TWI864291B - Chemically-amplified type positive photo sensitive resin composition, protective film, and device with protective film - Google Patents

Abstract

A chemically-amplified type positive photo sensitive resin composition, a protective film, and a device with protective film are provided. The chemically-amplified type positive photo sensitive resin composition has good sensitivity and adhesion property when developing. The chemically-amplified type positive photo sensitive resin composition includes a resin with acid dissociation group (A), a photoacid generator (B), a solvent (C), a silane compound (D) and a block isocyanate compound (E). The silane compound (D) has a structure as shown in formula (D-1). (R ¹O) _nR ³ _(3-n)-Si-C _mH _2m-S-Si(R ²) ₃formula (D-1)

Description

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

The present invention relates to a chemically amplified positive photosensitive resin composition, in particular to a chemically amplified positive photosensitive resin having the advantages of good sensitivity and developing adhesion, as well as a protective film prepared therefrom and a device comprising the protective film.

Display elements such as thin film transistor type liquid crystal display elements or organic electroluminescence devices (organic EL elements) usually include insulating films such as interlayer insulating films or planarizing films, and such insulating films are usually formed using radiation-sensitive compositions. In order to meet the requirements of patterning performance, positive photosensitive resin compositions containing acid generators such as naphthoquinone diazide (see Japanese Patent Publication No. 2001-354822) are usually used, but many other photosensitive compositions have been proposed in recent years.

For example, Japanese Patent Publication No. 2004-4669 is about a positive type chemical amplification material that forms a hardened film for display elements. The positive type chemical amplification material has a higher sensitivity than the positive type photosensitive resin composition using an acid generator such as naphthoquinone dinitride. 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 decomposed by the action of an acid. Although the acid-dissociable resin itself is insoluble or poorly soluble in an alkaline aqueous solution, the protective group is decomposed by the action of an acid and becomes soluble in an alkaline aqueous solution. In addition, for example, Japanese Patent Publication No. 2004-264623, Japanese Patent Publication No. 2011-215596, and Japanese Patent Publication No. 2008-304902 also propose positive photosensitive compositions containing a resin having an acetal structure and/or a ketone structure and an epoxy group and an acid generator.

In addition to having high photosensitivity, the hardened film must also be fully adhered to the substrate after development and not easily peeled off, so that an ideal pattern can be formed.

However, current photosensitive resin compositions still have problems with poor development adhesion and sensitivity, and are still not accepted by the industry.

In view of this, the present invention provides a chemically amplified positive photosensitive resin composition, which can improve the above-mentioned problems of poor development adhesion and sensitivity.

The present invention provides a chemically amplified positive photosensitive resin composition, comprising: a resin containing an acid-dissociable group (A), a photoacid generator (B), a solvent (C), a silane compound (D), and a blocked isocyanate compound (E).

The silane compound (D) has a structure as shown in the following formula (D-1).

(R ¹ O) _n R ³ _(3-n) -Si-C _m H _2m -S-Si(R ² ) ₃ formula (D-1)

In formula (D-1), R ¹ represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms.

^R2 each independently represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 10 carbon atoms, an unsubstituted or substituted alkenyl group having 2 to 10 carbon atoms, or an unsubstituted or substituted organooxy group having 1 to 20 carbon atoms.

R ³ represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms.

n is an integer from 1 to 3; and m is an integer from 1 to 3.

In one embodiment of the present invention, the above-mentioned resin containing acid-dissociable groups (A) includes a resin containing acid-dissociable groups (A1), and the resin containing acid-dissociable groups (A1) is a copolymer formed by copolymerizing a first mixture. The first mixture includes an unsaturated carboxylic acid monomer (a1-1), an acid-dissociable group-containing monomer (a1-2) having an acid-dissociable group represented by the following formula (a1-II), and an unsaturated monomer containing a lactone structure (a1-3).

In formula (a1-II), R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group, an alicyclic alkyl group or an aryl group, wherein the hydrogen atom possessed by the alkyl group, the alicyclic alkyl group or the aryl group may be partially or completely substituted, and R ¹¹ and R ¹² are not hydrogen atoms at the same time. R ¹³ is an alkyl group, an alicyclic alkyl group, an aralkyl group or an aryl group, wherein the hydrogen atom possessed by the alkyl group, the alicyclic alkyl group, the aralkyl group and the aryl group may be partially or completely substituted. R ¹¹ and R ¹³ may be bonded to each other and form a cyclic ether structure together with the carbon atom bonded to R ¹¹ and the oxygen atom bonded to R ¹³ .

In one embodiment of the present invention, the unsaturated monomer (a1-3) containing a lactone structure is a compound represented by the following formula (a1-III):

In formula (a1-III), ^RX1 is a hydrogen atom or an alkyl group; ^RA2 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. When _n2 is greater than 1, the plurality of ^RA2s may be the same or different. ^A1 is a single bond or a divalent linking group; ^Z2 is a monocyclic or polycyclic structure containing -OC(=O)-; and _n2 is an integer greater than 0.

In one embodiment of the present invention, the photoacid generator (B) comprises a photoacid generator (B1) having the following structure (B-1):

In formula (B-1), R ²¹ represents a halogenated alkyl group having 1 to 12 carbon atoms or a halogenated aryl group having 6 to 10 carbon atoms, R ²² represents an alkyl group having 1 to 6 carbon atoms, and R ²³ represents a halogenated alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms.

In one embodiment of the present invention, the compound further comprises an alkaline compound (F) represented by the following formula (F-1): N(Y) _x (Z) _3-x Formula (F-1):

In formula (F-1), Y each independently represents an alkyl group with 4 or more carbon atoms, a cycloalkyl group with 3 or more carbon atoms, a phenyl group, or an aralkyl group; Z each independently represents a hydrogen atom or an alkyl group with 3 or less carbon atoms; and x represents an integer from 1 to 3.

In one embodiment of the present invention, the above-mentioned blocked isocyanate compound (E) is a compound having a blocked structure formed by any one of an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound.

In one embodiment of the present invention, the amount of the resin (A) containing an acid-dissociable group is 100 parts by weight, the amount of the photoacid generator (B) is 0.3 parts by weight to 3 parts by weight, the amount of the solvent (C) is 150 parts by weight to 1200 parts by weight, the amount of the silane compound (D) is 0.5 parts by weight to 5 parts by weight, and the amount of the blocked isocyanate compound (E) is 0.5 parts by weight to 5 parts by weight.

In one embodiment of the present invention, the amount of the resin (A) containing an acid-dissociable group is 100 parts by weight, and the amount of the resin (A1) containing an acid-dissociable group is 50 parts by weight to 100 parts by weight.

In one embodiment of the present invention, the amount of the resin (A) containing an acid-dissociable group is 100 parts by weight, and the amount of the photoacid generator (B1) is 0.3 parts by weight to 3 parts by weight.

In one embodiment of the present invention, the amount of the resin (A) containing an acid-dissociable group is 100 parts by weight, and the amount of the alkaline compound (F) is 0.05 to 0.5 parts by weight.

The present invention further provides a protective film formed by coating the chemically amplified positive photosensitive resin composition as described above on a substrate, and then performing pre-baking, exposure, development and post-baking treatments.

The present invention further provides a component with a protective film, comprising: a substrate, and the protective film as described above, and the protective film is attached to the substrate.

Based on the above, the chemically amplified positive photosensitive resin composition of the present invention uses a silane compound (D) with a specific structure and a blocked isocyanate compound (E). Therefore, the chemically amplified positive photosensitive resin composition can improve the technical problems of poor development adhesion and sensitivity in the previous technology.

In order to make the above features and advantages of the present invention more clearly understood, the following is a specific example and a detailed description with the accompanying drawings.

<Chemically amplified positive photosensitive resin composition>

The present invention provides a chemically amplified positive photosensitive resin composition, comprising: a resin containing an acid-dissociable group (A), a photoacid generator (B), a solvent (C), a silane compound (D), and a blocked isocyanate compound (E), and optionally an alkaline compound (F) and an additive (G). The silane compound (D) has a structure shown in formula (D-1).

Resin containing acid-dissociable groups (A)

The resin (A) containing an acid-dissociable group includes the resin (A1) containing an acid-dissociable group and other resins (A2) containing an acid-dissociable group.

Resin containing acid-dissociable groups (A1)

The resin containing an acid-dissociable group (A1) is a copolymer formed by copolymerizing the first mixture. The first mixture includes an unsaturated carboxylic acid monomer (a1-1), an acid-dissociable group-containing monomer (a1-2) having an acid-dissociable group represented by formula (a1-II), and an unsaturated monomer containing a lactone structure (a1-3). In addition, the first mixture may include other unsaturated monomers (a1-4) as appropriate.

Unsaturated carboxylic acid monomer (a1-1)

Unsaturated carboxylic acid monomer (a1-1) refers to a compound containing a carboxylic acid group or a carboxylic anhydride structure and an unsaturated bond for polymerization. Its structure is not particularly limited and may 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.

Specific examples of unsaturated monocarboxylic acid compounds include: (meth) acrylic acid, butenoic acid, α-chloroacrylic acid, ethyl acrylic acid, cinnamic acid, 2-(meth)acryloylethoxysuccinate, 2-(meth)acryloylethoxyhexahydrophthalate, 2-(meth)acryloylethoxyphthalate, ω-carboxy polycaprolactone polyol monoacrylate (trade name ARONIX M-5300, manufactured by Toa Gosei).

Specific examples of unsaturated dicarboxylic acid compounds include maleic acid, fumaric acid, methyl fumaric acid, itaconic acid, leuconic acid, etc.

In the specific example of the present invention, the unsaturated dicarboxylic acid anhydride compound is the anhydride compound of the aforementioned unsaturated dicarboxylic acid compound.

