Chemical amplification positive photosensitive resin composition, protective film, and component

Abstract

The present application provides a kind of chemical amplification positive photosensitive resin composition, protective film and assembly.The chemical amplification positive photosensitive resin composition includes resin (A), photoacid generator (B), solvent (C) and epoxy compound (D).The present application further includes the protective film prepared by using the chemical amplification positive photosensitive resin composition, and the assembly including the protective film.The protective film has good developing adhesion and chemical resistance, and can be applied to thin film transistor substrate flat film, interlayer insulating film or optical waveguide core material or cladding material.

Description

Technical Field

[0001] This invention relates to a chemically amplified positive photosensitive resin composition, a protective film formed therefrom, and a component having the protective film. In particular, it provides a positive photosensitive resin composition for forming a protective film with excellent adhesion and chemical resistance after exposure and development. This protective film is suitable for planarization films, interlayer insulating films, or core materials or coatings for optical waveguides in thin-film transistor (TFT) substrates of liquid crystal display components, organic EL display components, etc. Background Technology

[0002] Display components such as thin-film transistor liquid crystal displays (TFT-LCDs) or organic electroluminescence devices (OLEDs) typically include insulating films such as interlayer insulating films or planarization films. These insulating films are usually formed using radiosensitive linear compositions. From the viewpoint of patterning performance, it is conventionally known to use positive radiosensitive linear resin compositions that utilize acid-generating agents such as naphthoquinone diazide (see Japanese Patent Application Publication No. 2001-354822) as such radiosensitive linear compositions; however, various other radiosensitive linear compositions have been proposed in recent years.

[0003] For example, a positive chemical amplification material has been proposed, the purpose of which is to form a hardened film for display components with higher sensitivity than the aforementioned positive radiosensitive linear resin composition using acid-generating agents such as naphthoquinone diazide (see Japanese Patent Application Publication No. 2004-4669). The positive chemical amplification material contains a crosslinking agent, an acid-generating agent, and an acid-dissociating resin. The acid-dissociating resin has protecting groups that can be dissociated by the action of acid. Although the acid-dissociating resin itself is insoluble or sparingly soluble in alkaline aqueous solutions, it becomes soluble in alkaline aqueous solutions by dissociating the protecting groups using the action of acid. Furthermore, positive radiosensitive linear compositions containing resins having acetal and / or ketal structures and epoxy groups, as well as acid-generating agents, have also been proposed (see Japanese Patent Application Publication Nos. 2004-264623, 2011-215596, and 2008-304902).

[0004] In addition to high radiation sensitivity, these radiosensitive linear resin compositions also require storage stability where viscosity remains unchanged even after long-term storage. This ensures that the hardened film formed from these radiosensitive linear resin compositions exhibits chemical resistance, preventing swelling due to developing solutions or similar substances. Furthermore, the pattern formed on the hardened film achieves the following: after development, the pattern adheres tightly to the substrate and is difficult to peel off; the hardened film possesses sufficient transparency; and even after exposure and subsequent storage, the pattern remains tightly adhered to the substrate and is difficult to peel off.

[0005] However, the development adhesion and chemical resistance of films obtained from current photosensitive resin compositions are still not acceptable to the industry. Summary of the Invention

[0006] One aspect of the present invention is to provide a chemically amplified positive photosensitive resin composition. In some embodiments, this chemically amplified positive photosensitive resin composition may comprise a resin (A), a photoacid generator (B), a solvent (C), and an epoxy compound (D), as detailed below.

[0007] Resin (A)

[0008] The resin (A) is obtained by copolymerization of a monomer mixture. In some embodiments, the monomer mixture includes at least an unsaturated carboxylic acid monomer (a-1) and a monomer containing an acid-dissociable group (a-2).

[0009] Unsaturated carboxylic acid monomer (a-1)

[0010] The unsaturated carboxylic acid monomer (a-1) of the present invention refers to a compound containing a carboxylic acid group or 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 acid anhydride compounds, polycyclic unsaturated carboxylic acid compounds, polycyclic unsaturated dicarboxylic acid compounds, and polycyclic unsaturated dicarboxylic acid anhydride compounds.

[0011] Specific examples of the aforementioned unsaturated monocarboxylic acid compounds include: (meth)acrylic acid, butenoic acid, α-chloroacrylic acid, ethylacrylic acid, cinnamic acid, 2-(meth)acryloylethoxysuccinate, 2-(meth)acryloylethoxyhexahydrophthalic acid ester, 2-(meth)acryloylethoxyphthalic acid ester, and omega-carboxylated polycaprolactone polyol monoacrylate (trade name ARONIX M-5300, manufactured by Toa Synthetic).

[0012] Specific examples of the aforementioned unsaturated dicarboxylic acid compounds include maleic acid, fumaric acid, methyl fumaric acid, itaconic acid, and citraconic acid. In a specific example of the present invention, the unsaturated dicarboxylic acid anhydride compound is an anhydride compound of the aforementioned unsaturated dicarboxylic acid compounds.

[0013] Specific examples of the aforementioned 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, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene.

[0014] Specific examples of the aforementioned polycyclic unsaturated dicarboxylic acid compounds include: 5,6-dicarboxylic acid bicyclic [2.2.1]hept-2-ene.

[0015] The aforementioned polycyclic unsaturated dicarboxylic acid anhydride compounds are the anhydride compounds of the aforementioned polycyclic unsaturated dicarboxylic acid compounds.

[0016] Preferred examples of the unsaturated carboxylic acid monomer (a-1) are acrylic acid, methacrylic acid, maleic anhydride, 2-methacryloylethoxysuccinate, 2-methacryloylethoxyhexahydrophthalic acid, or combinations thereof.

[0017] The amount of monomer mixture used is 100 parts by weight, and the amount of unsaturated carboxylic acid monomer (a-1) used is 3 to 50 parts by weight, preferably 3 to 45 parts by weight, and more preferably 3 to 40 parts by weight.

[0018] Monomers containing acid-dissociable groups (a-2)

[0019] In some embodiments, the monomer (a-2) containing an acid-dissociating group in the monomer mixture has an acid-dissociating group as shown in formula (1). The acid-dissociating group of the monomer (a-2) dissociates upon exposure by the action of the acid generated from the photoacid generator (B) described later, and generates a polar group, thus the resin (A) that was originally insoluble or sparingly soluble in alkaline aqueous solution becomes soluble in alkaline aqueous solution.

[0020]

[0021] The monomer (a-2) containing the acid-dissociable group is not particularly limited as long as it has the structure of formula (1). The monomer (a-2) containing the acid-dissociable group of formula (1) can be easily dissociated by an acid. In formula (1), R... 1 and R 2 Each is independently a hydrogen atom, alkyl, alicyclic hydrocarbon group, or aryl group, wherein some or all of the hydrogen atoms of the alkyl, alicyclic hydrocarbon group, or aryl group may be substituted; and R 1 and R 2 Not both are hydrogen atoms; R 3 It is an alkyl, alicyclic hydrocarbon, aralkyl, or aryl group, wherein R 3Some or all of the hydrogen atoms in the alkyl, alicyclic hydrocarbon, aralkyl, and aryl groups may be substituted; R 1 With R 3 They can be mutually bonded and with R 1 The bonded carbon atoms and R 3 The bonded oxygen atoms together form a cyclic ether structure; and * 1 Represents the bond joint.

[0022] The above R 1 and R 2 Examples of alicyclic hydrocarbon groups represented include those with 3 to 20 carbon atoms. Furthermore, these alicyclic hydrocarbon groups with 3 to 20 carbon atoms can be polycyclic. Examples of the aforementioned alicyclic hydrocarbon groups with 3 to 20 carbon atoms include: cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, borneol, norborneol, adamantyl, etc.

[0023] The above R 1 and R 2 Examples of aryl groups represented include aryl groups with 6 to 14 carbon atoms. These aryl groups with 6 to 14 carbon atoms can be monocyclic, composed of linked monocyclic rings, or condensed rings. Examples of aryl groups with 6 to 14 carbon atoms include phenyl and naphthyl groups.

[0024] The above R 1 and R 2 The substituents that can be substituted, such as alkyl, alicyclic hydrocarbon, and aryl groups, include: halogen atoms, hydroxyl groups, nitro groups, cyano groups, carboxyl groups, carbonyl groups, alicyclic hydrocarbon groups (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, borneol, norborneol, adamantyl, etc.), aryl groups (e.g., phenyl, naphthyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, propoxy, n-butoxy, pentoxy, hexoxy, heptoxy, octoxy, etc., with 1 to 20 carbon atoms), acyl groups (e.g., acetyl, propionyl, butyryl, isobutyryl, etc., with 2 to 20 carbon atoms), and acyloxy groups (e.g., acetoxy, propionyloxy, butyryloxy, terbutyryloxy, ter...). Acyloxy groups with 2 to 10 carbon atoms, such as valeryloxy, alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, etc., with 2 to 20 carbon atoms), haloalkyl groups (e.g., straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-tetradecyl, n-octadecyl, etc.; branched alkyl groups such as isopropyl, isobutyl, tributyl, neopentyl, 2-hexyl, 3-hexyl, etc.; alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, adamantyl, etc.; groups obtained by substituting some or all of the hydrogen atoms of the above groups with halogen atoms), hydroxyalkyl groups (e.g., hydroxymethyl, etc.).

