylsulfonyloxy)naphthalene ditoluene imide

[0258] B-2-2 (5-p-Toluenesulfonyloxyimino)-Sh-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile

[0259] C-1 Propylene glycol methyl ether acetate

[0260] C-2 Diethylene glycol methyl ethyl ether

[0261] D-1 9,10-dimethoxyanthracene

[0262] D-2 9,10-diethoxyanthracene

[0263] D-3 9,10-di(n-propoxy)anthracene

[0264] D-4 9,10-di(n-butoxy)anthracene

[0265] From the results in Table 2, it can be seen that if the first mixture used for polymerizing the resin (A-1) containing an acid dissociable group does not include the unsaturated monomer (a-2) containing two olefinic groups, the high temperature and high humidity reliability of the obtained cured film is poor. If the chemically amplified positive photosensitive resin composition of the present invention does not include the compound (B-1) containing an oxime sulfonate group, the development adhesion of the obtained cured film is poor.

[0266] Secondly, if the aforementioned first mixture includes an unsaturated monomer (a-3) containing a maleimide group, the high temperature and high humidity reliability of the obtained hardened film can be further improved. If the aforementioned oxime sulfonate group compound (B-1) has a structure as shown in formula (b-1), and A1 represents an alkyl group or a phenyl group substituted with a substituent having a carbon number of 1 to 6; A2 represents an alkyl group, a phenyl group or a nitrile group having a carbon number of 1 to 6; A3 to A7 independently represent a hydrogen atom, an alkyl group or a phenyl group having a carbon number of 1 to 6 and substituted or not substituted with an ether group (-O-) or a thioether group (-S-), and at least one of A3 to A7 contains an alkyl group having an ether group or a thioether group, the development adhesion of the obtained hardened film can be further improved. In addition, if the chemically amplified positive photosensitive resin composition of the present invention contains a sensitizer (D), the development adhesion of the obtained hardened film can be further improved.

[0267] It should be added that, although the present invention uses specific compounds, compositions, reaction conditions, processes, analysis methods or specific instruments as examples to illustrate the chemically amplified positive photosensitive resin composition, the cured film and the device having the cured film of the present invention, anyone with common knowledge in the technical field to which the present invention belongs will know that the present invention is not limited thereto, and the chemically amplified positive photosensitive resin composition, the cured film and the device having the cured film of the present invention may also be carried out using other compounds, compositions, reaction conditions, processes, analysis methods or instruments without departing from the spirit and scope of the present invention.

[0268] Although the present invention has been disclosed as above in the form of an implementation method, it is not intended to limit the present invention. Anyone with common knowledge in the technical field to which the present invention belongs can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be based on the scope defined by the attached claims.

Claims

1. A chemically amplified positive-type photosensitive resin composition, characterized in that: Include: A resin (A); a photoacid generator (B); and a solvent (C); The resin (A) comprises a resin (A-1) containing an acid-dissociable group, and the resin (A-1) containing an acid-dissociable group comprises a repeating unit containing an acid-dissociable group and a repeating unit having at least one structure selected from the following formulas (I-1) to (I-4); In formula (I-1) to formula (I-4), R1, R2, R3, R4, R5 and R6 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms; The photoacid generator (B) comprises a compound (B-1) having an oxime sulfonate group as shown in the following formula (b-1): In formula (b-1), A1 represents an alkyl group having 1 to 10 carbon atoms and which may be substituted or unsubstituted by a substituent; A2 represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, or a nitrile group; and A3 to A7 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and which may be substituted or unsubstituted by an ether group (-O-) or a thioether group (-S-), or an aryl group.

2. The chemically amplified positive-type photosensitive resin composition according to claim 1, characterized in that: The resin (A-1) containing an acid dissociable group further comprises a repeating unit represented by the following formula (II): In formula (II), R7 represents a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, a phenyl group which may be substituted with a substituent, a benzyl group, or a cycloalkyl group having 3 to 6 carbon atoms.

3. The chemically amplified positive-type photosensitive resin composition according to claim 1, characterized in that: The resin (A-1) containing an acid-dissociable group is formed by copolymerizing a first mixture, wherein the first mixture includes an unsaturated monomer (a-1) containing an acid-dissociable group and an unsaturated monomer (a-2) having a structure represented by formula (a2-1) or (a2-2) and two olefinic groups: In formula (a2-1) and formula (a2-2), R1, R2 and R3 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms.

4. The chemically amplified positive-type photosensitive resin composition according to claim 3, characterized in that: The first mixture further comprises an unsaturated monomer (a-3) containing a maleimide group as shown in the following formula (a3-1): In formula (a3-1), R7 represents a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, a phenyl group which may be substituted with a substituent, a benzyl group, or a cycloalkyl group having 3 to 6 carbon atoms.

5. The chemically amplified positive-type photosensitive resin composition according to claim 1, characterized in that: A1 represents an alkyl group or phenyl group having 1 to 6 carbon atoms which may be substituted or unsubstituted by a substituent; A2 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group or a nitrile group (-CN); A3 to A7 independently represent a hydrogen atom, an alkyl group or phenyl group having 1 to 6 carbon atoms which may be substituted or unsubstituted by an ether group (-O-) or a thioether group (-S-), and at least one of A3 to A7 comprises an alkyl group substituted by an ether group (-O-) or a thioether group (-S-).

6. The chemically amplified positive-type photosensitive resin composition according to claim 1, characterized in that: It also contains a sensitizer (D) represented by the following formula (d-1): In formula (d-1), X1 and X2 independently represent an alkyl group, an aralkyl group, an alkoxyalkyl group, an aryloxyalkyl group or a glycidyl group; X3 and X4 independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group or a halogen atom; r1 and r2 independently represent an integer from 0 to 2, and the sum of r1 and r2 is 0 to 2, wherein multiple X3 and X4 are the same or different.

7. The chemically amplified positive-type photosensitive resin composition according to claim 1, characterized in that: Based on an amount of 100 parts by weight of the resin (A), an amount of the resin (A-1) containing an acid-dissociable group is 30 parts by weight to 100 parts by weight, an amount of the photoacid generator (B) is 0.3 parts by weight to 20 parts by weight, an amount of the oxime sulfonate group compound (B-1) is 0.3 parts by weight to 15 parts by weight, and an amount of the solvent (C) is 50 parts by weight to 1500 parts by weight.

8. The chemically amplified positive-type photosensitive resin composition according to claim 3, characterized in that: Based on 100 parts by weight of the first mixture, the unsaturated monomer (a-2) is used in an amount of 2 parts by weight to 30 parts by weight.

9. The chemically amplified positive-type photosensitive resin composition according to claim 4, characterized in that: Based on 100 parts by weight of the first mixture, the unsaturated monomer (a-3) is used in an amount of 1 to 24 parts by weight.

10. The chemically amplified positive-type photosensitive resin composition according to claim 6, characterized in that: Based on 100 parts by weight of the resin (A), the sensitizer (D) is used in an amount of 0.01 to 0.75 parts by weight.

11. A hardened film, characterized in that: The method is formed by coating the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 10 on a substrate, and then performing pre-baking, exposure, development and post-baking treatments.

12. A component having a hardened film, characterized in that: The invention comprises a substrate and a hardened film according to claim 11, wherein the hardened film is attached to the substrate.

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