Specific examples of polycyclic unsaturated carboxylic acid compounds include: 5-carboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene.

Specific example of polycyclic unsaturated dicarboxylic acid compounds: 5,6-dicarboxylic acid bicyclo[2.2.1]hept-2-ene.

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

Preferred examples of unsaturated carboxylic acid monomers (a1-1) are acrylic acid, methacrylic acid, maleic anhydride, 2-methacryloylethoxysuccinate, 2-methacryloylethoxyhexahydrophthalic acid or a combination thereof.

The unsaturated carboxylic acid monomer (a1-1) can be used alone or in combination. Based on 100 parts by weight of the total amount of the first 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.

Monomer containing acid-dissociable group (a1-2)

The acid-dissociable group-containing monomer (a1-2) has an acid-dissociable group represented by the following formula (a1-II):

In formula (a1-II), R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group, an alicyclic alkyl group or an aryl group, wherein the hydrogen atom possessed by the alkyl group, the alicyclic alkyl group or the aryl group may be partially or completely substituted, and R ¹¹ and R ¹² are not hydrogen atoms at the same time; R ¹³ is an alkyl group, an alicyclic alkyl group, an aralkyl group or an aryl group, wherein the hydrogen atom possessed by the alkyl group, the alicyclic alkyl group, the aralkyl group and the aryl group may be partially or completely substituted; 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.

The acid-dissociable group of the monomer (a1-2) containing an acid-dissociable group is dissociated by the action of the acid generated from the photoacid generator (B) described later during exposure to generate a polar group, so that the resin (A) containing an acid-dissociable group that is originally insoluble or poorly soluble in an alkaline aqueous solution becomes soluble in an alkaline aqueous solution.

The monomer (a1-2) containing an acid-dissociable group is not particularly limited as long as it has a structure represented by formula (a1-II). The monomer (a1-2) containing an acid-dissociable group can be easily dissociated by an acid.

Examples of the alicyclic alkyl group represented by R ¹¹ and R ¹² include alicyclic alkyl groups having 3 to 20 carbon atoms. In addition, the alicyclic alkyl group having 3 to 20 carbon atoms may be polycyclic. Examples of the alicyclic alkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bornyl, norbornyl, adamantyl, and the like.

Examples of the aryl group represented by R ¹¹ and R ¹² include aryl groups having 6 to 14 carbon atoms. The aryl group having 6 to 14 carbon atoms may be a single ring, a structure formed by connecting single rings, or a condensed ring. Examples of the aryl group having 6 to 14 carbon atoms include phenyl and naphthyl.

From R ¹¹ and R Examples of the substituents of the substituted alkyl, alicyclic alkyl and aryl groups represented by ¹² include halogen atoms, hydroxyl groups, nitro groups, cyano groups, carboxyl groups, carbonyl groups, alicyclic alkyl groups (e.g., cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, bornyl groups, norbornyl groups and adamantyl groups), aryl groups (e.g., phenyl groups and naphthyl groups), alkoxy groups (e.g., methoxy groups, ethoxy groups, propoxy groups, n-butoxy groups, pentyl groups, hexyl groups, heptyl groups and octyl groups having 1 to 20 carbon atoms), acyl groups (e.g., acetyl groups, propionyl groups, butyryl groups and isobutyryl groups having 2 to 20 carbon atoms), acyloxy groups (e.g., acetyloxy groups, propionyl groups, butyryl groups, tert-butyryl groups, tert-butyloxy ... The present invention also includes acyloxy groups having 2 to 10 carbon atoms such as tripentyloxy, etc.), alkoxycarbonyl groups (for example, alkoxycarbonyl groups having 2 to 20 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, etc.), halogenated alkyl groups (for example, linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-tetradecyl, n-octadecyl, branched alkyl groups such as isopropyl, isobutyl, t-butyl, neopentyl, 2-hexyl, 3-hexyl, etc.; alicyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, adamantyl, etc.; groups obtained by replacing some or all of the hydrogen atoms of the above groups with halogen atoms), hydroxyalkyl groups (for example, hydroxymethyl, etc.), and the like.

The alkyl group, alicyclic hydrocarbon group, and aryl group represented by R ¹³ can be applied to the explanations of the groups represented by R ¹¹ and R ^12. In addition, the alkyl group represented by R ¹³ is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group, an ethyl group, and an n-propyl group. Examples of the aralkyl group represented by R ¹³ include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and the like.

R ¹¹ and R ¹³ may be bonded to each other to form a cyclic ether structure, preferably a cyclic ether structure having 3 to 20 ring members, more preferably a cyclic ether structure having 5 to 8 ring members, and even more preferably tetrahydrofuran and tetrahydropyran.

Examples of the group represented by formula (a1-II) include the group represented by the following formula, etc.

Examples of the acid-dissociable group-containing monomer (a1-2) include: 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-tert-butoxyethyl methacrylate, 1-(2-chloroethoxy)ethyl methacrylate, 1-(2-ethylhexyloxy)ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1-(2-cyclohexylethoxy)ethyl methacrylate, 1-benzyloxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 2-tetrahydrofuranyl methacrylate, methacrylate), 1-ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-tert-butoxyethyl acrylate, 1-(2-chloroethoxy)ethyl acrylate, 1-(2-ethylhexyloxy)ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, 1-(2-cyclohexylethoxy)ethyl acrylate, 1-benzyloxy Ethyl 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)ethoxybenzene Ethylene or m-1-(2-ethylhexyloxy)ethoxystyrene, p-1-n-propoxyethoxystyrene or m-1-n-propoxyethoxystyrene, p-1-cyclohexyloxyethoxystyrene or m-1-cyclohexyloxyethoxystyrene, p-1-(2-cyclohexylethoxy)ethoxystyrene or m-1-(2-cyclohexylethoxy)ethoxystyrene, p-1-benzyloxyethoxystyrene or m-1-benzyloxyethoxystyrene, etc.

The monomer (a1-2) containing an acid-dissociable group is preferably 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 1-benzyloxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 2-tetrahydrofuranyl methacrylate, and more preferably 2-tetrahydropyranyl methacrylate and 2-tetrahydrofuranyl methacrylate.

Based on the total usage of the first mixture being 100 parts by weight, the usage of the monomer (a1-2) containing an acid-dissociable group is 15 to 70 parts by weight, preferably 17 to 68 parts by weight, and more preferably 20 to 65 parts by weight.

If the monomer (a1-2) containing an acid-dissociable group is used in the first mixture of the resin (A1) containing an acid-dissociable group in the chemically amplified positive photosensitive resin composition of the present invention, better sensitivity can be obtained.

Unsaturated monomers containing lactone structure (a1-3)

The unsaturated monomer (a1-3) containing a lactone structure is a compound represented by the following formula (a1-III):

In formula (a1-III), ^RX1 is a hydrogen atom or an alkyl group; ^RA2 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; when _n2 is greater than 1, the plurality of ^RA2s may be the same or different; ^A1 is a single bond or a divalent linking group; ^Z2 is a monocyclic or polycyclic structure containing -OC(=O)-; and _n2 is an integer greater than 0.

The alkyl group represented by ^RX1 is preferably 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 (especially a fluorine atom).

^RA2 is preferably an alkyl group having 1 to 4 carbon atoms or a cyano group.

The divalent linking group of A ¹ can be exemplified by: linear, branched or cyclic alkylene groups, arylene groups, divalent groups such as -O-, -COO-, -S-, -NR"-, -CO-, -NR"CO-, -SO ₂ -, or groups containing combinations of these groups, R" is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. The divalent linking group of A ¹ is preferably a group containing at least one of -O-, -COO-, -S-, -NH- and -CO-, or a group containing a combination of these groups and -(CH ₂ ) _m -, m is an integer from 1 to 10, preferably an integer from 1 to 6, and more preferably an integer from 1 to 4.

^Z2 is preferably a monocyclic structure. When ^Z2 represents a monocyclic structure, it is preferably a lactone structure with 5 to 7 members, and more preferably a lactone structure with 5 or 6 members. When ^Z2 represents a polycyclic structure, it is preferably another ring structure condensed on the lactone structure to form a bicyclic structure or a spirocyclic structure. Other ring structures include cyclic alkyl groups with 3 to 20 carbon atoms, heterocyclic groups with 3 to 20 carbon atoms, and the like. The heterocyclic group is not particularly limited, and may include one 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 examples thereof include oxacyclopentane ring, oxane ring, and dioxane ring.

_n2 is preferably an integer from 0 to 4, more preferably an integer from 0 to 2, and further preferably 0. When _n2 represents an integer greater than 2, the plurality of ^RA2s may be the same or different. In addition, the plurality of ^RA2s may be bonded to each other to form a ring, but preferably they are not bonded to each other to form a ring.

The unsaturated monomer (a1-3) containing a lactone structure is preferably a compound represented by the following formula (a1-III-1):

In formula (a1-III-1), ^RX2 is a hydrogen atom or an alkyl group; ^RA3 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; when _n3 is greater than 1, the plurality of ^RA3s may be the same or different; ^A2 is a single bond or a divalent linking group; ^Z3 is a monocyclic or polycyclic structure containing -OC(=O)-; _n3 is an integer greater than 0; ^X1 is an oxygen atom or -NR"-, and R" is a hydrogen atom or an alkyl group.

The alkyl group represented by ^RX2 is preferably 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.

^RA3 is preferably an alkyl group having 1 to 4 carbon atoms or a cyano group.

The divalent linking group of A ² can be exemplified by: linear, branched or cyclic alkylene groups, arylene groups, divalent groups such as -O-, -COO-, -S-, -NR"-, -CO-, -NR"CO-, -SO ₂ -, or groups containing combinations of these groups, R" is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. Among them, the divalent linking group of A ² is preferably a group containing at least one of -COO-, -CO-, or a combination of these groups and -(CH ₂ ) _m -, m is an integer from 1 to 10, preferably an integer from 1 to 6, and more preferably an integer from 1 to 4. ^{A 2} is particularly preferably a single bond.

