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

Abstract

The invention relates to a chemically amplified positive photosensitive resin composition, a hardened film and an element with the hardened film. The chemically amplified positive photosensitive resin composition includes an acid-dissociable resin (A), a photoacid generator (B), a solvent (C), and a blocked isocyanate silane compound (D). A cured film comprising a chemically amplified positive photosensitive resin composition has a measured internal stress of 40 MPa or less. A hardened film prepared from the chemically amplified positive photosensitive resin composition has good long-term chemical resistance and high-temperature and high-humidity reliability.

Description

TECHNICAL FIELD

[0001] The present application relates to a chemically amplified positive photosensitive resin composition, and in particular to a chemically amplified positive photosensitive resin composition having good high-temperature high-humidity reliability and long-term chemical resistance, a hardened film prepared therefrom, and a device comprising the hardened film. BACKGROUND

[0002] In electronic devices such as thin film transistor liquid crystal display devices, organic electroluminescent devices (organic EL devices), semiconductor devices, or photosensitive devices, an interlayer insulating film or a planarization film is generally included, and the interlayer insulating film or the planarization film is generally formed using a photosensitive composition. In order to meet the requirements for patterning properties, a positive photosensitive resin composition including an acid generator such as a naphthoquinone diazide compound is generally used (see Patent Document 1), but other photosensitive compositions have been proposed in recent years.

[0003] For example, Patent Document 2 is directed to a positive chemically amplified material that forms a hardened film for a display device, and the positive chemically amplified material has higher sensitivity than the aforementioned positive photosensitive resin composition using an acid generator such as a naphthoquinone diazide compound. The positive chemically amplified material contains a crosslinking agent, an acid generator, and an acid-dissociable resin, and the acid-dissociable resin has a protective group that is dissociated by the action of an acid. Although the acid-dissociable resin itself is insoluble or hardly soluble in an alkaline aqueous solution, the protective group is dissociated by the action of an acid to make the acid-dissociable resin soluble in an alkaline aqueous solution. In addition, for example, Patent Documents 3 to 5 propose a positive photosensitive composition containing a resin having an acetal structure and / or a ketal structure and an epoxy group and an acid generator.

[0004] As the layout design of display devices becomes more complex and the number of layers increases, the time during which the hardened film is in contact with chemicals during the process also increases, and the types of chemicals with which the hardened film must be in contact also increase, which can cause changes in long-term chemical resistance. In addition, due to the demand for increased lifetime of display devices, the challenge to achieve new standards for high-temperature high-humidity reliability of hardened films is also increasing.

[0005] [Patent Document]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open (kokai) No. 2001-354822

[0007] [Patent Document 2] Japanese Patent Application Laid-Open (kokai) No. 2004-004669

[0008] [Patent Document 3] Japanese Patent Application Laid-Open (kokai) No. 2004-264623

[0009] [Patent Document 4] Japanese Patent Application Laid-Open (JP-A) No. 2011-215596

[0010] [Patent Document 5] Japanese Patent Application Laid-Open (JP-A) No. 2008-304902 SUMMARY

[0011] Accordingly, the present application enhances the adhesion between layers by controlling the internal stress of the material itself of the chemically amplified positive photosensitive resin composition and the combination of the blocked isocyanate silane compound, thereby enhancing the long-term durability and high-temperature high-humidity reliability of the hardened film, effectively coping with the increasingly complex layout design of display elements, and also prolonging the service life of the display elements.

[0012] The present application provides a chemically amplified positive photosensitive resin composition, comprising: an acid dissociable resin (A), a photo-acid generator (B), a solvent (C), and a blocked isocyanate silane compound (D), wherein the internal stress of the hardened film formed by the chemically amplified positive photosensitive resin composition is 40 MPa or less.

[0013] In one embodiment of the present application, the internal stress of the hardened film formed by the chemically amplified positive photosensitive resin composition described above is 35 MPa or less.

[0014] In one embodiment of the present application, the internal stress of the hardened film formed by the chemically amplified positive photosensitive resin composition described above is 30 MPa or less.