[0025] The above R3 The alkyl, alicyclic hydrocarbon, and aryl groups represented can be applied using the above-mentioned R. 1 and R 2 Explanation of each group represented. Furthermore, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably methyl, ethyl, or n-propyl. The above R... 3 Examples of aralkyl groups that can be represented include: benzyl, phenethyl, naphthylmethyl, naphthylethyl, etc.

[0026] The above R 1 With R 3 The cyclic ether structure that can be formed by mutual bonding is preferably a cyclic ether structure with 3 to 20 ring members, more preferably a cyclic ether structure with 5 to 8 ring members, and even more preferably a tetrahydrofuran or a tetrahydropyran.

[0027] The group represented by the above formula (1) can be exemplified by groups represented by the following formulas, wherein, in these specific examples, * 1 The same definition as in equation (1) is used.

[0028]

[0029] Examples of the monomers (a-2) containing acid-dissociative groups mentioned above include: 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-tert-butoxyethyl methacrylate, 1-(2-chloroethoxy)ethyl methacrylate, 1-(2-ethylhexyloxy)ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1-(2-cyclohexylethoxy)ethyl methacrylate, 1-benzyloxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, and 2-tetrahydrofuranyl methacrylate. methacrylate), 1-ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-tert-butoxyethyl acrylate, 1-(2-chloroethoxy)ethyl acrylate, 1-(2-ethylhexyloxy)ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, 1-(2-cyclohexylethoxy)ethyl acrylate, 1-benzyloxyethyl acrylate, 2-tetrahydropyranyl acrylate, 5,6-di(1-methoxyethoxycarbonyl)-2-norbornene, 5,6-di(1-(cyclohexyloxy)ethoxycarbonyl)-2-norbornene, 5,6-di(1-(benzyloxy)ethoxycarbonyl)-2-norbornene, p-1-ethoxyethoxystyrene or m-1-ethoxyethoxystyrene, p-1-methoxyethoxystyrene or m-1-methoxyethoxystyrene, p-1- Butoxyethoxystyrene or m-1-butoxyethoxystyrene, p-1-isobutoxyethoxystyrene or m-1-isobutoxyethoxystyrene, p-1-(1,1-dimethylethoxy)ethoxystyrene or m-1-(1,1-dimethylethoxy)ethoxystyrene, p-1-(2-chloroethoxy)ethoxystyrene or m-1-(2-chloroethoxy)ethoxystyrene, p-1-(2-ethylhexyloxy)ethoxystyrene or m-1-(2-ethylhexyloxy)ethoxystyrene, p-1-propoxyethoxystyrene or m-1-propoxyethoxystyrene, p-1-cyclohexyloxyethoxystyrene or m-1-cyclohexyloxyethoxystyrene, p-1-(2-cyclohexylethoxy)ethoxystyrene or m-1-(2-cyclohexylethoxy)ethoxystyrene, p-1-benzyloxyethoxystyrene or m-1-benzyloxyethoxystyrene, etc.

[0030] The monomers (a-2) containing acid-dissociable groups are preferably 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 1-benzyloxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, and 2-tetrahydrofuranyl methacrylate, and more preferably 2-tetrahydropyranyl methacrylate and 2-tetrahydrofuranyl methacrylate.

[0031] Based on the amount of monomer mixture used being 100 parts by weight, the amount of monomer (a-2) containing acid-dissociating protecting groups used being 10 to 97 parts by weight, preferably 15 to 80 parts by weight, and more preferably 20 to 70 parts by weight. If monomer (a-2) containing acid-dissociating protecting groups is not used in the monomer mixture, the protective film made from the resin composition will have poor development adhesion and chemical resistance.

[0032] Unsaturated monomers containing lactone structures (a-3)

[0033] In some embodiments, the monomer mixture may further comprise unsaturated monomers (a-3) containing a lactone structure. Preferably, the lactone structure used in this invention is a lactone structure forming a five-membered to seven-membered ring, and more preferably a lactone structure forming a five-membered or six-membered ring.

[0034] Furthermore, in the unsaturated monomer (a-3) containing a lactone structure used in this invention, other ring structures can also be cyclically condensed onto the lactone structure to form a polycyclic structure in the formation of a five- to seven-membered ring lactone structure, but preferably, the other ring structures do not cyclically condense onto the lactone structure. Preferably, when other ring structures cyclically condense onto the lactone structure forming a five- to seven-membered ring, the other ring structures cyclically condense in the form of a bicyclic structure or a spirocyclic structure. Examples of other ring structures include cyclic hydrocarbon groups with 3 to 20 carbon atoms, heterocyclic groups with 3 to 20 carbon atoms, etc. The heterocyclic group is not particularly limited, and examples include those in which one or more atoms constituting the ring are heteroatoms, or aromatic heterocyclic groups. In addition, the heterocyclic group is preferably a five-membered ring or a six-membered ring, and more preferably a five-membered ring. Specifically, the heterocyclic group preferably contains at least one oxygen atom, for example: oxocyclic pentane ring, oxane ring, dioxane ring, etc.

[0035] In the case of unsaturated monomers (a-3) containing lactone structures, where other ring structures are cyclically condensed on the lactone structure to form a polycyclic structure, the number of other ring structures cyclically condensed on the lactone structure is preferably 1 to 5, more preferably 1 to 3.

[0036] Furthermore, this lactone structure may or may not have substituents, but it is preferred that it is unsubstituent. There are no particular limitations on the substituents, but examples include: alkyl groups with 1 to 8 carbon atoms, cycloalkyl groups with 3 to 7 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, alkoxycarbonyl groups with 2 to 8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, acid-degradable groups, etc. Alkyl groups with 1 to 4 carbon atoms and cyano groups are more preferred.

[0037] As an alkyl group, it is preferred to be a straight-chain alkyl group with 1 to 6 carbon atoms, a branched alkyl group with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, and more preferably a straight-chain alkyl group with 1 to 3 carbon atoms.

[0038] When the lactone structure has substituents, the number of substituents is not particularly limited, but is preferably 1 to 4, more preferably 1 or 2. When the lactone structure has multiple substituents, the substituents may be the same or different from each other. Furthermore, when other ring structures are cyclically condensed on the lactone structure, these other ring structures may also have substituents.

[0039] In some embodiments, preferably, the unsaturated monomer (a-3) containing a lactone structure may comprise a portion of the structure shown in formula (3):

[0040]

[0041] In equation (3), R 8 Represents substituents, n = 7 R 8 Each is independent and either the same or different; Z 1 This represents a single-ring or multi-ring structure containing -OC (=O)-; n7 represents an integer greater than or equal to 0; and, * 3 This is the bonding point.

[0042] In equation (3), R 8 Represents substituents, n = 7 R 8 They are independent and can be the same or different. R 8 The substituents that can be present in the aforementioned lactone structure have the same meaning, and the preferred range is also the same.

[0043] In equation (3), Z 1 This indicates a monocyclic or polycyclic structure containing -OC (=O)-, preferably a monocyclic structure. In Z 1 In the case of a monocyclic structure, a five- to seven-membered lactone structure is preferred, and a five- or six-membered lactone structure is even more preferred. In Z 1 In the case of a polycyclic structure, it is preferred that other ring structures are condensed onto the lactone structure in the form of a bicyclic or spirocyclic structure. "Other ring structures" has the same meaning as the aforementioned "other ring structures," and the preferred range is also the same.

[0044] In equation (3), n7 represents an integer greater than or equal to 0, preferably an integer between 0 and 4, more preferably an integer between 0 and 2, and even more preferably 0. When n7 represents an integer greater than or equal to 2, the multiple substituents may be the same or different from each other. In addition, the multiple substituents may also bond with each other to form a ring, but it is preferred that they do not bond with each other to form a ring.

[0045] In some embodiments, the unsaturated monomer (a-3) containing the lactone structure is preferably represented by the following formula (3-1).

[0046]

[0047] In equation (3-1), R 8a Represents a hydrogen atom or an alkyl group. R 8b Represents substituents, n = 8 R 8b They are independent and can be the same or different. A 1 Represents a linker base with a single bond or a divalent bond. Z 2 This represents a monocyclic or polycyclic structure containing the base represented by -OC (=O). n8 represents an integer greater than or equal to 0.

[0048] In equation (3-1), R 8a This indicates a hydrogen atom or an alkyl group. The alkyl group is preferably a straight-chain or branched alkyl group with 1 to 3 carbon atoms, and more preferably a methyl group. The alkyl group may have substituents. Substituents are preferably hydroxyl groups or halogen atoms (especially fluorine atoms).

[0049] In equation (3-1), R 8b Represents substituents, n = 8 R 8b They are independent and can be the same or different. R 8b The substituents that can be present in the lactone structure described above have the same meaning and the preferred range is also the same.