^Z3 is preferably a monocyclic structure. When ^Z3 represents a monocyclic structure, it is preferably a lactone structure with 5 to 7 members, and more preferably a lactone structure with 5 or 6 members. When ^Z3 represents a polycyclic structure, it is preferably another ring structure condensed on the lactone structure to form a bicyclic structure or a spirocyclic structure. Other ring structures include cyclic alkyl groups with 3 to 20 carbon atoms, heterocyclic groups with 3 to 20 carbon atoms, and the like. The heterocyclic group is not particularly limited, and may include one 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 examples thereof include oxacyclopentane ring, oxane ring, and dioxane ring.

_n3 is preferably an integer from 0 to 4, more preferably an integer from 0 to 2, and further preferably 0. When _n3 represents an integer greater than 2, the plurality of ^RA3 may be the same or different. In addition, the plurality of ^RA3 may be bonded to each other to form a ring, but preferably they are not bonded to each other to form a ring.

^X1 is preferably an oxygen atom. If ^X1 is -NR"-, R" can be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom.

The compound represented by formula (a1-III) preferably contains a structure represented by any one of the following formulas (LC1-1) to (LC1-21):

In formula (LC1-1) to formula (LC1-21), _Rb2 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. When n4 is greater than 1, multiple _Rb2 may be the same or different.

The structures represented by Formula (LC1-1) to Formula (LC1-21) may or may not have Rb ₂ ; preferably, they do not have Rb _{2 ,} that is, n4 is 0. Rb ₂ is preferably an alkyl group having 1 to 4 carbon atoms or a cyano group.

n4 is preferably an integer from 0 to 4, more preferably an integer from 0 to 2, and further preferably 0. When n4 represents an integer greater than 2, a plurality of _Rb2 may be the same or different. In addition, a plurality of _Rb2 may also be bonded to each other to form a ring, but preferably they are not bonded to each other to form a ring.

The compound represented by formula (a1-III) preferably contains 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 contains a structure represented by formula (LC1-1), formula (LC1-4) or formula (LC1-17).

Specific examples of the compound represented by formula (a1-III) include compounds represented by the following formulas (a1-III-2) to (a1-III-22):

The definition of R ^8e in formula (a1-III-2) to formula (a1-III-22) is the same as the definition of R ^X2 above.

Specific examples of the unsaturated monomer (a1-3) containing a lactone structure include compounds represented by the following formulas (a1-III-23) to (a1-III-33), preferably compounds represented by the following formulas (a1-III-23) to (a1-III-28):

Based on the total usage of the first mixture being 100 parts by weight, the usage of the unsaturated monomer (a1-3) containing a lactone structure is 1 to 15 parts by weight, preferably 1 to 14 parts by weight, and more preferably 2 to 13 parts by weight.

If an unsaturated monomer (a1-3) containing a lactone structure is used in the first mixture of the resin (A1) containing an acid-dissociable group in the chemically amplified positive photosensitive resin composition of the present invention, better sensitivity can be obtained.

Other unsaturated monomers (a1-4)

Other unsaturated monomers (a1-4) include unsaturated monomers containing epoxy groups, alkyl (meth)acrylates, cycloalkyl (meth)acrylates, aryl (meth)acrylates, unsaturated dicarboxylic acid diesters, hydroxyalkyl (meth)acrylates, polyethers of (meth)acrylates, aromatic vinyl compounds, and other unsaturated compounds other than the above.

The epoxy-containing unsaturated monomer may include but is not limited to epoxy-containing (meth)acrylate compounds, epoxy-containing α-alkylacrylate compounds, epoxypropyl ether compounds, ethylenically unsaturated monomers having an oxycyclobutane group as shown in formula (a1-IV), and any combination thereof:

In formula (a1-IV), R ¹⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a hydrogen atom, a fluorine atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms or a perfluoroalkyl group having 1 to 4 carbon atoms; and a is an integer from 1 to 6.

Specific examples of epoxy group-containing (meth)acrylate compounds include: epoxypropyl (meth)acrylate, 2-methyl epoxypropyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxyhexyl (meth)acrylate, and 3,4-epoxyhexylmethyl (meth)acrylate.

Specific examples of epoxy-containing α-alkyl acrylate compounds include: α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, and α-ethyl acrylate 6,7-epoxyheptyl acrylate.

Specific examples of epoxypropane compounds include o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, and p-vinylbenzylglycidylether.

Specific examples of the ethylenically unsaturated monomer having an oxacyclobutane group as represented by formula (a1-IV) may include but are not limited to methacrylate compounds, acrylate compounds, or unsaturated monomers having structures represented by the following formulas (a1-IV-1) to (a1-IV-4):

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-(methacryloyloxymethyl)-3-methyloxetane [3-(methacryloyloxymethyl)-3-methyloxetane; MOXMA], 3-(methacryloyloxymethyl)-2-methyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane alkane, 3-(methacryloyloxymethyl)-2,2-difluorooxycyclobutane, 3-(methacryloyloxymethyl)-2,2,4-trifluorooxycyclobutane, 3-(methacryloyloxymethyl)-2,2,4,4-tetrafluorooxycyclobutane, 3-(methacryloyloxyethyl)oxycyclobutane, 3-(methacryloyloxyethyl)-3-ethyloxycyclobutane, 2-ethyl-3-(methacryloyloxyethyl)oxycyclobutane, 3-(methacryloyloxyethyl)-2,2,4,4-tetrafluorooxycyclobutane Compounds such as (1,2-difluoro-3-(methacryloyloxyethyl)-2-trifluoromethyloxycyclobutane, (3-(methacryloyloxyethyl)-2-pentafluoroethyloxycyclobutane, (3-(methacryloyloxyethyl)-2-phenyloxycyclobutane, (2,2-difluoro-3-(methacryloyloxyethyl)oxycyclobutane, (3-(methacryloyloxyethyl)-2,2,4-trifluorooxycyclobutane or (3-(methacryloyloxyethyl)-2,2,4,4-tetrafluorooxycyclobutane).

The acrylate compound may include but is not limited to 3-(acryloyloxymethyl)oxycyclobutane, 3-(acryloyloxymethyl)-3-ethyloxycyclobutane, 3-(acryloyloxymethyl)-3-methyloxycyclobutane, 3-(acryloyloxymethyl)-2-methyloxycyclobutane, 3-(acryloyloxymethyl)-2-trifluoromethylcyclobutane, 3-(Acryloyloxymethyl)-2-pentafluoroethyloxycyclobutane, 3-(Acryloyloxymethyl)-2-phenyloxycyclobutane, 3-(Acryloyloxymethyl)-2,2-difluorooxycyclobutane, 3-(Acryloyloxymethyl)-2,2,4-trifluorooxycyclobutane, 3-(Acryloyloxymethyl)- 2,2,4,4-tetrafluorooxycyclobutane, 3-(acryloyloxyethyl)oxycyclobutane, 3-(acryloyloxyethyl)-3-ethyloxycyclobutane, 2-ethyl-3-(acryloyloxyethyl)oxycyclobutane, 3-(acryloyloxyethyl)-2-trifluoromethyloxycyclobutane, 3-(acryloyloxyethyl)-2- Compounds such as pentafluoroethyloxycyclobutane, 3-(acryloyloxyethyl)-2-phenyloxycyclobutane, 2,2-difluoro-3-(acryloyloxyethyl)oxycyclobutane, 3-(acryloyloxyethyl)-2,2,4-trifluorooxycyclobutane or 3-(acryloyloxyethyl)-2,2,4,4-tetrafluorooxycyclobutane.

In some embodiments, the unsaturated monomer containing an epoxide group may further include other ethylenically unsaturated monomers having an oxadiazole group, such as 3-methyl-3-(vinyloxymethyl)oxadiazole [3-methyl-3-(vinyloxymethyl)oxadiazole; MOXV], 3-ethyl-3-(vinyloxymethyl)oxadiazole [3-ethyl-3-(vinyloxymethyl)oxadiazole; EOXV], 3-propyl-3-(vinyloxymethyl)oxadiazole, 3-methyl-3-(2-vinyloxyethyl)oxadiazole, 3-ethyl-3-(2-vinyloxyethyl)oxadiazole, 3-propyl-3-(2 -vinyloxyethyl)oxycyclobutane, 3-methyl-3-(3-vinyloxypropyl)oxycyclobutane, 3-ethyl-3-(3-vinyloxypropyl)oxycyclobutane, 3-propyl-3-(3-vinyloxypropyl)oxycyclobutane, 3-methyl-3-(3-vinyloxybutyl)oxycyclobutane, 3-ethyl-3-(3-vinyloxybutyl)oxycyclobutane )cyclohexyl butane, 3-propyl-3-(3-vinyloxybutyl)cyclohexyl butane, ethylene glycol [(3-ethyl-3-cyclohexylbutyl)methyl] vinyl ether, propylene glycol [(3-ethyl-3-cyclohexylbutyl)methyl] vinyl ether or 3,3-bis[(vinyloxy)methyl]cyclohexyl butane having a cyclohexyl butane group.

Specific examples of alkyl (meth)acrylates include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, dibutyl (meth)acrylate, and tertiary butyl (meth)acrylate.

Specific examples of cyclo(meth)acrylates include cyclohexyl(meth)acrylate, 2-methylcyclohexyl(meth)acrylate, tricyclo[5.2.1.0 ^2.6 ]dec-8-yl(meth)acrylate (or dicyclopentyl(meth)acrylate), dicyclopentyloxyethyl(meth)acrylate, isobornyl(meth)acrylate, and tetrahydrofuran(meth)acrylate.