[0015] In one embodiment of the present application, the blocked isocyanate silane compound (D) described above has a structure represented by the following formula (D-1):

[0016]

[0017] In formula (D-1), R 1 and R 2 each independently represent an alkyl group; n represents an integer of 1 to 3; L represents a divalent linking group; X represents -O- or -NR'-; R' represents a hydrogen atom, an alkyl group, or a group capable of forming a cyclic structure in combination with Y; and Y represents a hydrogen atom or a monovalent organic group.

[0018] In one embodiment of the present application, the blocked isocyanate silane compound (D) described above has at least one selected from the group consisting of the structures represented by the following formula (D-2) and formula (D-3):

[0019]

[0020] In formulae (D-2) and (D-3), R 1 and R 2 each independently represents an alkyl group; R 3 to R 6 each independently represents a hydrogen atom, a monovalent organic group, R 3 and R 4 or R 5 and R 6 may be linked to each other to form a cyclic structure; n represents an integer of 1 to 3; and L represents a divalent linking group.

[0021] In one embodiment of the present application, the blocked isocyanate silane compound (D) described above has a structure represented by formula (D-2) described above.

[0022] In one embodiment of the present application, the acid-dissociable resin (A) described above includes a repeating unit (A-2) having a crosslinkable group.

[0023] In one embodiment of the present application, the repeating unit (A-2) having a crosslinkable group described above includes a repeating unit (A-2-1) having an epoxy group and a repeating unit (A-2-2) having an oxetane group.

[0024] In one embodiment of the present application, the acid-dissociable resin (A) described above is formed by copolymerization of a monomer mixture including an unsaturated monomer (a-1) having an acid-dissociable group, an unsaturated monomer (a-2) having a crosslinkable group, and an alkyl (meth)acrylate monomer (a-3).

[0025] In one embodiment of the present application, the content of the blocked isocyanate silane compound (D) is 0.01 to 10% by weight, based on the total weight of 100% by weight of the solid content of the chemically amplified positive photosensitive resin composition described above.

[0026] The present application further provides a hardened film formed by applying the chemically amplified positive photosensitive resin composition described above to a substrate, and then performing a pre-baking process, an exposure process, a development process, and a post-baking process.

[0027] The present application further provides a device having a hardened film, including: a substrate, and a hardened film described above provided on the substrate.

[0028] Based on the above, the present application improves the adhesion between layers by controlling the internal stress of the material itself of the chemically amplified positive photosensitive resin composition and the combination of the blocked isocyanate silane compound, thereby enhancing the long-term durability and high-temperature and high-humidity reliability of the hardened film, effectively coping with the increasingly complex layout design of display devices, and also prolonging the service life of the display device.

[0029] To make the above features and advantages of the present application more obvious and easy to understand, the following embodiments are described in detail as follows. DETAILED DESCRIPTION

[0030] <Chemical Amplification Positive Photosensitive Resin Composition>

[0031] The present application provides a chemical amplification positive photosensitive resin composition, comprising: an acid dissociable resin (A), a photo-acid generator (B), a solvent (C), and a blocked isocyanate silane compound (D), and optionally, a sensitizer (E) and an additive (F). The hardened film formed by the chemical amplification positive photosensitive resin composition has an internal stress of 40 MPa or less.

[0032] <Internal Stress of Hardened Film>

[0033] In the present embodiment, the hardened film formed by the chemical amplification positive photosensitive resin composition has an internal stress of 40 MPa or less, preferably 35 MPa or less, and more preferably 30 MPa or less.

[0034] When the hardened film formed by the chemical amplification positive photosensitive resin composition has an internal stress of 40 MPa or less, the hardened film formed by the chemical amplification positive photosensitive resin composition has good high-temperature and high-humidity reliability and long-term chemical resistance.

[0035] On the contrary, when the hardened film formed by the chemical amplification positive photosensitive resin composition has an internal stress greater than 40 MPa, the hardened film formed by the chemical amplification positive photosensitive resin composition has poor high-temperature and high-humidity reliability and long-term chemical resistance.

[0036] The hardened film formed by the chemical amplification positive photosensitive resin composition has an internal stress of 0 MPa or more.