[0050] In equation (3-1), A 1 This indicates a single-bonded or divalent linking group. Examples of divalent linking groups include: straight-chain, branched-chain, or cyclic alkyl or aryl groups, -O-, -COO-, -S-, -NR"-, -CO-, -NR"CO-, -SO2-, etc., or combinations containing these groups. Here, R" represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. Preferably, the divalent linking group contains at least one of -O-, -COO-, -S-, -NH-, and -CO-, or these groups combined with -(CH2). m - (m is an integer from 1 to 10, preferably an integer from 1 to 6, and even more preferably an integer from 1 to 4) is a group of combinations.

[0051] In equation (3-1), Z 2This indicates a monocyclic or polycyclic structure containing the group represented by -OC (=O)-, and is consistent with Z in formula (3). 1 The meanings are the same, and the preferred ranges are also the same.

[0052] In equation (3-1), n8 represents an integer greater than 0, and has the same meaning as n1 in general equation (3), and the preferred range is also the same.

[0053] In some other embodiments, the unsaturated monomer (a-3) containing the lactone structure is preferably represented by the structure of the following formula (3-2).

[0054]

[0055] In equation (3-2), R 8c Represents a hydrogen atom or an alkyl group. R 8d Indicates substituents, n9 R 8d They are independent and can be the same or different. A 2 Represents a linker base with a single bond or a divalent bond. Z 3 This represents a monocyclic or polycyclic structure containing the base represented by -OC (=O). n9 represents an integer greater than 0. X 1 R' represents an oxygen atom or -NR'-. R' represents a hydrogen atom or an alkyl group.

[0056] In equation (3-2), R 8d Indicates substituents, n9 R 8d They are independent and can be the same or different. R 8d The substituents that can be present in the lactone structure described above have the same meaning and the preferred range is also the same.

[0057] In equation (3-2), A 2 This represents a single-bond or divalent linker. As a divalent linker, it relates to A in equation (3-1). 1 The same meaning applies when referring to a divalent linker. A preferred divalent linker may be one containing at least one of -COO- or -CO-, or these groups combined with -(CH2). m - (m is an integer from 1 to 10, preferably an integer from 1 to 6, and even more preferably an integer from 1 to 4) combinations. A in equation (3-2) 2 A single key is especially preferred.

[0058] In equation (3-2), Z 3 This indicates a monocyclic or polycyclic structure containing the group represented by -OC (=O)-, and is consistent with Z in formula (3-1). 1 The meanings are the same, and the preferred ranges are also the same.

[0059] In equation (3-2), n9 represents an integer greater than or equal to 0, and has the same meaning as n8 in equation (3-1), and the preferred range is also the same.

[0060] In equation (3-2), X 1 "R" indicates an oxygen atom or -NR"-, preferably an oxygen atom. "R" indicates a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom.

[0061] Specific examples of the lactone-containing unsaturated monomers (a-3) of the present invention can be listed in formulas (3-3) to (3-23), but the present invention is not limited to these examples. The R shown here... 8e R can represent equation (3-1) 8a R in equation (3-2) 8c .

[0062]

[0063]

[0064]

[0065] The monomer mixture of the present invention may contain two or more unsaturated monomers (a-3) containing a lactone structure. Based on 100 parts by weight of the monomer mixture, the amount of the unsaturated monomer (a-3) containing a lactone structure used is 2 to 20 parts by weight, preferably 2 to 15 parts by weight, and more preferably 2 to 10 parts by weight. When the monomer mixture includes the unsaturated monomer (a-3) containing a lactone structure, the developability and adhesion of the protective film formed from this composition can be further improved.

[0066] Unsaturated monomers containing epoxy groups (a-4)

[0067] In some embodiments, the monomer mixture used to synthesize the resin (A) of the chemically amplified positive photosensitive resin composition of the present invention may further include epoxy-containing unsaturated monomers (a-4).

[0068] The epoxy-containing unsaturated monomer (a-4) may include, but is not limited to, epoxy-containing (meth)acrylate compounds, epoxy-containing α-alkyl acrylate compounds, epoxy propylene ether compounds, vinyl unsaturated monomers having oxetane as shown in formula (4), and any combination thereof.

[0069]

[0070] In equation (4), R 9 Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 10 Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 11 R12 R 13 and R 14 Each of the following can independently represent a hydrogen atom, a fluorine atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, or a perfluoroalkyl group having 1 to 4 carbon atoms; and a represents an integer from 1 to 6.

[0071] Specific examples of the aforementioned epoxy-containing (meth)acrylate compounds include: glycidyl (meth)acrylate, 2-methyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and 3,4-epoxycyclohexyl methyl (meth)acrylate.

[0072] Specific examples of the aforementioned epoxy-containing α-alkyl acrylate compounds include: α-ethyl acrylate glycidyl acrylate, α-n-propyl acrylate glycidyl acrylate, α-n-butyl acrylate glycidyl acrylate, and α-ethyl acrylate 6,7-epoxyheptyl acrylate.

[0073] Specific examples of the aforementioned glycidyl ether compounds include: o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, and p-vinylbenzylglycidylether.

[0074] Specific examples of the oxocyclic butyl vinyl unsaturated monomers shown in formula (4) may include, but are not limited to, methacrylate compounds or acrylate compounds.

[0075] The aforementioned methacrylate compounds may include, but are not limited to, 3-(methacryloyloxy)oxetane [OXMA], 3-(methacryloyloxy)-3-ethyloxetane [EOXMA] (as shown in formula (4-3)), 3-(methacryloyloxy)-3-methyloxetane [MOXMA] (as shown in formula (4-1)), 3-(methacryloyloxy)-2-methyloxetane, 3-(methacryloyloxy)-2-trifluoromethyloxetane, 3-(methacryloyloxy)-2-pentafluoroethyloxetane, 3-(methacryloyloxy)-2- Phenylacetane, 3-(methacryloylmethoxy)-2,2-difluorooxetane, 3-(methacryloylmethoxy)-2,2,4-trifluorooxetane, 3-(methacryloylmethoxy)-2,2,4,4-tetrafluorooxetane, 3-(methacryloylethoxy)oxetane, 3-(methacryloylethoxy)-3-ethyloxetane, 2-ethyl-3-(methacryloylethoxy)oxetane, 3-( Compounds of (methacryloylethoxy)-2-trifluoromethyloxetane, 3-(methacryloylethoxy)-2-pentafluoroethyloxetane, 3-(methacryloylethoxy)-2-phenyloxetane, 2,2-difluoro-3-(methacryloylethoxy)oxetane, 3-(methacryloylethoxy)-2,2,4-trifluorooxetane, or 3-(methacryloylethoxy)-2,2,4,4-tetrafluorooxetane, etc.

[0076] The aforementioned acrylate compounds may include, but are not limited to, 3-(acryloylmethoxy)oxetane, 3-(acryloylmethoxy)-3-ethyloxetane (as shown in formula (4-4)), 3-(acryloylmethoxy)-3-methyloxetane (as shown in formula (4-2)), 3-(acryloylmethoxy)-2-methyloxetane, 3-(acryloylmethoxy)-2-trifluoromethyloxetane, 3-(acryloylmethoxy)-2-pentafluoroethyloxetane, 3-(acryloylmethoxy)-2-phenyloxetane, 3-(acryloylmethoxy)-2,2-difluorooxetane, and 3-(acryloylmethoxy)-2,2,4-trifluorooxetane. Compounds of 3-(acryloylmethoxy)-2,2,4,4-tetrafluorooxetane, 3-(acryloylethoxy)oxetane, 3-(acryloylethoxy)-3-ethyloxetane, 2-ethyl-3-(acryloylethoxy)oxetane, 3-(acryloylethoxy)-2-trifluoromethyloxetane, 3-(acryloylethoxy)-2-pentafluoroethyloxetane, 3-(acryloylethoxy)-2-phenyloxetane, 2,2-difluoro-3-(acryloylethoxy)oxetane, 3-(acryloylethoxy)-2,2,4-trifluorooxetane, or 3-(acryloylethoxy)-2,2,4,4-tetrafluorooxetane, etc.

[0077]

[0078] In some embodiments, the epoxy-containing unsaturated monomer (a-4) may further comprise other vinyl unsaturated monomers having an oxetyl group, such as: 3-methyl-3-(vinyloxy)oxetane [MOXV], 3-ethyl-3-(vinyloxy)oxetane [EOXV], 3-propyl-3-(vinyloxy)oxetane, 3-methyl-3-(2-vinylethoxy)oxetane, 3-ethyl-3-(2-vinylethoxy)oxetane, 3-propyl-3-(2- Vinyl ether compounds containing oxetyl groups, such as ethylene ethoxy)oxetane, 3-methyl-3-(3-ethylenepropoxy)oxetane, 3-ethyl-3-(3-ethylenepropoxy)oxetane, 3-propyl-3-(3-ethylenepropoxy)oxetane, 3-methyl-3-(3-ethylenebutoxy)oxetane, 3-ethyl-3-(3-ethylenebutoxy)oxetane, 3-propyl-3-(3-ethylenebutoxy)oxetane, ethylene glycol [(3-ethyl-3-oxetyl)methyl]vinyl ether, propylene glycol [(3-ethyl-3-oxetyl)methyl]vinyl ether, or 3,3-bis[(ethyleneoxy)methyl]oxetane.