Specific examples of (meth) aryl acrylates include: phenyl (meth) acrylate, benzyl (meth) acrylate.

Specific examples of unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, and diethyl itaconate.

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

Specific examples of polyethers of (meth)acrylates include polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate.

Specific examples of aromatic vinyl compounds include: styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene.

Specific examples of other unsaturated compounds other than the above 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, and N-(9-acridinyl)maleimide.

Other unsaturated monomers (a1-4) can be used alone or in combination. Based on the total usage of the first mixture of 100 parts by weight, the usage of other unsaturated monomers (a1-4) is 5 to 95 parts by weight, preferably 10 to 90 parts by weight, and more preferably 15 to 80 parts by weight.

Other resins containing acid-dissociable groups (A2)

As other resins (A2) containing acid-dissociable groups, there are no particular restrictions as long as they contain acid-dissociable groups and are different from the resins (A1) containing acid-dissociable groups. For example, a copolymer formed by copolymerization of the second mixture can be cited. The second mixture is different from the first mixture mentioned above in that the second mixture does not include an unsaturated monomer (a1-3) containing a lactone structure.

In addition, the specific examples of the unsaturated carboxylic acid monomer (a1-1), the acid-dissociable group-containing monomer (a1-2), and the other unsaturated monomer (a1-4) used in the production process of the other acid-dissociable group-containing resin (A2) are the same as the unsaturated carboxylic acid monomer (a1-1), the acid-dissociable group-containing monomer (a1-2), and the other unsaturated monomer (a1-4) used in the production process of the acid-dissociable group-containing resin (A1), and thus will not be described in detail here.

Synthesis method of resin (A) containing acid-dissociable groups

The synthesis method of the resin (A) containing an acid-dissociable group 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 produce the resin (A) containing an acid-dissociable group. For example, it is preferably synthesized by the following method: a solution containing a monomer and a free radical polymerization initiator is dripped into 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 dripped into a solution containing a reaction solvent or a monomer to carry out a polymerization reaction; a plurality of solutions containing each monomer and a solution containing a free radical polymerization initiator are dripped into a solution containing a reaction solvent or a monomer to carry out a polymerization reaction, etc.

The solvent used in the polymerization reaction of the acid-liquidable group-containing resin (A) includes, for example, the same solvents as those described below as solvent (C).

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, lauryl peroxide, tert-butylperoxytrimethylacetate, 1,1'-bis-(tert-butylperoxy)cyclohexane; hydrogen peroxide, etc.

In the polymerization reaction of the resin (A) containing an acid-dissociable group, a molecular weight regulator may be used in an appropriate amount to adjust the molecular weight. Examples of the molecular weight regulator include chloroform, carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolic acid, 3-tert-propionic acid, etc.

The polystyrene-equivalent weight average molecular weight (Mw) of the acid-dissociable group-containing resin (A1) 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.

The polystyrene-equivalent weight average molecular weight (Mw) of the other acid-dissociable group-containing resin (A2) obtained by colloid permeation chromatography is 2,000 to 32,000, preferably 3,000 to 22,000, and more preferably 4,000 to 12,000.

Based on the usage of 100 parts by weight of the resin (A) containing an acid-dissociable group, the usage of the resin (A1) containing an acid-dissociable group is 50 to 100 parts by weight, preferably 60 to 100 parts by weight, and more preferably 80 to 100 parts by weight.

If a resin (A1) containing an acid-dissociable group is used in a chemically amplified positive photosensitive resin composition, better sensitivity can be obtained.

Photoacid generator (B)

The photoacid generator (B) includes a photoacid generator (B1) having a structure of formula (B-1) and other photoacid generators (B2).

Photoacid generator (B1)

The photoacid generator (B1) has a structure represented by the following formula (B-1):

In formula (B-1), R ²¹ represents a halogenated alkyl group having 1 to 12 carbon atoms or a halogenated aryl group having 6 to 10 carbon atoms, R ²² represents an alkyl group having 1 to 6 carbon atoms, and R ²³ represents a halogenated alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms.

The alkyl group with carbon number of 1 to 6 can be a straight chain or a branched chain. For example, the alkyl group with carbon number of 1 to 4 can be methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl or hexyl.

Halogenated alkyl groups with 1 to 12 carbon atoms, such as alkyl groups with 1 to 8 carbon atoms, alkyl groups with 1 to 6 carbon atoms, or alkyl groups with 1 to 4 carbon atoms, which are mono- or poly-substituted with halogens. The degree of halogenation of the alkyl groups ranges from one hydrogen atom being substituted with halogens to all hydrogen atoms being substituted with halogens. Examples of the alkyl groups include fluoromethyl, trifluoromethyl, trichloromethyl, or 2-fluoropropyl, among which trifluoromethyl or trichloromethyl is preferred.

The halogen alkyl group having 1 to 12 carbon atoms can be exemplified by CF ₃ , C _p HF _2p , C _q F _2q+1 , wherein q represents an integer of 2 to 8, or an integer of 2 to 6, 2 to 4, 3 or 2; and p represents an integer of 1 to 8, or an integer of 1 to 6, 1 to 4, 1 to 3, 2 or 1.

Halogenated aryl groups with 6 to 10 carbon atoms are, for example, aryl groups substituted with one or more halogen atoms. For example, phenyl or naphthyl groups substituted with one or more halogen atoms, wherein the phenyl group is substituted with halogen atoms 1 to 5 times, or 1, 2 or 3 times, preferably 1 or 2 times; the naphthyl group is substituted with halogen atoms 1 to 7 times, or 1, 2 or 3 times, preferably 1 or 2 times.

Halogens are fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine, more preferably fluorine and chlorine, and even more preferably fluorine.

In the method for preparing the photoacid generator (B1), the method described in the prior art literature can be used, for example, to react the corresponding oxime, sulfonyl halide, especially chloride or anhydride, with an alkali or a mixture of alkalis in an inert solvent, or to react in an alkaline solvent; wherein the inert solvent can be tert-butyl methyl ether, tetrahydrofuran (THF), dimethoxyethane, dimethylacetamide (DMA) or dimethylformamide; the alkali or the mixture of alkalis can be trimethylamine, pyridine or 2,6-lutidine; the alkaline solvent can be pyridine. The method for preparing the photoacid generator (B1) is illustrated by the following example:

Wherein, R ²¹ , R ²² and R ²³ have the same definitions as above and are not further described herein. Hal represents a halogen atom, preferably chlorine.

The temperature of the above reaction is not particularly limited, for example, it can be -15℃~50℃, preferably 0℃~25℃.

^R21 is preferably a halogenalkyl group having 1 to 12 carbon atoms.

^R22 is preferably an alkyl group having 1 to 4 carbon atoms; more preferably a methyl group.

R ²³ is preferably a halogenalkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, more preferably n-propyl, -CH ₃ or -CF ₃ , further preferably -CH ₃ or -CF ₃ .

Specific examples of the photoacid generator (B1) include compounds represented by the following formulas (B-1-1) to (B-1-5):

Based on the usage of 100 parts by weight of the resin (A) containing an acid-dissociable group, the usage of the photoacid generator (B1) is 0.3 to 3 parts by weight, preferably 0.4 to 2.8 parts by weight, and more preferably 0.5 to 2.6 parts by weight.

If a photoacid generator (B1) is used in the chemically amplified positive photosensitive resin composition, better sensitivity can be obtained.

Other photoacid generators (B2)

Other photoacid generators (B2) may contain, in addition to oxime sulfonate compounds and N-sulfonyloxy amide compounds containing oxime sulfonate groups, onium salts, halogen-containing compounds, diazomethane compounds, sulfonate compounds, carboxylate compounds, etc.

The oxime sulfonate compound is a compound including an oxime sulfonate group represented by the following formula (B-2):

In formula (B-2), R ²⁶ is an alkyl group, alicyclic hydrocarbon group or aryl group having 1 to 20 carbon atoms, wherein the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group or aryl group may be partially or completely substituted; * is a bonding site.

The alkyl group represented by R ²⁶ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms.

The monovalent alicyclic hydrocarbon group represented by R ²⁶ is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms.

The aryl group represented by R ²⁶ is preferably an aryl group having 6 to 20 carbon atoms, more preferably phenyl, naphthyl, tolyl, or xylyl.

The substituents include, for example, alkyl groups with 1 to 5 carbon atoms, alkoxy groups, pendoxy groups, halogen atoms, etc.

Examples of the compound including an oxime sulfonate group represented by formula (B-2) include oxime sulfonate compounds represented by the following formulas (B-2-1) to (B-2-3):

In formula (B-2-1) to formula (B-2-3), R ²⁶ has the same meaning as R ²⁶ in formula (B-2). In formula (B-2-1) and formula (B-2-2), R ²⁷ is an alkyl group having 1 to 12 carbon atoms or a fluoroalkyl group having 1 to 12 carbon atoms. In formula (B-2-3), X is 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 Xs may be the same or different from each other.

The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom.

Examples of the oxime sulfonate compound represented by formula (B-2-3) include compounds represented by the following formulas (B-2-4) to (B-2-8):

The compounds represented by formula (B-2-4) to formula (B-2-8) are respectively: (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-α-(4-methoxyphenyl)acetonitrile, and the above compounds available on the market can be used.