[0037] Specifically, as the internal stress obtaining method of the hardened film formed by the chemical amplification positive photosensitive resin composition, reference can be made to the description of the <Manufacturing Method of Hardened Film and Element> described later, but the present embodiment is not limited thereto. Specifically, the manufacturing method of the hardened film is as follows:

[0038] The aforementioned chemical amplification positive photosensitive resin composition prepared was applied on a 0.7 mm glass substrate (100 mm x 100 mm) by spin coating. Then, a coating film with a film thickness of 3 μm was formed under heating conditions of 110°C for 2 minutes. Then, rinsing was performed using a 23°C aqueous solution of tetramethylammonium hydroxide (TMAH) with a concentration of 2.38 mass% for 70 seconds, and then pure water for 15 seconds. Then, the coating film was irradiated with a mercury lamp at 200 mJ / cm 2ultraviolet rays. Thereafter, heating is performed using an oven at 230°C for 30 minutes to form a hardened film.

[0039] [Method for measuring internal stress]

[0040] The internal stress of the hardened film can be measured using the following equation (1). Specifically, it can be measured by a contact type film thickness meter (Elcometer®xt, manufactured by Bruker). xt, manufactured by Bruker).

[0041]

[0042] In equation (1), σ represents the internal stress of the hardened film, E s represents the Young's modulus of the substrate, V s represents the Poisson ratio of the substrate, t s represents the thickness of the substrate, t f represents the film thickness of the hardened film, and 1 / R is calculated from the following equation (2):

[0043]

[0044] In equation (2), R before represents the radius of curvature of the substrate, R after represents the radius of curvature of the substrate containing the hardened film.

[0045] Each component of the photosensitive resin composition used in the present application will be described in detail below.

[0046] [Acid-dissociable resin (A)]

[0047] The acid-dissociable resin (A) includes a repeating unit (A-1) containing an acid-dissociable group. In some embodiments, the acid-dissociable resin (A) of the present application can optionally include a repeating unit (A-2) having a cross-linkable group.

[0048] In some embodiments, the acid-dissociable resin (A) of the present application can optionally include a repeating unit (A-2) having a cross-linkable group, wherein the repeating unit (A-2) having a cross-linkable group can further include a repeating unit (A-2-1) having an epoxy group and a repeating unit (A-2-2) having an oxetane group.

[0049] Notably, the acid-dissociable resin (A) is obtained by copolymerization of a monomer mixture and contains an acid-dissociable protecting group. Specifically, the monomer mixture includes an unsaturated monomer (a-1) having an acid-dissociable group.

[0050] Further, the monomer mixture of the acid-dissociable resin (A) can optionally and selectively contain an unsaturated monomer (a-2) having a cross-linkable group, an alkyl (meth)acrylate monomer (a-3), an unsaturated monomer (a-4) containing a maleimide group, an unsaturated carboxylic acid monomer (a-5), an unsaturated monomer (a-6) containing a lactone structure, and other unsaturated monomers (a-7).

[0051] Here, the total amount of monomers of the monomer mixture of the acid-dissociable resin (A) refers to the total weight parts of the unsaturated monomer (a-1) having an acid-dissociable group, the unsaturated monomer (a-2) having a cross-linkable group, the alkyl (meth)acrylate monomer (a-3), the unsaturated monomer (a-4) containing a maleimide group, the unsaturated carboxylic acid monomer (a-5), the unsaturated monomer (a-6) containing a lactone structure, and the other unsaturated monomers (a-7).

[0052] If the monomer mixture of the acid-dissociable resin (A) of the chemically amplified positive photosensitive resin composition of the present application contains the unsaturated monomer (a-1) having an acid-dissociable group, the unsaturated monomer (a-2) having a cross-linkable group, and the alkyl (meth)acrylate monomer (a-3), the hardened film produced therefrom has better long-term chemical resistance.

[0053] Based on the total weight of the solid components of the chemically amplified positive photosensitive resin composition being 100 wt%, the content of the acid-dissociable resin (A) is 75 wt% to 99 wt%, preferably 80 wt% to 97 wt%, and more preferably 85 wt% to 95 wt%.

[0054] [unsaturated monomer (a-1) having an acid-dissociable group]

[0055] The unsaturated monomer (a-1) having an acid-dissociable group has a structure represented by the following formula (a1-1).