[0079] Preferably, the amount of 3-(methacryloylmethoxy)oxetane, 3-(methacryloylmethoxy)-3-methyloxetane, 3-(methacryloylmethoxy)-3-ethyloxetane, 3-(acryloylmethoxy)-3-methyloxetane, or 3-(acryloylmethoxy)-3-ethyloxetane in the monomer mixture is 100 parts by weight, and the amount of the epoxy-containing unsaturated monomer (a-4) is 10 to 90 parts by weight, more preferably 15 to 80 parts by weight, and even more preferably 20 to 70 parts by weight. When the monomer mixture includes the epoxy-containing unsaturated monomer (a-4), the chemical resistance of the protective film obtained from the resin composition can be further improved.

[0080] Other unsaturated monomers (a-5)

[0081] The monomer mixture used to form resin (A) may further contain other unsaturated monomers (a-5). In some embodiments, the other unsaturated monomers (a-5) may include, but are not limited to, alkyl (meth)acrylates, alicyclic (meth)acrylates, aryl (meth)acrylates, unsaturated dicarboxylic acid diesters, hydroxyalkyl (meth)acrylates, polyethers of (meth)acrylates, aromatic vinyl compounds, and other unsaturated compounds not mentioned above.

[0082] Specific examples of the aforementioned alkyl methacrylates include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, butyl methacrylate, and tertiary butyl methacrylate.

[0083] Specific examples of the aforementioned cyclohexyl (meth)acrylates include: cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and tricyclo[5.2.1.0] 2，6 Decyl-8-yl(meth)acrylate (or dicyclopentyl(meth)acrylate), dicyclopentoxyethyl(meth)acrylate, isobornyl(meth)acrylate, tetrahydrofuran(meth)acrylate.

[0084] Specific examples of the aforementioned aryl methacrylates include: phenyl methacrylate and benzyl methacrylate.

[0085] Specific examples of the aforementioned unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, and diethyl itaconic acid.

[0086] Specific examples of the aforementioned hydroxyalkyl methacrylates include: 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0087] Specific examples of the aforementioned (meth)acrylate polyethers include: polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate.

[0088] Specific examples of the aforementioned aromatic ethylene compounds include: styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene.

[0089] Other unsaturated compounds not mentioned above include, for example: acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, ethylene ethyl ester, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylidenemaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N-succinimide-6-maleimide hexanoate, N-succinimide-3-maleimide propionate, and N-(9-acridyl)maleimide.

[0090] The amount of monomer mixture used is 100 parts by weight, and the amount of other unsaturated monomer (a-5) used is 0 to 75 parts by weight, preferably 0 to 65 parts by weight, and more preferably 0 to 55 parts by weight.

[0091] Preparation of resin (A)

[0092] The solvents used in the manufacture of the resin (A) of the present invention may include, but are not limited to, alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbons, ketones, and esters.

[0093] Specific examples of the aforementioned alcohols include: methanol, ethanol, benzyl alcohol, 2-phenylethanol, and 3-phenyl-1-propanol. Specific examples of the aforementioned ethers include: tetrahydrofuran. Specific examples of the aforementioned glycol ethers include: ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. Specific examples of the aforementioned ethylene glycol alkyl ether acetates include: ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, and ethylene glycol methyl ether acetate. Specific examples of the aforementioned diethylene glycols include: diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. Specific examples of the aforementioned dipropylene glycols include: dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol methyl ethyl ether. Specific examples of the aforementioned propylene glycol monoalkyl ethers include: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether. Specific examples of the aforementioned propylene glycol alkyl ether acetates include: propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate. Specific examples of the aforementioned propylene glycol alkyl ether propionates include: propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate. Specific examples of the aforementioned aromatic hydrocarbons include: toluene and xylene. Specific examples of the aforementioned ketones include: methyl ethyl ketone, cyclohexanone, and diacetone alcohol. Specific examples of the aforementioned esters include: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 3-methoxybutylacetate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl ester, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate.

[0094] Preferred examples of solvents used in the manufacture of the resin (A) of the present invention are diethylene glycol dimethyl ether and propylene glycol methyl ether acetate. These solvents may be used alone or in combination.

[0095] Specific examples of polymerization initiators used in the manufacture of the resin (A) of the present invention are azo compounds or peroxides. Examples of the aforementioned azo compounds include: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile), 2,2'-azobis(2-methylbutyronitrile), 4,4'-azobis(4-cyanopentanoic acid), and 2,2'-azobis(dimethyl-2-methylpropionate). Examples of the aforementioned peroxides include: benzoyl peroxide, dilauroyl peroxide, tert-butylperoxypivalate, 1,1-di(tert-butylperoxy)cyclohexane, and hydrogen peroxide. The above polymerization initiators can be used alone or in combination.

[0096] In the polymerization reaction of resin (A), a molecular weight adjuster can be used to adjust the molecular weight. Examples of such adjusters include chloroform, carbon tetrabromide, n-hexylthiol, n-octylthiol, n-dodecylthiol, tert-dodecyl mercaptan, thioglycolic acid, and 3-mercaptopropionic acid. Based on the amount of the monomer mixture used being 100 parts by weight, the amount of this molecular weight adjuster can be from 1 part by weight to 15 parts by weight, preferably from 1.5 parts by weight to 14 parts by weight, and more preferably from 2 parts by weight to 12 parts by weight.

[0097] The weight-average molecular weight of the resin (A) of the present invention, determined by gel permeation chromatography (GPC), based on polystyrene, is generally from 3,000 to 100,000, preferably from 4,000 to 80,000, and even more preferably from 5,000 to 60,000. The molecular weight of the resin (A) of the present invention can be adjusted using a single resin or by combining two or more resins with different molecular weights.

[0098] Photoacid generator (B)

[0099] The photoacid generator (B) is a compound that generates acid through irradiation with radiation, and may be at least one selected from oxime sulfonate compounds represented by the following formula (5) and N-sulfonyloxyimide compounds. The radiation may be, for example, visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays, etc. Because the chemically amplified positive photosensitive resin composition of the present invention contains the photoacid generator (B), the chemically amplified positive photosensitive resin composition can exhibit radiation-sensitive (or photosensitizing) properties and can have good radiation sensitivity. The photoacid generator (B) in the chemically amplified positive photosensitive resin composition, as described below, may be in the form of a compound, or may be incorporated into the resin (A) as part of the polymer constituting the resin (A), or may be a combination of these two forms. These photoacid generators (B) may be used alone or in combination of two or more.

[0100] In addition to containing oxime sulfonate compounds with oxime sulfonate groups and N-sulfonyloxyimide compounds, photoacid generator (B) may also contain: onium salts, halogenated compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylic acid ester compounds, etc.

[0101] In some embodiments, the oxime sulfonate compound is a compound comprising an oxime sulfonate group of the following formula (5).

[0102]

[0103] In equation (5), R 15 It is an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a group in which the hydrogen atoms of the above groups are partially or completely substituted; and, * 4 This is the bonding point.

[0104] The R 15 The alkyl group represented is preferably a straight-chain or branched alkyl group having 1 to 12 carbon atoms.

[0105] The R 15 The monovalent alicyclic hydrocarbon group represented is preferably an alicyclic hydrocarbon group with 4 to 12 carbon atoms.

[0106] The R 15 The aryl group represented is preferably an aryl group with 6 to 20 carbon atoms, and more preferably a phenyl, naphthyl, tolyl, or xylyl group.

[0107] Examples of substituents include alkyl groups, alkoxy groups, lateral oxy groups, halogen atoms, etc., having 1 to 5 carbon atoms.

[0108] Compounds containing the oxime sulfonate group represented by formula (5) can be listed as oxime sulfonate compounds represented by formulas (5-1) to (5-3) below.

[0109]

[0110] In equations (5-1) to (5-3), R 16 R of structural formula (5) 15 The same meaning applies. In equations (5-1) and (5-2), R 17 The alkyl group has 1 to 12 carbon atoms, and the fluoroalkyl group has 1 to 12 carbon atoms. In formula (5-3), X is an alkyl, alkoxy, or halogen atom. i is an integer from 0 to 3. Where i is 2 or 3, multiple Xs may be the same or different.

[0111] The alkyl group represented by X is preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a straight-chain 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.

[0112] The oxime sulfonate compounds represented by formula (5-3) can be exemplified by compounds represented by formulas (5-4) to (5-8) below.

[0113]

[0114]

[0115] The compounds represented by formulas (5-4) to (5-8) are respectively: (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, and 4-methylphenylsulfonyloxyimino-α-(4-methoxyphenyl)acetonitrile. Commercially available compounds of the above can be used.