Examples of the N-sulfonyloxy imide compounds include N-(trifluoromethylsulfonyloxy) dimethicone, N-(camphorsulfonyloxy) dimethicone, N-(4-methylphenylsulfonyloxy) dimethicone, N-(2-trifluoromethylphenylsulfonyloxy) dimethicone, N-(4-fluorophenylsulfonyloxy) dimethicone, N-(trifluoromethylsulfonyloxy) o-phenylenediamine, N-(camphorsulfonyloxy) dimethicone, N-(2-trifluoromethylphenylsulfonyloxy) dimethicone, N-(4-fluorophenylsulfonyloxy) dimethicone, N-(trifluoromethylsulfonyloxy) o-phenylenediamine, N-(camphorsulfonyloxy) dimethicone, N-(4-methylphenyl ... sulfonyloxy) phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy) diphenyl phthalimide, N-(camphorsulfonyloxy) diphenyl phthalimide, (4-methylphenylsulfonyloxy) diphenyl phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide N-(4-fluorophenylsulfonyloxy)diphenylcis-1-butene diimide, N-(phenylsulfonyloxy)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 ,3-dicarboxylic acid imide, N-(nonafluorobutanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(camphorsulfonyloxy)-7-oxahedralbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(trifluoromethylsulfonyloxy)-7-oxahedralbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(4-methylphenylsulfonyloxy)-7-oxahedralbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide Olefin-2,3-dicarboxylic acid imide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxahedralbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(4-fluorophenylsulfonyloxy)-7-oxahedralbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide imide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxy imide, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxy imide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxy imide, N-(2-trifluoromethylphenyl) N-((trifluoromethylsulfonyl)oxy)naphthalene dicarboxylic acid imide, ... 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 dimethyl imide, N-(ethylsulfonyloxy)naphthalene dimethyl imide, N-(propylsulfonyloxy)naphthalene dimethyl imide, N-(butylsulfonyloxy)naphthalene dimethyl imide, N-(pentylsulfonyloxy)naphthalene dimethyl imide, N-(hexylsulfonyloxy)naphthalene dimethyl imide, N-(heptylsulfonyloxy)naphthalene dimethyl imide, N-(octylsulfonyloxy)naphthalene dimethyl imide, N-(nonylsulfonyloxy)naphthalene dimethyl imide, etc.

The onium salts, halogen-containing compounds, diazomethane compounds, sulfonate compounds, carboxylate compounds, etc. may use compounds described in Japanese Patent Publication No. 2011-232632. For example: benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate.

Based on the usage of 100 parts by weight of the resin (A) containing an acid-dissociable group, the usage of the photoacid generator (B) is 0.3 to 3 parts by weight, preferably 0.4 to 2.9 parts by weight, and more preferably 0.5 to 2.8 parts by weight.

Solvent (C)

There is no particular restriction on the type of solvent (C). Specific examples of solvent (C) include compounds containing alcoholic hydroxyl groups or cyclic compounds containing carbonyl groups.

Specific examples of compounds containing alcoholic hydroxyl groups 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 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 (PGEE), propylene glycol mono-methyl ether acetate (PGMEA), propylene glycol mono-n-propyl ether (PGEE), propylene glycol mono-methyl ether acetate (PGMEA), propylene glycol mono-n-propyl ether (PGEE), propylene glycol mono-methyl ether acetate (PGMEA), propylene glycol mono-methyl ether acetate ...MEA), propylene glycol mono-methyl ether acetate (PGEE), propylene glycol mono-methyl ether acetate (PGMEA), propylene glycol mono-methyl ether acetate (PGMEA 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. It is worth noting that the alcoholic hydroxyl-containing compound is preferably diacetone alcohol, ethyl lactate, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate or a combination thereof. The alcoholic hydroxyl-containing compound can be used alone or in combination.

Specific examples of carbonyl-containing cyclic compounds are γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methyl pyrrolidone, cyclohexanone or cycloheptanone. It is worth noting that the carbonyl-containing cyclic compound is preferably γ-butyrolactone, N-methyl pyrrolidone, cyclohexanone or a combination thereof. The carbonyl-containing cyclic compound can be used alone or in combination.

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

Other solvents may also be contained within the scope that does not impair the effects of the present invention. 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-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.

Based on the usage of 100 parts by weight of the resin (A) containing an acid-dissociable group, the usage of the solvent (C) is 150 to 1200 parts by weight, preferably 180 to 1100 parts by weight, and more preferably 200 to 1000 parts by weight.

Silane compounds (D)

The silane compound (D) has a structure as shown in the following formula (D-1): (R ¹ O) _n R ³ _(3-n) -Si-C _m H _2m -S-Si(R ² ) ₃ Formula (D-1)

In formula (D-1), R ¹ represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms.

^R2 each independently represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 10 carbon atoms, an unsubstituted or substituted alkenyl group having 2 to 10 carbon atoms, or an unsubstituted or substituted organooxy group having 1 to 20 carbon atoms.

R ³ represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms.

n is an integer from 1 to 3; and m is an integer from 1 to 3.

The above structure can be specifically shown as the following formula (D-2) or formula (D-3).

(R ¹ O) _n Me _(3-n) -Si-C ₃ H ₆ -S-Si-Ph(R ⁴ ) ₂ formula (D-2)

In formula (D-2), R ¹ and n are the same as R ¹ and n in formula (D-1).

^R4 each independently represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 10 carbon atoms, an unsubstituted or substituted alkenyl group having 2 to 10 carbon atoms, or an unsubstituted or substituted organooxy group having 1 to 20 carbon atoms.

Me represents methyl; Ph represents phenyl.

(R ¹ O) _n Me _(3-n) -Si-C ₃ H ₆ -S-Si-OR ⁵ (R ⁴ ) ₂ formula (D-3)

In the formula (D-3), R ¹ , n, R ⁴ , and Me are the same as R ¹ , n, R ⁴ , and Me in the formula (D-2).

R ⁵ represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 10 carbon atoms, or an unsubstituted or substituted alkenyl group having 2 to 10 carbon atoms.

More specifically, the silane compound (D) has a structure as shown in the following formula (D-4) to formula (D-9):

In formula (D-4) to formula (D-9), R ¹ , n, Me, and Ph are the same as R ¹ , n, Me, and Ph in formula (D-2) and formula (D-3); and Et represents an ethyl group.

More specifically, R ¹ in formula (D-4) to formula (D-9) represents an ethyl group.

The alkyl and aryl groups represented by R ¹ include, for example, methyl, ethyl, propyl, butyl, and phenyl groups; methyl and ethyl groups are preferred, and ethyl groups are more preferred. The alkyl groups represented by R ² include, for example, methyl, ethyl, 3-butyl, octyl, decyl, and dodecyl groups; the aryl groups represented by R ² include, for example, phenyl, xylyl, and tolyl groups; the aralkyl groups represented by R ^{2 include, for example, benzyl groups; the alkenyl groups represented by R 2 include} , for example, vinyl, propenyl, and pentenyl groups; the organic oxy groups represented by R ² include, for example, alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, octyloxy, and dodecyloxy groups; aryloxy groups such as phenoxy groups; and alkenyloxy groups such as vinyloxy, propenyloxy, and pentenyloxy groups. Among them, alkyl groups having 1 to 6 carbon atoms, phenyl groups, and alkoxy groups having 1 to 20 carbon atoms are preferred; alkyl groups having 1 to 4 carbon atoms, phenyl groups, and alkoxy groups having 1 to 12 carbon atoms are more preferred. The alkyl or aryl group represented by R ³ is, for example, methyl, ethyl, phenyl, etc.; preferably, methyl. The alkyl group represented by R ⁴ is, for example, methyl, ethyl, tert-butyl, octyl, decyl, dodecyl, etc.; the aryl group represented by R ⁴ is, for example, phenyl, xylyl, tolyl, etc.; the aralkyl group represented by R ⁴ is, for example, benzyl, etc.; the alkenyl group represented by R ⁴ is, for example, vinyl, propenyl, pentenyl, etc.; the organic oxy group represented by R ⁴ is, for example, alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, octyloxy, dodecyloxy, etc.; aryloxy groups such as phenoxy, vinyloxy, propenyloxy, pentenyloxy, etc.; preferably, the same as R ² . The alkyl group, aryl group, aralkyl group, alkenyl group represented by R ⁵ may be, for example, methyl group, ethyl group, propyl group, butyl group, tert-butyl group, octyl group, decyl group, dodecyl group, phenyl group, benzyl group, vinyl group, propenyl group, pentenyl group, etc.; preferably, the alkyl group has 1 to 12 carbon atoms.

Specific examples of the silane compound (D) include compounds represented by the following formulas (D-10) to (D-17):

The silane compound (D) of the present invention is prepared, for example, by dehydrogenating a silane compound having one or more alkyl groups with a silane compound having one or more Si-H bonds in the presence of a catalyst.

Since the by-product of the above-mentioned manufacturing method of the present invention is hydrogen, there is no filter and the reaction can be carried out well under solvent-free conditions, which is a manufacturing method with extremely high productivity.

When producing the silane compound (D), a solvent may be used as needed. The solvent is not particularly limited as long as it is non-reactive with the raw material silane compound having an alkyl group or a silane compound having a Si-H bond. Specifically, examples include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and decane, ether solvents such as diethyl ether, tetrahydrofuran, and 1,4-dioxane, amide solvents such as dimethylformamide and N-methylpyrrolidone, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene.

At this time, regarding the preparation of the silane compounds (D) of the above formulas (D-1) to (D-9), a silane compound having a silane group represented by the following formula (D-i) and a silane compound having a Si-H bond represented by the following formula (D-ii) can be reacted in the presence of a catalyst to form a sulfur-silicon bond.

In formula (Di) and formula (D-ii), R ¹ , R ² , R ³ , n, and m are the same as R ¹ , R ² , R ³ , n, and m in formula (D-1).