[0116] Examples of the aforementioned N-sulfonyloxy imide compounds include: N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylcis-butene diimide, N-(camphorsulfonyloxy)diphenylcis-butene diimide, (4-methylphenyl) N-(2-trifluoromethylphenylsulfonyloxy)diphenylcis-butene diimide, N-(4-fluorophenylsulfonyloxy)diphenylcis-butene diimide, N-(phenylsulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxylic acid diimide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxylic acid diimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxylic acid diimide, N-(nonafluorobutyryloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxylic acid diimide, N-(camphorsulfonyl ... Carboxyl imide, N-(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl imide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl imide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl imide, N-(4-methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl imide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl imide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl imide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept -5-ene-2,3-dicarboxylic imide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5-ene-2,3-dicarboxylic imide, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylic imide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylic imide, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylic imide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylic imide, N-(2-trifluoro ...1] Heptane-5,6-oxy-2,3-dicarboxylic imide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylic imide, N-(trifluoromethylsulfonyloxy)naphthalene dicarboximide, N-(camphorsulfonyloxy)naphthalene dicarboximide, N-(4-methylphenylsulfonyloxy)naphthalene dicarboximide, N-(phenylsulfonyloxy)naphthalene dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)naphthalene dicarboximide, N-(4-fluorophenylsulfonyloxy)naphthalene dicarboximide, N-(pentafluoroethylsulfonyloxy)naphthalene dicarboximide, N-(heptafluoropropylsulfonyloxy)naphthalene dicarboximide, N- (Non-fluorobutylsulfonyloxy)naphthalenedicarboximide, N-(ethylsulfonyloxy)naphthalenedicarboximide, N-(propylsulfonyloxy)naphthalenedicarboximide, N-(butylsulfonyloxy)naphthalenedicarboximide, N-(pentylsulfonyloxy)naphthalenedicarboximide, N-(hexylsulfonyloxy)naphthalenedicarboximide, N-(heptylsulfonyloxy)naphthalenedicarboximide, N-(octylsulfonyloxy)naphthalenedicarboximide, N-(nonylsulfonyloxy)naphthalenedicarboximide, etc.

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

[0118] Based on the amount of resin (A) used being 100 parts by weight, the amount of photoacid generating agent (B) used being 0.1 to 10 parts by weight, preferably 0.1 to 8 parts by weight, and more preferably 0.1 to 5 parts by weight. When the resin composition contains a photoacid generating agent (B) with the structure shown in formula (5), the chemical resistance of the protective film made from this resin composition can be further improved.

[0119] Solvent (C)

[0120] There are no particular limitations on the type of solvent (C) used in this invention. Specific examples of solvent (C) include compounds containing alcoholic hydroxyl groups or cyclic compounds containing carbonyl groups.

[0121] Specific examples of compounds containing an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (also known as diacetone alcohol, abbreviated DAA), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether (PGEE), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol mono-n-propyl ether, and propylene glycol mono-n-butyl ether. The compounds containing hydroxyl groups include propylene glycol mono-t-butyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, or combinations thereof. It is noteworthy that compounds containing hydroxyl groups are preferably diacetone alcohol, ethyl lactate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, or combinations thereof. Compounds containing hydroxyl groups can be used alone or in combination.

[0122] Specific examples of carbonyl-containing cyclic compounds include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methyl pyrrolidone, cyclohexanone, or cycloheptanone. It is noteworthy that γ-butyrolactone, N-methyl pyrrolidone, cyclohexanone, or combinations thereof are preferred carbonyl-containing cyclic compounds. Carbonyl-containing cyclic compounds can be used alone or in combination.

[0123] Compounds containing hydroxyl groups can be used in combination with cyclic compounds containing carbonyl groups, and there are no particular limitations on their weight ratio. The weight ratio of the hydroxyl-containing compound to the cyclic compound containing carbonyl groups is preferably 99 / 1 to 50 / 50; more preferably 95 / 5 to 60 / 40.

[0124] Other solvents may be included without impairing the effects of the present invention. Specific examples of 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.

[0125] The amount of resin (A) used is 100 parts by weight, and the amount of solvent (C) used is 200 to 2000 parts by weight, preferably 200 to 1500 parts by weight, and even more preferably 200 to 1000 parts by weight.

[0126] Epoxy compounds (D)

[0127] The epoxy compound (D) used in this invention has the structure shown in formula (2).

[0128] A-(B) n1 (2)

[0129] In equation (2), A represents a nitrogen-containing cyclic group with a valence of (n1), B represents the structure shown in equation (2-1), and n1 represents an integer from 2 to 8.

[0130]

[0131] In equation (2-1), R 4 and R 5 Each of the following can be independently represented as either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R 6 The following characters represent hydrocarbon groups with a valence of (n4+1); n2 represents an integer of 1; n3 represents an integer of 2; n4 represents an integer from 2 to 5; n5 represents an integer of 0 or 1; n6 represents an integer of 0 or 1; and * 2 This is the bond between B and A.

[0132] The structure shown in formula (2) above includes epoxy compounds with the structures shown in formula (2-2), formula (2-3) or formula (2-4).

[0133]

[0134] In equations (2-2), (2-3), and (2-4), A represents a nitrogen-containing cyclic group with an (n1) valence; R4 and R 5 R represents either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 6 The (n4+1) valence hydrocarbon group represents an integer from 2 to 8; n2 represents an integer of 1; n3 represents an integer of 2; and n4 represents an integer from 2 to 5.

[0135] In formulas (2), (2-1), (2-2), (2-3), and (2-4), A can be, for example, a nitrogen-containing cyclic group with (n1) hydrogen atoms removed from a trialkyl isocyanurate, or a nitrogen-containing cyclic group with (n1) hydrogen atoms removed from isocyanuric acid, cyanuric acid, hydantoin, or barbituric acid.

[0136] R 4 and R 5Each of these can be independently represented by a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, dibutyl, tributyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2-methyl-2-ethyl-n-propyl, 2-methyl-2-methyl-n-propyl, 2,2 -Dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3 -Dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-n-butyl Methyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl, etc.

[0137] R 6 This indicates a (n4+1) valence hydrocarbon group. Examples of hydrocarbon groups include (n4+1) valence hydrocarbon groups obtained by removing (n4+1) hydrogen atoms from the aforementioned alkyl groups.

[0138] In formula (2), structures corresponding to B substituted on A can be listed below as alkyl esters, alkyl groups and alkoxy groups with epoxy groups.

[0139]

[0140] In equations (2-8) to (2-11), n5 represents an integer of 0 or 1; n6 represents an integer of 0 or 1.

[0141] Furthermore, the structures corresponding to the nitrogen-containing cyclic group of A in formula (2) can be listed as shown in formulas (2-5) to (2-7) below, where B can be the polyfunctional epoxy group shown in formulas (2-8) to (2-11) above.

[0142]

[0143] In equation (2-5), R 7 It refers to a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0144] In some embodiments, the epoxy compound represented by formula (2-2) above can be prepared by reacting a carboxylic acid or a carboxylic acid anhydride having the structure described above with an enol to obtain a compound (intermediate) having unsaturated bonds. This intermediate is then reacted with a peroxide to produce the epoxy compound. Furthermore, the intermediate can be prepared by any method, not limited to the reaction of a carboxylic acid or carboxylic anhydride with an enol. By reacting this intermediate having the unsaturated bonds with a peroxide, the epoxy compound represented by formula (2-2) above can be prepared.

[0145] Enols corresponding to the B (alkyl ester group with polyfunctional epoxy group) substituted on A as described above can be listed as follows.

[0146]

[0147] As A represents a (n1) valence nitrogen-containing cyclic carboxylic acid, examples of tricarboxyalkyl isocyanurates (the alkyl group may be an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms) are listed below.

[0148]

[0149] In equation (2-13-1), R 7 It refers to a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0150] Examples of compounds (intermediates) with unsaturated bonds obtained by reacting a carboxylic acid or carboxylic anhydride having the structure of A above with an enol include those of formula (2-2-1).

[0151]

[0152] In equation (2-2-1), A represents a (n1) valence nitrogen-containing cyclic group, and R 4 and R 5 Each of the following independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 6It represents a (n4+1) valence hydrocarbon group, where n1 represents an integer from 2 to 8, n2 represents an integer from 1, n3 represents an integer from 2, and n4 represents an integer from 2 to 5.

[0153] In some embodiments, the epoxy compound (D) represented by formula (2-2) used in this invention can be obtained, for example, by reacting compounds of formula (2-12-1) and formula (2-13-2), as shown in the following specific method.

[0154]

[0155] First, a carboxylic acid and an enol are reacted to synthesize an intermediate (olefin). This reaction is carried out in a solvent such as toluene, using a catalyst such as p-toluenesulfonic acid or sulfuric acid, at a temperature of room temperature (e.g., 20°C) to 110°C for more than 0 hours to less than or equal to 100 hours. Then, the unsaturated compound (intermediate) is oxidized by a peroxide to obtain an epoxy compound. The peroxide can be, for example, m-chloroperbenzoic acid, peracetic acid, or hydrogen peroxide-tungstic acid. This peroxidation reaction is carried out in a solvent such as chloroform at a temperature of 0°C to 60°C for 1 hour to 200 hours. The above reaction can be carried out using an anhydride instead of a tricarboxylic acid compound as a starting material. Furthermore, when the carboxylic acid used is poorly soluble in solvents such as toluene, the intermediate (olefin) can be synthesized by esterifying the carboxylic acid with an alcohol such as methanol, followed by transesterification with an enol; or by reacting the carboxylic acid and enol with a condensing agent such as carbodiimide; or by converting the carboxylic acid to an acyl chloride using a thionyl chloride, followed by reaction with an enol.

[0156] The epoxy compound represented by the above formula (2-3) can be manufactured by reacting a nitrogen-containing cyclic compound with an A structure (this compound has an NH group) with an enol or allyl halide with a desaturable group, and then reacting the resulting compound with unsaturated bonds (intermediate) with a peroxide.

[0157] Furthermore, the epoxy compound represented by the above formula (2-3) can be manufactured by reacting a nitrogen-containing compound with structure A (which has an NH group) with an epoxy compound having unsaturated bonds, then reacting the resulting alcohol compound with an enol or allyl halide having a desaturable group, and then reacting the resulting compound (intermediate) with a peroxide.

[0158] Enols and allyl halides having a desaturable group corresponding to B substituted on A can be obtained, for example, by reacting compounds represented by the above formulas (2-12-1), (2-12-2), (2-12-3), and (2-12-4) with methanesulfonyl halides, trifluoromethanesulfonic anhydrides, toluenesulfonyl halides, nitrobenzenesulfonyl halides, acetic halides, acetic anhydrides, trifluoroacetic anhydrides, phosphorus oxychloride, phosphorus oxybromooxychloride, sulfoxide halides, sulfur halides, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc., as shown below, with compounds represented by the following formulas (2-12-5), (2-12-6), (2-12-7), and (2-12-8).

[0159]

[0160] In formulas (2-12-5), (2-12-6), (2-12-7), and (2-12-8), Y represents methanesulfonyloxy, trifluoromethanesulfonyloxy, toluenesulfonyloxy, nitrobenzenesulfonyloxy, acetoxy, trifluoroacetoxy, chlorine atom, bromine atom, or iodine atom.

[0161] The nitrogen-containing compounds with the structure A (which have an NH group) are listed below.

[0162]

[0163] An intermediate obtained by reacting a nitrogen-containing cyclic compound with structure A (which has an NH group) with an enol or allyl halide having a desaturable group can be exemplified by formula (2-3-1).

[0164]

[0165] In equation (2-3-1), A represents a (n1) valence nitrogen-containing cyclic group, and R 4 and R 5 Each of the following independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 6 It represents a (n4+1) valence hydrocarbon group, where n1 represents an integer from 2 to 8, n2 represents an integer from 1, n3 represents an integer from 2, and n4 represents an integer from 2 to 5.

[0166] In some embodiments, the epoxy compound represented by formula (2-3) used in this invention can be obtained, for example, by reacting compounds of formula (2-12-5) and formula (2-13-3), as shown in the following specific method.

[0167]

[0168] First, an intermediate (olefin) is synthesized by reacting a nitrogen-containing cyclic compound (containing an NH group) with an enol having a descalable group. This reaction is carried out in solvents such as dimethylformamide (DMF) using bases such as sodium hydride, potassium carbonate, potassium tert-butoxide, or triethylamine, at a temperature above room temperature (e.g., 20°C) and below the boiling point of the solvent for a period greater than 0 hours to equal to or less than 100 hours. Then, this unsaturated compound is oxidized with a peroxide to obtain an epoxy compound. Examples of peroxides that can be used include m-chloroperbenzoic acid, peracetic acid, and hydrogen peroxide-tungstic acid. This reaction is carried out in solvents such as chloroform at a temperature between 0°C and 60°C for 10 to 200 hours.

[0169] Furthermore, the epoxy compounds represented by the above formulas (2-4) can be manufactured, for example, by reacting an alcohol having the structure of the above A with an enol or allyl halide having a desaturable group, and then reacting the resulting compound (intermediate) with an unsaturated bond with a peroxide.

[0170] As descalable enols or allyl halides having a group corresponding to B substituted on A, compounds represented by formulas (2-12-1), (2-12-2), (2-12-3), and (2-12-4) can be reacted with methanesulfonyl halides, trifluoromethanesulfonic anhydrides, toluenesulfonyl halides, nitrobenzenesulfonyl halides, acetyl halides, acetic anhydrides, trifluoroacetic anhydrides, phosphorus oxychloride, phosphorus oxybromooxychloride, sulfoxide halides, sulfur halides, hydrogen chloride, hydrogen bromide, or hydrogen iodide to obtain compounds represented by formulas (2-12-5), (2-12-6), (2-12-7), and (2-12-8).

[0171] As A represents an alcohol with a (n1) valence nitrogen-containing cyclic group, the following alcohols can be cited as examples.

[0172]

[0173] In equation (2-13-4), R 7 It refers to a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0174] An unsaturated compound (intermediate) obtained by reacting an alcohol having the structure of A above with an enol or allyl halide having a desaturable group can be exemplified by formula (2-4-1).

[0175]

[0176] In equation (2-4-1), A represents a (n1) valence nitrogen-containing cyclic group, and R 4 and R 5 Each of the following independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 6It represents a (n4+1) valence hydrocarbon group, where n1 represents an integer from 2 to 8, n2 represents an integer from 1, n3 represents an integer from 2, and n4 represents an integer from 2 to 5.

[0177] In some embodiments, the epoxy compound represented by formula (2-4) used in this invention can be obtained, for example, by reacting compounds of formula (2-12-5) and formula (2-13-5), as shown in the following specific method.

[0178]

[0179] First, an intermediate (olefin) is synthesized by reacting an alcohol with an enol having a descalable group. This reaction is carried out in solvents such as ethers or amides, using bases such as sodium hydroxide, potassium carbonate, potassium terbutoxide, or triethylamine, at a temperature above room temperature (e.g., 20°C) and below the boiling point of the solvent, for a period greater than 0 hours and less than or equal to 100 hours. Then, this unsaturated compound is oxidized with a peroxide to obtain an epoxy compound. The peroxide can be, for example, m-chloroperbenzoic acid, peracetic acid, or hydrogen peroxide-tungstic acid. This reaction is carried out in solvents such as chloroform at a temperature between 0°C and 60°C for a period of 1 hour to 200 hours.

[0180] The epoxy compound represented by formula (2-4) above can be manufactured, for example, by reacting cyanuric chloride with allyl alcohols represented by formulas (2-12-1), (2-12-2), (2-12-3), and (2-12-4), and then, as described above, reacting the resulting compound (intermediate) with unsaturated bonds with a peroxide.

[0181]

[0182] In some embodiments, epoxy compounds as shown in formula (2-2) may be listed as formulas (2-2-2) to (2-2-9).

[0183]

[0184]

[0185] In some embodiments, epoxy compounds as shown in formula (2-3) may be listed as formulas (2-3-2) to (2-3-5).

[0186]

[0187] In some embodiments, epoxy compounds as shown in formula (2-4) may be listed as formulas (2-4-2) to (2-4-10).

[0188]

[0189] In some preferred embodiments, the epoxy compound (D) of the present invention preferably has the structure shown in formula (2-2).

[0190] The amount of resin (A) used is 100 parts by weight, and the amount of epoxy compound (D) used is 1 to 20 parts by weight, preferably 1 to 15 parts by weight, and more preferably 1 to 10 parts by weight. If epoxy compound (D) is not used, the protective film made from the resin composition has poor development adhesion and chemical resistance.

[0191] Other additives (E)

[0192] Optionally, the chemically amplified positive photosensitive resin composition of the present invention may include other additives (E). Specifically, specific examples of other additives (E) are sensitizers, adhesion auxiliary agents, surfactants, solubility promoters, defoamers, or combinations thereof.

[0193] There are no particular restrictions on the type of sensitizer. Preferably, the sensitizer is a compound containing a phenolic hydroxyl group, for example:

[0194] (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-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane or bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane, etc.;

[0195] (2) Bisphenol type compounds: 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.;

[0196] (3) Polynuclear branched compounds: 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.

[0197] (4) Condensation-type phenol compounds: such as 1,1-bis(4-hydroxyphenyl)cyclohexane, etc.

[0198] (5) Polyhydroxy benzophenones: such as 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4,2',4'-tetrahydroxybenzophenone, 2,4,6,3',4'-pentahydroxybenzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone, 2,4,6,3',4',5'-hexahydroxybenzophenone, or 2,3,4,3',4',5'-hexahydroxybenzophenone, etc.; or

[0199] (6) Combinations of the above-mentioned types of compounds containing phenolic hydroxyl groups.

[0200] Based on the amount of resin (A) used being 100 parts by weight, the amount of sensitizer used being 5 to 50 parts by weight; preferably 8 to 40 parts by weight; and even more preferably 10 to 35 parts by weight.

[0201] Specific examples of adhesion promoters include melamine compounds and silane compounds. The function of adhesion promoters is to increase the adhesion between films formed from photocurable polysiloxane compositions and components or substrates.

[0202] Specific examples of commercially available melamine include products manufactured by Mitsui Chemicals under the trade names Cymel-300 or Cymel-303; or products manufactured by Sanwa Chemicals under the trade names MW-30MH, MW-30, MS-11, MS-001, MX-750, or MX-706.

[0203] When melamine compound is used as an adhesion promoter, the amount of melamine compound used is 0 to 20 parts by weight based on 100 parts by weight of resin (A); preferably 0.5 to 18 parts by weight; and more preferably 1.0 to 15 parts by weight.

[0204] Specific examples of silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyldimethylmethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, or commercially available products manufactured by Shin-Etsu Chemical Co., Ltd. (trade names such as KBM403), etc.