When manufacturing the silane compound (D), among the necessary raw materials, specific examples of silane compounds having a silane group include α-butylmethyltrimethoxysilane, α-butylmethylmethyldimethoxysilane, α-butylmethyldimethylmethoxysilane, α-butylmethyltriethoxysilane, α-butylmethylmethyldiethoxysilane, α-butylmethyldimethylethoxysilane, γ-butylpropyltrimethoxysilane, γ-butylpropylmethyldimethoxysilane, γ-butylpropyldimethylmethoxysilane, γ-butylpropyltriethoxysilane, γ-butylpropylmethyldiethoxysilane, γ-butylpropyldimethylethoxysilane, etc., but are not limited thereto.

When manufacturing the silane compound (D), specific examples of organic compounds having Si-H bonds among the necessary raw materials include trimethylsilane, ethyldimethylsilane, diethylmethylsilane, triethylsilane, tert-butyldimethylsilane, tert-butyldiphenylsilane, triisopropylsilane, tri-n-butylsilane, triisobutylsilane, dimethylphenylsilane, diphenylmethylsilane, dimethyl-n-octylsilane, decyldimethylsilane, dodecyldimethylsilane, dimethylvinylsilane, triphenylsilane, trimethoxysilane, triethoxysilane, tributoxysilane, dimethylethoxysilane, dimethylbutoxysilane, dimethyloctyloxysilane, dimethyldodecyloxysilane, etc., but are not limited thereto.

When preparing the silane compound (D), a catalyst is necessary, such as a transition metal catalyst or a Lewis acid catalyst. The transition metal catalyst is, for example, a ruthenium catalyst, a rhodium catalyst, a palladium catalyst, an iridium catalyst, a platinum catalyst, a gold catalyst, etc., and a rhodium catalyst is preferred, and a RhCl(PPh ₃ ) ₃ catalyst is more preferred.

In addition, Lewis acid catalysts such as aluminum chloride, aluminum sulfate, tin chloride, tin chloride sulfate, iron chloride, boron trifluoride, pentafluorophenylboric acid, etc., especially pentafluorophenylboric acid is preferred.

When manufacturing the silane compound (D), in terms of reactivity and productivity, the ratio of the silane compound having a butyl group to the organic silicon compound having a Si-H bond is preferably in the range of 0.5 to 1.5 mol, especially 0.9 to 1.1 mol, relative to 1 mol of the butyl group.

When manufacturing the silane compound (D), in terms of reactivity and productivity, the ratio of the silane compound having a butyl group to the catalyst is preferably in the range of 0.000001 to 0.1 mol, particularly 0.000001 to 0.001 mol, relative to 1 mol of the butyl group.

When manufacturing the silane compound (D), the reaction temperature is not particularly limited. It is usually room temperature to below the boiling point of the reaction raw materials or organic solvents, preferably 50 to 150°C, and more preferably 60 to 120°C. The reaction time is not particularly limited as long as it is a time that allows the reaction to proceed. It is preferably about 30 minutes to 24 hours, and more preferably about 1 to 10 hours.

Based on the usage of 100 parts by weight of the resin (A) containing an acid-dissociable group, the usage of the silane compound (D) is 0.5 to 5 parts by weight; preferably 0.6 to 4.8 parts by weight; and more preferably 0.7 to 4.5 parts by weight.

If the silane compound (D) is not used in the chemically amplified positive photosensitive resin composition, its developing adhesion is poor.

Blocked isocyanate compounds (E)

As the blocked isocyanate compound (E), there is no particular limitation as long as it is a compound having a blocked isocyanate group. From the perspective of curability, a compound having two or more blocked isocyanate groups in one molecule is preferred. There is no particular upper limit on the number of blocked isocyanate groups, but it is preferably 6 or less.

The skeleton of the blocked isocyanate compound (E) is not particularly limited. As long as it is a compound having an isocyanate group in the molecule, the blocked isocyanate compound (E) can be obtained by blocking the isocyanate group in the above compound.

Examples of compounds having an isocyanate group in the molecule include aliphatic isocyanate compounds, alicyclic isocyanate compounds, or aromatic isocyanate compounds. More specifically, examples include: 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (1,6-hexamethylene diisocyanate), and 1,6-hexamethylene diisocyanate. diisocyanate, HDI), 1,3-propyl diisocyanate, 1,4-butyl diisocyanate, 2,2,4-trimethylhexyl diisocyanate, 2,4,4-trimethylhexyl diisocyanate, 1,9-nonyl diisocyanate, 1,10-decyl diisocyanate, 1,4-cyclohexyl diisocyanate, 2,2'-diethyl ether diisocyanate, 4,4'-diphenylmethane diisocyanate (4,4'-Diphenylmethane diisocyanate, 4,4'-MDI), o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 4,4'-diisocyanate dicyclohexylmethane, 1,3-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanatemethyl)cyclohexane, 1,5-naphthyl diisocyanate, p-xylene diisocyanate Isocyanate compounds such as phenyl diisocyanate, 4,4'-diisocyanate-3,3'-xylyl methane, 4,4'-diisocyanate diphenyl ether, tetrachlorophenyl diisocyanate, norbornyl diisocyanate, 1,3-hydroxylene diisocyanate, 1,4-hydroxylene diisocyanate, and polymers of these isocyanate compounds.

Among them, it is preferred to use any one selected from the following group as the compound having an isocyanate group in the molecule: toluene-2,4-diisocyanate (2,4-Toluene diisocyanate, 2,4-TDI), toluene-2,6-diisocyanate (2,6-Toluene diisocyanate, 2,6-TDI), isophorone diisocyanate (Isophorone diisocyanate, IPDI), 1,6-hexamethylene diisocyanate (1,6-Hexamethylene diisocyanate, HDI), 4,4'-diphenylmethane diisocyanate (4,4'-Diphenylmethane diisocyanate, 4,4'-MDI) and polymers of these isocyanate compounds. It is more preferable to use any one selected from 1,6-hexyl diisocyanate, isophorone diisocyanate and polymers of these isocyanate compounds as the compound having an isocyanate group in the molecule.

As for the polymer of isocyanate compound, there is no special limitation as long as it is a dimer or above. For example, it can be listed as: dimer (Biuret), tricyclic polymer (Isocyanurate) and adduct. The dimer is preferred.

The main structures of isocyanate compounds include dicondensation type, tricyclic polymerization type, addition type and difunctional prepolymerization type.

As the end-capping agent for forming the end-capping structure of the blocked isocyanate compound (E), there can be listed: oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, thiol compounds, imidazole compounds and imide compounds. Preferably, it is selected from any one of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds and pyrazole compounds. From the perspective of storage stability, it is more preferably selected from any one of oxime compounds, lactam compounds, phenol compounds and alcohol compounds. From the perspective of the transparency of the cured film, it is more preferably selected from any one of oxime compounds, lactam compounds, alcohol compounds, amine compounds, active methylene compounds and pyrazole compounds.

If the blocked isocyanate compound (E) contains a compound having a blocking structure formed by any one of an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound, the developing adhesion is better.

As oxime compounds, there are: aldoxime and ketoxime. Specific examples are: formaldehyde oxime, cyclohexylformaldehyde oxime, acetone oxime, butanone oxime, cyclohexanone oxime, benzophenone oxime, etc.

As lactam compounds, there are: caprolactam, 2-pyrrolidone, etc.

As phenolic compounds, there are: phenol, naphthol, cresol, xylenol, halogen-substituted phenol, etc.

As alcohol compounds, there can be listed: methanol, ethanol, n-propanol, n-butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, alkyl alcohol lactate, etc.

As amine compounds, primary amines and secondary amines can be listed. For example, aromatic amines, aliphatic amines, alicyclic amines, butanone oxime, cyclohexanone oxime, benzophenone oxime, etc. Specific examples are aniline, diphenylamine, cyclohexylamine, polyethyleneimine, etc.

As active methylene compounds, they include: diethyl malonate, dimethyl malonate, ethyl acetylacetate, methyl acetylacetate, etc.

As pyrazole compounds, there are: pyrazole, methylpyrazole, dimethylpyrazole, etc.

As thiol compounds, there can be listed: alkyl thiols, aryl thiols, etc.

Specific examples of the blocked isocyanate compound (E) include compounds represented by the following formulas (E-1) to (E-10):

The blocked isocyanate compound (E) can be used alone or in combination of two or more. Based on 100 parts by weight of the resin (A) containing an acid-dissociable group, the amount of the blocked isocyanate compound (E) used is 0.5 to 5 parts by weight; preferably 0.4 to 4.8 parts by weight; and more preferably 0.5 to 4.5 parts by weight.

If the blocked isocyanate compound (E) is not used in the chemically amplified positive photosensitive resin composition, the developing adhesion is poor.

Alkaline compounds (F)

There is no particular limitation on the alkaline compound (F) as long as it is compatible with the chemically amplified positive photosensitive resin composition, and examples thereof include compounds described in Japanese Patent Publication No. 9-006001.

The alkaline compound (F) preferably includes a compound represented by formula (F-1): N(Y) _x (Z) _3-x Formula (F-1)

In formula (F-1), Y each independently represents an alkyl group with 4 or more carbon atoms, a cycloalkyl group with 3 or more carbon atoms, a phenyl group, or an aralkyl group; Z each independently represents a hydrogen atom or an alkyl group with 3 or less carbon atoms; and x represents an integer from 1 to 3.

The compound represented by formula (F-1) is preferably a compound in which x is 2 or 3 and the groups represented by Y are the same.

If the carbon number of the alkyl group Y is less than 4, it is difficult to improve the stability of the photoresist over time. The carbon number is preferably 5 or more, especially 8 or more. There is no particular upper limit, but from the perspective of confirming the stability effect over time or commercial acquisition, it is 20 or less, especially 15 or less. In addition, when it exceeds 20, the alkaline strength is weakened, which reduces the storage stability effect.

The alkyl group may be a straight chain or a branched chain. Specifically, n-decyl, n-octyl, n-pentyl, etc. are preferred.