[0205] When a silane compound is used as an adhesion promoter, the amount of the silane compound used is 0 to 2 parts by weight, based on 100 parts by weight of resin (A); preferably 0.05 to 1 part by weight; and more preferably 0.1 to 0.8 parts by weight.

[0206] Specific examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane surfactants, fluorinated surfactants, or combinations thereof.

[0207] Examples of surfactants include (1) polyethylene glycol alkyl ethers: polyethylene glycol dodecyl ether, etc.; (2) polyethylene glycol alkylphenyl ethers: polyethylene glycol octylphenyl ether, polyethylene glycol nonylphenyl 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) tertiaryamine modified polyurethanes, etc. Specific examples of commercially available surfactants include KP (manufactured by Shin-Etsu Chemical Industry), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow (manufactured by Kyoeisha Oil & Fat Chemical Industry), F-Top (manufactured by Tochem Products Co., Ltd.), Megaface (manufactured by Dai Nippon Inki Chemical Industry (DIC), Fluorade (manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Asahi Glass), SINOPOL E8008 (manufactured by Chuji Synthetic Chemicals), F-475 (manufactured by Dai Nippon Inki Chemical Industry), or combinations thereof.

[0208] The amount of resin (A) used is 100 parts by weight, and the amount of surfactant used is 0.5 parts by weight to 50 parts by weight; preferably 1 part by weight to 40 parts by weight; and more preferably 3 to 30 parts by weight.

[0209] 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).

[0210] Based on the amount of resin (A) used being 100 parts by weight, the amount of defoamer used being 1 to 10 parts by weight; preferably 2 to 9 parts by weight; and even more preferably 3 to 8 parts by weight.

[0211] Examples of solubility promoters include N-hydroxydicarboxylicimides and compounds containing phenolic hydroxyl groups. A specific example of a solubility promoter is the compound containing phenolic hydroxyl groups used in o-naphthoquinone diazidesulfonate (B).

[0212] Based on the amount of resin (A) used being 100 parts by weight, the amount of dissolution accelerator used being 1 to 20 parts by weight; preferably 2 to 15 parts by weight; and even more preferably 3 to 10 parts by weight.

[0213] A specific example of a chemically amplified positive photosensitive resin composition is prepared by placing the resin (A), photoacid generator (B), solvent (C), and epoxy compound (D) in a stirrer and stirring them to mix them uniformly into a solution. If necessary, other additives (E) may be added.

[0214] The present invention also provides a protective film comprising coating the above-mentioned chemically amplified positive photosensitive resin composition onto a substrate, and then subjecting it to pre-baking, exposure, development and post-baking treatments.

[0215] The present invention further provides an assembly having a protective film, comprising a substrate and the protective film.

[0216] Methods for forming protective films

[0217] In some embodiments, the chemically amplified positive photosensitive resin composition of the present invention can be used as a forming material for a protective film of a display component. Additionally, the present invention also includes a protective film for a display component formed from the chemically amplified positive photosensitive resin composition.

[0218] The method for forming the protective film includes the following steps:

[0219] (1) The step of forming a coating on a substrate using a chemically amplified positive photosensitive resin composition (hereinafter also referred to as "step (1)");

[0220] (2) The step of irradiating at least a portion of the above coating with radiation (hereinafter also referred to as "step (2)");

[0221] (3) The step of developing the above-mentioned coating after irradiation (hereinafter also referred to as "step (3)"); and

[0222] (4) The step of heating the above-mentioned coating after development (hereinafter also referred to as "step (4)").

[0223] According to this formation method, a protective film for display components with excellent surface hardness, solvent resistance, heat resistance, and voltage retention can be formed. Furthermore, by using a chemically amplified positive photosensitive resin composition with good sensitivity, a protective film for display components with fine and intricate patterns can be easily formed. Therefore, the formed protective film for display components is suitable for display components such as liquid crystal display components and organic EL display components.

[0224] [Step (1)]

[0225] In this step, a chemically amplified positive photosensitive resin composition is coated onto a substrate to form a coating film. Preferably, the solvent is removed by pre-baking the coating.

[0226] Substrates can be, for example, glass, quartz, silicon, and resin. Resins can be, for example, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, ring-opening polymers of cyclic olefins, and their hydrides. Pre-baking conditions vary depending on the type and proportion of each component, and can be set to 70°C to 120°C for approximately 1 to 10 minutes.

[0227] [Step (2)]

[0228] In this step, at least a portion of the formed coating is exposed to radiation. Exposure is typically performed through a photomask with a predetermined pattern. The radiation used for exposure is preferably in the wavelength range of 190 nm to 450 nm, more preferably ultraviolet radiation including 365 nm. The exposure dose is obtained by measuring the intensity of the radiation at a wavelength of 365 nm using an illuminance meter (OAI model 356, manufactured by OAI Optical Associates), preferably 500 J / m². 2 Up to 6,000 J / m 2 The optimal value is 1,500 J / m³. 2 Up to 1,800 J / m 2 .

[0229] [Step (3)]

[0230] In this step, the coating film after irradiation is developed. By developing the exposed coating film, unwanted portions (the irradiated portions) are removed to form a predetermined pattern. The developing solution used in the developing step is preferably an alkaline aqueous solution. Examples of alkaline solutions include: inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and amines; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

[0231] In alkaline aqueous solutions, appropriate amounts of water-soluble organic solvents such as methanol and ethanol, or surfactants, can be added. From the viewpoint of obtaining suitable developability, the concentration of alkali in the alkaline aqueous solution is preferably 0.1% by mass or more and 5% by mass or less. Examples of developing methods include: the puddle method, immersion method, agitated immersion method, and spray method. The developing time varies depending on the composition of the chemically amplified positive photosensitive resin, ranging from approximately 10 seconds to 180 seconds. After developing, the coating is rinsed, for example, with running water for 30 to 90 seconds, and then air-dried using, for example, compressed air or compressed nitrogen, to form the desired pattern.

[0232] [Step (4)]

[0233] In this step, the developed coating is heated. During heating, the patterned film is heated using a heating device such as a heating plate or oven to promote the curing reaction of resin (A) and obtain a cured product. The heating temperature is, for example, around 120°C to 250°C. The heating time varies depending on the type of heating machine; for example, it is around 5 to 30 minutes on a heating plate and around 30 to 90 minutes in an oven. Alternatively, a staged baking method involving two or more heating steps can be used. In this way, a patterned film corresponding to the protective film for the target display component can be formed on the surface of the substrate. Furthermore, the application of the cured film is not limited to protective films for display components; it can also be used as a spacer or interlayer insulating film.

[0234] The thickness of the protective film formed for the display component is 0.1 μm to 8 μm, preferably 0.1 μm to 6 μm, and even more preferably 0.1 μm to 4 μm. Detailed Implementation

[0235] The following examples, embodiments, and comparative examples illustrate the method for manufacturing the chemically amplified positive photosensitive resin composition of the present invention and its applications.

[0236] Preparation of resin (A)

[0237] Preparation Example A-1

[0238] A nitrogen inlet, stirrer, heater, condenser, and thermometer were installed on a 1000 mL four-necked conical flask. After introducing nitrogen, 3 parts by weight of methacrylic acid (hereinafter referred to as MAA), 97 parts by weight of 1-ethoxyethyl methacrylate (a-2-1), 10 parts by weight of 2,2'-azobis(2,4-dimethylpentanonitrile) (hereinafter referred to as ADVN), and 240 parts by weight of diethylene glycol dimethyl ether (hereinafter referred to as Diglyme) solvent were added. The above components were then slowly stirred to raise the solution to 70°C, and polycondensation was carried out at this temperature for 6 hours. After the solvent was evaporated, resin (A-1) was obtained.

[0239] Preparation Examples A-2 to A-12 and Comparative Preparation Examples A'-1 to A'-2

[0240] The preparation of resins (A-2) to (A-12) and comparative examples A'-1 to A'-2 were similar to those of the aforementioned resin (A-1), wherein the types and amounts of monomers used are shown in Table 1. However, the amounts of solvent, catalyst, and molecular weight modifier used, the reaction temperature, and the reaction time for polycondensation differ from those of the aforementioned resin (A-1), which are also shown in Table 1.

[0241]

[0242]

[0243] Example 1

[0244] Preparation of chemically amplified positive photosensitive resin composition

[0245] 100 parts by weight of resin (A-1), 0.1 parts by weight of (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile (B-3), and 1 part by weight of epoxy compound (D-1) represented by formula (2-2-2) are added to 200 parts by weight of propylene glycol methyl ether acetate (C-1) and stirred evenly with a shaking stirrer to obtain the chemically amplified positive photosensitive resin composition of Example 1.

[0246] Form a protective film

[0247] A coating of approximately 3 μm was obtained on a plain glass substrate (100×100×0.7 mm) by spin coating. Following a pre-baking at 110°C for 2 minutes, a positive photoresist mask was placed between the exposure unit and the coating, and the coating was irradiated with ultraviolet light from the exposure unit at an energy of 800 J / m². 2The exposed coating was immersed in a 2.38% TMAH aqueous solution at 23°C for 70 seconds. After removing the exposed portion, it was rinsed with water. Finally, it was baked at 220°C for 45 minutes to obtain the protective film on the unexposed glass substrate of Example 1. The specific conditions and evaluation results of Example 1 are shown in Table 2.

[0248] Examples 2 to 16 and Comparative Examples 1 to 7

[0249] The chemically amplified positive photosensitive resin compositions and protective films of Examples 2 to 16 and Comparative Examples 1 to 7 were obtained using the same method as in Example 1. The difference was that the composition or dosage, etc., of Examples 2 to 16 and Comparative Examples 1 to 7 were changed. Specific conditions and evaluation results for Examples 2 to 16 and Comparative Examples 1 to 7 are shown in Tables 2 and 3.

[0250] Table 2

[0251]

[0252] Table 3

[0253]

[0254]

[0255] Evaluation method

[0256] (1) Adhesion of the film:

[0257] After forming a coating of a chemically amplified positive photosensitive resin composition using the above-described method, the coating is irradiated with a mercury lamp at 80 mJ / cm² through a patterned photoresist having a line and spatial pattern with a width of 1 μm to 10 μm. 2 The ultraviolet light was then applied. Next, a 2.38% (w / w) aqueous solution of tetramethylammonium hydroxide was used for development at 25°C for 70 seconds, followed by rinsing with ultrapure water for 1 minute. The separation of lines and spatial patterns with widths of 1 μm to 10 μm after rinsing was observed under a microscope as an evaluation of the development adhesion.

[0258] ◎: Patternless peeling.

[0259] ○: A small amount of the pattern has been peeled off.

[0260] △: Part of the pattern has been peeled off.

[0261] ╳: The entire surface of the pattern is peeled off.

[0262] (2) Chemical resistance:

[0263] After forming a coating of chemically amplified positive photosensitive resin composition using the above-described method, the coating is calcined in an oven heated to 230°C for 30 minutes to form a hardened film. The hardened film is then immersed in N-methylpyrrolidone solvent heated to 40°C for 6 minutes, and the change rate (%) of film thickness before and after immersion is calculated as an indicator of chemical resistance.

[0264] ◎: Film thickness change rate <5%.

[0265] ○: 5%≦Film thickness change rate<10%.

[0266] △: 10%≦ film thickness change rate <15%.

[0267] △: 15%≦ film thickness change rate.

[0268] As shown in Table 2, when the chemically amplified positive photosensitive resin composition contains an epoxy compound (D) and the monomer mixture forming the resin (A) uses a monomer containing an acid-dissociable group (a-2), the protective film formed by this resin composition can exhibit good development adhesion and chemical resistance. In some embodiments, when the monomer mixture forming the resin (A) of the resin composition includes an unsaturated monomer containing a lactone structure (a-3), the development adhesion of the protective film can be further improved. In other embodiments, when the monomer mixture forming the resin (A) of the resin composition includes an unsaturated monomer containing an epoxy group with a specific structure (a-4), or when the resin composition uses a specific photoacid generator (B), the chemical resistance of the protective film can be further improved. On the other hand, as shown in Table 3, if the chemically amplified positive photosensitive resin composition does not use an epoxy compound (D), the protective film formed by this resin composition exhibits poor development adhesion and chemical resistance.

[0269] Although the present invention has been disclosed above with several embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field to which the present invention pertains may make various modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the scope of the claims.

Claims

1. A chemically amplified positive photosensitive resin composition, characterized by comprising: The chemical amplification positive photosensitive resin composition includes: a resin (A) obtained by copolymerization of a monomer mixture including an unsaturated carboxylic acid monomer (a-1) and an acid-dissociable group-containing monomer (a-2) represented by formula (1); (1) In the formula (1), the R 1 and the R 2 are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, or an aryl group, in which a part or all of the hydrogen atoms of the alkyl group, the alicyclic hydrocarbon group, or the aryl group can be substituted; and the R 1 and the R 2 are not simultaneously a hydrogen atom; the R 3 is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group, or an aryl group; in which a part or all of the hydrogen atoms of the alkyl group, the alicyclic hydrocarbon group, the aralkyl group, and the aryl group of the R 3 may be substituted; the R 1 and the R 3 may be mutually bonded to form a cyclic ether structure together with the carbon atom to which the R 1 is bonded and the oxygen atom to which the R 3 is bonded; and the 1 represents a bonding site. a photoacid generator (B); a solvent (C); and an epoxy compound (D) having a structure represented by formula (2): A-(B) n1 (2) In formula (2), A represents an n1-valent nitrogen-containing ring group, B represents a structure represented by formula (2-1), and n1 represents an integer of 2 to 8; (2-1) In the formula (2-1), the R 4 and the R 5 each independently represent a hydrogen atom; the R 6 represents a hydrocarbon group having a valence of n4+1; the n2 represents 1; the n3 represents 2; the n4 represents 2 or 3; the n5 represents 0 or 1; the n6 represents 0 or 1; and the 2 is a bond between the B and the A.

2. The chemically amplified positive photosensitive resin composition according to claim 1, characterized by the structure represented by formula (2) includes a structure represented by formula (2-2), formula (2-3), or formula (2-4): (2-2) (2-3) (2-4) In the formula (2-2), the formula (2-3) and the formula (2-4), the A represents a nitrogen-containing ring group having an n1 valence; the R 4 and the R 5 respectively independently represent a hydrogen atom, the R 6 represents a hydrocarbon group having an n4+1 valence, the n1 represents an integer of 2 to 8; the n2 represents 1, the n3 represents 2; and the n4 represents 2 or 3.

3. The chemically amplified positive photosensitive resin composition according to claim 1, characterized by formula (2) includes a structure represented by formula (2-5) to formula (2-7): (2-5) (2-6) (2-7) In the formula (2-5), R 7 represents a hydrogen atom or an alkyl group having a carbon number of 1 to 10, and B represents a structure represented by the formula (2-1).

4. The chemically amplified positive photosensitive resin composition according to claim 1, characterized by comprising: the monomer mixture further includes an unsaturated monomer (a-3) containing a lactone structure.

5. The chemically amplified positive photosensitive resin composition according to claim 4, characterized by the unsaturated monomer (a-3) containing a lactone structure includes a partial structure represented by formula (3): (3) In the formula (3), the R 8 represents a substituent, the R 8 are each independently the same or different; the Z 1 represents a monocyclic or polycyclic structure containing -O-C(=O)-; the n7 represents an integer of 0 or more; and the 3 is a bond.

6. The chemically amplified positive photosensitive resin composition according to claim 1, characterized by comprising: the monomer mixture further includes an unsaturated monomer (a-4) containing an epoxy group.

7. The chemically amplified positive photosensitive resin composition according to claim 6, characterized by the unsaturated monomer (a-4) containing an epoxy group has a structure represented by formula (4): (4) In the formula (4), the R 9 represents a hydrogen atom or an alkyl group having a carbon number of 1 to 4; the R 10 represents a hydrogen atom or an alkyl group having a carbon number of 1 to 4; the R 11 , the R 12 , the R 13 , and the R 14 independently represent a hydrogen atom, a fluorine atom, a phenyl group, an alkyl group having a carbon number of 1 to 4, or a perfluoroalkyl group having a carbon number of 1 to 4; and the a represents an integer of 1 to 6.

8. The chemically amplified positive photosensitive resin composition according to claim 1, characterized by comprising: the photoacid generator (B) is a compound containing an oxime sulfonate group represented by formula (5): (5) In the formula (5), the R 15 is an alkyl group having a carbon number of 1 to 20, an alicyclic hydrocarbon group having a carbon number of 3 to 20, an aryl group having a carbon number of 6 to 20, or a group in which the hydrogen atoms of the above groups are partially or entirely replaced; and the 4 is a bond.

9. The chemically amplified positive photosensitive resin composition according to claim 1, characterized by comprising: based on 100 parts by weight of the resin (A), the photoacid generator (B) is used in an amount of 0.1 parts by weight to 10 parts by weight, the solvent (C) is used in an amount of 200 parts by weight to 2000 parts by weight, and the epoxy compound (D) is used in an amount of 1 part by weight to 20 parts by weight.

10. The chemically amplified positive photosensitive resin composition according to claim 1, characterized by comprising: based on 100 parts by weight of the monomer mixture, the acid-dissociable group-containing monomer (a-2) is used in an amount of 10 parts by weight to 97 parts by weight.

11. The chemically amplified positive photosensitive resin composition according to claim 4, characterized by comprising: based on 100 parts by weight of the monomer mixture, the unsaturated monomer (a-3) containing a lactone structure is used in an amount of 2 parts by weight to 20 parts by weight.

12. The chemically amplified positive photosensitive resin composition according to claim 6, characterized by comprising: based on 100 parts by weight of the monomer mixture, the unsaturated monomer (a-4) containing an epoxy group is used in an amount of 10 parts by weight to 90 parts by weight.

13. A protective film characterized by comprising: The protective film is formed by applying the chemical amplification positive photosensitive resin composition according to any one of claims 1 to 12 to a substrate, and then performing a pre-baking process, an exposure process, a development process, and a post-baking process.

14. An assembly having a protective film, characterized by The component having a protective film includes a substrate and the protective film according to claim 13.

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