Among the cycloalkyl groups as group Y, cycloalkyl groups with 4 to 8 carbon atoms are commercially available and have excellent effects in improving stability over time, making them more suitable. Cyclohexyl groups with 6 carbon atoms are more preferred.

As the aralkyl group Y, the group represented by formula (F-1a) can be listed: -R'-P Formula (E-1a)

In formula (E-1a), R' represents an alkylene group; P represents an aromatic hydrocarbon group.

As the group P, phenyl, naphthyl, etc. can be listed, and phenyl is preferred. As the alkylene group R', the carbon number can be 1 or more, preferably 1 to 3.

The aralkyl group Y is preferably benzyl, phenylethyl, etc.

The alkyl group as the group Z can be a straight chain or a branched chain. Methyl and ethyl are particularly preferred.

The compound represented by formula (F-1) is preferably a tertiary amine compound. That is, if the compound represented by formula (F-1) has a group Z, the group Z is preferably an alkyl group.

The compound represented by formula (F-1) specifically includes tri-n-decylamine, methyl di-n-octylamine, tri-n-pentylamine, N,N-dicyclohexylmethylamine, tribenzylamine, etc.

The alkaline compound (F) can be used alone or in combination of two or more. Based on the usage of the resin (A) containing an acid-dissociable group of 100 parts by weight, the content of the alkaline compound (F) is 0.05 to 0.5 parts by weight, preferably 0.06 to 0.45 parts by weight, and more preferably 0.07 to 0.4 parts by weight.

If an alkaline compound (F) is used in a chemically amplified positive photosensitive resin composition, better developing adhesion can be achieved.

Additive(G)

Specific examples of additives (G) include sensitizers, adhesion auxiliary agents, surfactants, solubility promoters, defoamers, or combinations thereof.

There is no particular limitation on the type of sensitizer. The sensitizer is preferably a compound containing a phenolic hydroxyl group, and specific examples include: (1) trisphenol type compounds: 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-methylphenyl)-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; (2) bisphenol type compounds 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 compounds (polynuclear branched compounds 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) polyhydroxybenzophenones (polyhydroxybenzophenones) benzophenone): 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; or (6) a combination of the above compounds containing phenolic hydroxyl groups.

Based on the usage of 100 parts by weight of the resin (A) containing an acid-dissociable group, the usage of the sensitizer is 5 to 50 parts by weight; preferably 8 to 40 parts by weight; and more preferably 10 to 35 parts by weight.

Specific examples of adhesion aids include melamine compounds and silane compounds.

Specific examples of commercially available melamine products include Cymel-300 or Cymel-303 manufactured by Mitsui Chemicals, or MW-30MH, MW-30, MS-11, MS-001, MX-750 or MX-706 manufactured by Sanwa Chemicals.

When a melamine compound is used as an adhesion aid, based on 100 parts by weight of the resin (A) containing an acid-dissociable group, the amount of the melamine compound used is 0 to 20 parts by weight; preferably 0.5 to 18 parts by weight; and more preferably 1.0 to 15 parts by weight.

Specific examples of silane compounds include vinyl trimethoxysilane, vinyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, vinyl tri(2-methoxyethoxy)silane, nitrogen-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, nitrogen-(2-aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxypropyloxysilane, propyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-butyltrimethoxysilane or a commercial product manufactured by Shin-Etsu Chemical Co., Ltd. (trade name such as KBM403), etc.

When a silane compound is used as an adhesion promoter, based on 100 parts by weight of the resin (A) containing an acid-dissociable group, 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.

Specific examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane surfactants, fluorine surfactants or combinations thereof.

Examples of surfactants include (1) polyoxyethylene alkyl ethers: polyoxyethylene dodecyl ether, etc.; (2) polyoxyethylene phenyl ethers: polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, etc.; (3) polyethylene glycol diesters: polyethylene glycol dilaurate, polyethylene glycol distearate, etc.; (4) sorbitan fatty acid esters; and (5) fatty acid modified polyesters; and (6) tertiary amine modified polyurethanes, etc. Specific examples of commercially available 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 & Fat Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), Megaface (manufactured by Dainippon Ink Chemical Co., Ltd.), Fluorade (manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Asahi Glass Co., Ltd.), SINOPOL E8008 (manufactured by Chunichi Synthetic Chemical Co., Ltd.), F-475 (manufactured by Dainippon Ink Chemical Co., Ltd.), or a combination thereof.

Based on the usage of 100 parts by weight of the resin (A) containing acid-dissociable groups, the usage 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.

Examples of defoamers include Surfynol MD-20, Surfynol MD-30, EnviroGem AD01, EnviroGem AE01, EnviroGem AE02, Surfynol DF110D, Surfynol 104E, Surfynol 420, Surfynol DF37, Surfynol DF58, Surfynol DF66, Surfynol DF70, and Surfynol DF210 (manufactured by Air products), etc.

Based on the usage of 100 parts by weight of the resin (A) containing an acid-dissociable group, the usage of the defoaming agent is 1 to 10 parts by weight; preferably 2 to 9 parts by weight; and more preferably 3 to 8 parts by weight.

Examples of dissolution promoters include N-hydroxydicarboxylic imide compounds and compounds containing phenolic hydroxyl groups.

Based on the usage of 100 parts by weight of the resin (A) containing an acid-dissociable group, the usage of the dissolution promoter is 1 to 20 parts by weight; preferably 2 to 15 parts by weight; and more preferably 3 to 10 parts by weight.

<Method for producing a chemically amplified positive photosensitive resin composition>

The chemically amplified positive photosensitive resin composition of the present invention can be prepared by the following method: placing the resin containing acid-dissociable groups (A), the photoacid generator (B), the solvent (C), the silane compound (D) and the blocked isocyanate compound (E) in a stirrer and stirring them to uniformly mix them into a solution state. If necessary, an alkaline compound (F) and an additive (G) can be added.

<Method for forming protective film>

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

The present invention also provides a component with a protective film, comprising a substrate and the aforementioned protective film, wherein the protective film is attached to the substrate.

In some embodiments, the chemically amplified positive photosensitive resin composition of the present invention can be used as a material for forming a protective film of a display element. In addition, the present invention also includes a protective film for a display element formed by a chemically amplified positive photosensitive resin composition.

The method for forming the protective film comprises the following steps: a step of forming a coating 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 with radiation (hereinafter also referred to as "step (2)"); a step of developing the coating after irradiation with radiation (hereinafter also referred to as "step (3)"); and a step of heating the developed coating (hereinafter also referred to as "step (4)").

According to this formation method, a protective film for display elements with excellent surface hardness, solvent resistance, heat resistance and voltage retention can be formed. In addition, by using a chemically amplified positive photosensitive resin composition with good sensitivity, a protective film for display elements with fine and delicate patterns can be easily formed. Therefore, the formed protective film for display elements is suitable for display elements such as liquid crystal display elements and organic EL display elements.

Step (1): In this step, a chemically amplified positive photosensitive resin composition is applied to a substrate to form a coating film. Preferably, the solvent is removed by pre-baking the coated surface. Examples of substrates include glass, quartz, silicon substrates, resins, etc. Examples of resins include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, ring-opening polymers of cyclic olefins, and their hydrogenates. 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 1 minute to 10 minutes.

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

Step (3): In this step, the coating film after irradiation with radiation is developed. By developing the exposed coating film, the unnecessary part (the part irradiated with radiation) is removed to form a predetermined pattern. The developer used in the developing step is preferably an alkaline aqueous solution. Examples of the alkali include: inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and amines; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, etc.

In the alkaline aqueous solution, a water-soluble organic solvent or surfactant such as methanol or ethanol may be added in appropriate amounts. From the perspective of obtaining appropriate developing properties, the concentration of alkali in the alkaline aqueous solution is preferably above 0.1 mass % and below 5 mass %. The developing method may be, for example, puddle method, immersion method, shaking immersion method, spray method, etc. 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 process, the coating is air-dried by, for example, running water washing for 30 seconds to 90 seconds, and then compressed air or compressed nitrogen is used to form the desired pattern.

Step (4): In this step, the developed coating 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, about 120°C to 250°C. The heating time varies depending on the type of heating machine, for example, about 5 minutes to 30 minutes on a heating plate and about 30 minutes to 90 minutes in an oven. In addition, a stage baking method that performs the heating step more than twice can also be used. In this way, a patterned film corresponding to the protective film for the target display element can be formed on the surface of the substrate. In addition, the use of the above-mentioned cured film is not limited to a protective film for display elements, but can also be used as a spacer or an interlayer insulating film.

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

<Implementation Example>

Synthesis Example of Resin (A) Containing Acid-Isolatable Groups

Synthesis Example A1-1

A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were set on a four-necked conical flask with a volume of 1000 ml. After the nitrogen was introduced, 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 represented by formula (a1-III-23) (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-(methacryloylmethoxy)cyclobutane (hereinafter referred to as OXMA), 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 diethylene glycol dimethyl ether (hereinafter referred to as Diglyme) solvent. Then, slowly stir the above ingredients to raise the temperature of the solution to 70°C, and polymerize at this temperature for 6 hours. Then, after de-evaporating the solvent, the resin containing acid-dissociable groups (A1-1) of Synthesis Example A1-1 can be obtained.

Synthesis Example A1-2 to Synthesis Example A1-10, Synthesis Example A2-1, Synthesis Example A2-2

The synthesis method of the resin (A) containing an acid-dissociable group in Synthesis Examples A1-2 to A1-10, Synthesis Examples A2-1, and Synthesis Example A2-2 is the same as that in Synthesis Example A1-1. The difference lies in: changing the amount of each monomer, solvent, catalyst, reaction temperature, and polymerization reaction time. The formula is shown in Table 1 and Table 2.

In addition, the compounds corresponding to the abbreviations in Table 1 and Table 2 are shown below.

Examples of chemically amplified positive photosensitive resin compositions

Example 1

100 parts by weight of the resin (A1-1) containing an acid-dissociable group, 0.3 parts by weight of the compound represented by formula (B-1-1) (hereinafter referred to as B1-1), 0.5 parts by weight of the compound represented by formula (D-10) (hereinafter referred to as D-1) and 5.0 parts by weight of the compound represented by formula (E-1) (hereinafter referred to as E-1) are added to 150 parts by weight of propylene glycol methyl ether acetate (hereinafter referred to as C-1), and stirred evenly with a shaking type stirrer to obtain the chemically amplified positive photosensitive resin composition of Example 1.

Examples 2 to 12 and Comparative Examples 1 to 6

Examples 2 to 12 and Comparative Examples 1 to 6 use the same manufacturing method as the chemically amplified positive photosensitive resin composition of Example 1. The difference is that the type and amount of raw materials in the chemically amplified positive photosensitive resin composition are changed. The formula and evaluation results are shown in Table 3 and Table 4 respectively.

In addition, the compounds corresponding to the abbreviations in Table 1 and Table 2 are shown below.

Evaluation method

Imaging density

The chemically amplified positive photosensitive resin composition prepared in the embodiment and the comparative example was coated on a plain glass substrate (100×100×0.7 mm) by spin coating, and pre-baked at 110°C for 2 minutes to obtain a pre-baked coating film of about 3 μm. A line and space mask was placed between an exposure machine (model AG500-4N; manufactured by M&R Nano Technology) and the pre-baked coating film, and the pre-baked coating film was irradiated with 80 mJ/cm ² of ultraviolet light by the exposure machine. Next, the exposed coating was immersed in a 2.38 mass % tetramethylammonium hydroxide (TMAH) solution at 23°C, developed for 70 seconds and 90 seconds respectively, and then rinsed with ultrapure water for 1 minute. The peeling of the washed substrate was observed under a microscope to evaluate the development adhesion.

The evaluation criteria are as follows:

◎: No pattern peeling off at 70 seconds and 90 seconds of development

○: No pattern peeling after 70 seconds of development, very little pattern peeling after 90 seconds of development

△: A very small amount of the pattern peeled off at 70 seconds of development, and part of the pattern peeled off at 90 seconds of development

×: A portion of the pattern peeled off after 70 seconds of development, and the entire surface of the pattern peeled off after 90 seconds of development

××: The entire surface of the pattern peeled off at 70 seconds and 90 seconds of development

Sensitivity

After the chemically amplified positive photosensitive resin composition of the embodiment and the comparative example was coated on a glass substrate (100mm×100mm), it was preheated at 110°C for 120 seconds by proximity heating with a gap of about 1mm to form a photoresist film with a film thickness of 3μm. Then, selective exposure was performed using an i-line exposure device (device name: FX-702J, manufactured by Nikon Corporation, NA=0.14) and a test chart mask (scale line) capable of simultaneously drawing a photoresist pattern of 2.0μm L&S (line and space) and a photoresist pattern of 3.0μm L&S. Next, use a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 23°C for 70 seconds, rinse with pure water for 15 seconds, and spin dry. The exposure (Eop, unit: mJ) that can faithfully reproduce the 2.0μm L&S photoresist pattern is used as an indicator for sensitivity evaluation. The evaluation criteria are as follows:

◎: Exposure <60mJ

○: 60mJ≦Exposure<150mJ

△: 150mJ≦Exposure<300mJ

×: Exposure ≧300mJ

Evaluation results

From Table 3 and Table 4, it can be seen that compared with the chemically amplified positive photosensitive resin composition containing a silane compound (D) having a specific structure and a blocked isocyanate compound (E) (Examples 1 to 12), the chemically amplified positive photosensitive resin composition of Comparative Examples 1 to 6 that does not contain a silane compound (D) or a blocked isocyanate compound (E) has poor development adhesion.

In addition, when the chemically amplified positive photosensitive resin composition further contains a resin (A1) containing an acid-dissociable group (Examples 1 to 10), better sensitivity can be obtained.

In addition, when the chemically amplified positive photosensitive resin composition further contains a photoacid generator (B1) (Examples 1 to 7), better sensitivity can be obtained.

In addition, when the chemically amplified positive photosensitive resin composition further contains an alkaline compound (F) (Examples 2 to 8), better development adhesion can be obtained.

In summary, the chemically amplified positive photosensitive resin composition of the present invention uses a silane compound (D) with a specific structure and a blocked isocyanate compound (E). Therefore, the chemically amplified positive photosensitive resin composition can improve the technical problems of poor development adhesion and sensitivity in the prior art.

In addition, when the chemically amplified positive photosensitive resin composition further contains a resin (A1) containing an acid-dissociable group, better sensitivity can be obtained.

In addition, when the chemically amplified positive photosensitive resin composition contains a photoacid generator (B1), better sensitivity can be obtained.

In addition, when the chemically amplified positive photosensitive resin composition contains an alkaline compound (F), better development adhesion can be achieved.

Although the present invention has been disclosed as above by the embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the relevant technical field can make some 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 subject to the scope of the attached patent application.

Claims (11)

A chemically amplified positive photosensitive resin composition comprises: a resin (A) containing an acid-dissociable group; a photoacid generator (B); a solvent (C); a silane compound (D); and a blocked isocyanate compound (E), wherein the photoacid generator (B) comprises a photoacid generator (B1) having a structure represented by the following formula (B-1), and the silane compound (D) has a structure represented by the following formula (D-1).

In formula (B-1), R ²¹ represents a halogenated alkyl group having 1 to 12 carbon atoms or a halogenated aryl group having 6 to 10 carbon atoms, R ²² represents an alkyl group having 1 to 6 carbon atoms, and R ²³ represents a halogenated alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms. (R ¹ O) _n R ³ _(3-n) -Si-C _m H _2m -S-Si(R ² ) ₃ Formula (D-1) In formula (D-1), R ¹ represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms; R ^R2 each independently represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 10 carbon atoms, an unsubstituted or substituted alkenyl group having 2 to 10 carbon atoms, or an unsubstituted or substituted organooxy group having 1 to 20 carbon atoms; ^R3 represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms; n is an integer from 1 to 3; and m is an integer from 1 to 3. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein the resin containing an acid-dissociable group (A) includes a resin containing an acid-dissociable group (A1), and the resin containing an acid-dissociable group (A1) is a copolymer formed by copolymerizing a first mixture, wherein the first mixture includes an unsaturated carboxylic acid monomer (a1-1), an acid-dissociable group-containing monomer (a1-2) having an acid-dissociable group represented by the following formula (a1-II), and an unsaturated monomer containing a lactone structure (a1-3),

In formula (a1-II), R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group, an alicyclic alkyl group or an aryl group, wherein the hydrogen atom possessed by the alkyl group, the alicyclic alkyl group or the aryl group may be partially or completely substituted, and R ¹¹ and R ¹² are not hydrogen atoms at the same time; R ¹³ is an alkyl group, an alicyclic alkyl group, an aralkyl group or an aryl group, wherein the hydrogen atom possessed by the alkyl group, the alicyclic alkyl group, the aralkyl group and the aryl group may be partially or completely substituted; 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. The chemically amplified positive photosensitive resin composition as described in claim 2, wherein the unsaturated monomer (a1-3) containing a lactone structure is a compound represented by the following formula (a1-III),

In formula (a1-III), ^RX1 is a hydrogen atom or an alkyl group; ^RA2 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; when _n2 is greater than 1, the plurality of ^RA2s may be the same or different; ^A1 is a single bond or a divalent linking group; ^Z2 is a monocyclic or polycyclic structure containing -OC(=O)-; and _n2 is an integer greater than 0. The chemically amplified positive photosensitive resin composition as described in claim 1 further includes an alkaline compound (F) represented by the following formula (F-1): N(Y) _x (Z) _3-x Formula (F-1) In formula (F-1), Y each independently represents an alkyl group with a carbon number of 4 or more, a cycloalkyl group with a carbon number of 3 or more, a phenyl group or an aralkyl group; Z each independently represents a hydrogen atom or an alkyl group with a carbon number of 3 or less; and x represents an integer from 1 to 3. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein the blocked isocyanate compound (E) is a compound having a blocked structure formed by any one of an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein the amount of the resin (A) containing an acid-dissociable group is 100 parts by weight, the amount of the photoacid generator (B) is 0.3 parts by weight to 3 parts by weight, the amount of the solvent (C) is 150 parts by weight to 1200 parts by weight, the amount of the silane compound (D) is 0.5 parts by weight to 5 parts by weight, and the amount of the blocked isocyanate compound (E) is 0.5 parts by weight to 5 parts by weight. The chemically amplified positive photosensitive resin composition as described in claim 2, wherein the amount of the resin (A) containing acid-dissociable groups is 100 parts by weight, and the amount of the resin (A1) containing acid-dissociable groups is 50 parts by weight to 100 parts by weight. The chemically amplified positive photosensitive resin composition as described in claim 1, wherein the amount of the resin (A) containing acid-dissociable groups is 100 parts by weight, and the amount of the photoacid generator (B1) is 0.3 parts by weight to 3 parts by weight. The chemically amplified positive photosensitive resin composition as described in claim 4, wherein the amount of the resin (A) containing acid-dissociable groups is 100 parts by weight, and the amount of the alkaline compound (F) is 0.05 to 0.5 parts by weight. A protective film is formed by coating a chemically amplified positive photosensitive resin composition as described in any one of claims 1 to 9 on a substrate, and then performing pre-baking, exposure, development and post-baking treatments. A component with a protective film, comprising: a substrate; and a protective film as described in claim 10, wherein the protective film is attached to the substrate.