[0056]

[0057] In formula (a1-1), R8and R9independently represent a hydrogen atom, an alkyl group substituted or unsubstituted with a substituent, a cycloalkyl group, or an aryl group, and R8and R9cannot be a hydrogen atom at the same time; R 10 represents an alkyl group substituted or unsubstituted with a substituent, a cycloalkyl group, an aralkyl group, or an aryl group; R8and R 10 may be bonded to each other and the carbon atom to which R8is bonded and the oxygen atom to which R 10 are bonded together to form a cyclic ether structure; wherein the R8, R9, and R 10 The substituent of R8, R9, and R

[0058] The acid-dissociative groups of the unsaturated monomer (a-1) with acid-dissociative groups dissociate upon exposure by the acid generated from the photoacid generator (B) described later, and generate polar groups. Therefore, the acid-dissociative resin (A), which was originally insoluble or sparingly soluble in alkaline aqueous solutions, becomes soluble in alkaline aqueous solutions.

[0059] The unsaturated monomer (a-1) with an acid-dissociable group is not particularly limited as long as it has the structure shown in formula (a1-1). The unsaturated monomer (a-1) with an acid-dissociable group can be readily dissociated by acid.

[0060] The alicyclic hydrocarbon groups represented by R8 and R9 can be, for example, alicyclic hydrocarbon groups with 3 to 20 carbon atoms. Furthermore, these alicyclic hydrocarbon groups with 3 to 20 carbon atoms can be polycyclic. Examples of the aforementioned alicyclic hydrocarbon groups with 3 to 20 carbon atoms include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, borneol, norborneol, or adamantyl.

[0061] The aryl groups represented by R8 and R9 can be, for example, aryl groups with 6 to 14 carbon atoms. These aryl groups with 6 to 14 carbon atoms can be monocyclic, composed of linked monocyclic rings, or condensed rings. Examples of aryl groups with 6 to 14 carbon atoms include phenyl or naphthyl groups.

[0062] The substituents of the substituted alkyl, alicyclic hydrocarbon, and aryl groups represented by R8 and R9 can be, for example, halogen atoms, hydroxyl groups, or organic groups.

[0063] Organic groups can be, for example, nitro, cyano, carboxyl, carbonyl, alicyclic hydrocarbon groups (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, borneol, norborneol, or adamantyl), aryl (e.g., phenyl or naphthyl), alkoxy (e.g., methoxy, ethoxy, propoxy, n-butoxy, pentoxy, hexoxy, heptoxy, octoxy, etc., with 1 to 20 carbon atoms), acyl (e.g., acetyl, propionyl, butyryl, isobutyryl, etc., with 2 to 20 carbon atoms), and acyloxy (e.g., acetoxy, propionyloxy, butyryloxy, tert-butyryloxy, tert-pentyloxy, etc., with 2 to 10 carbon atoms). Substituents of alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, etc., with 2 to 20 carbon atoms), haloalkyl (e.g., straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-tetradecyl, n-octadecyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, neopentyl, 2-hexyl, 3-hexyl; alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, adamantyl, etc., obtained by substituting some or all of the hydrogen atoms of the above groups with halogen atoms), or hydroxyalkyl (e.g., hydroxymethyl).

[0064] R10 The alkyl group, alicyclic hydrocarbon group and aryl group represented by R8and R9may be the same as the alkyl group, alicyclic hydrocarbon group and aryl group described above. Furthermore, R 10 The alkyl group represented by R8and R9is preferably an alkyl group having a carbon number of 1 to 6, more preferably a methyl group, an ethyl group or an n-propyl group. R 10 The aralkyl group represented by R8and R9may be, for example, a benzyl group, a phenethyl group, a naphthylmethyl group or a naphthylethyl group, etc.

[0065] R8and R 10 The cyclic ether structure formed by the mutual bonding of R8and R9is preferably a cyclic ether structure having a ring member number of 3 to 20, more preferably a cyclic ether structure having a ring member number of 5 to 8, and particularly preferably, for example, a tetrahydrofuran or a tetrahydropyran.

[0066] The structure represented by formula (a1-1) can be, for example, a group represented by the following formula.

[0067]

[0068] The unsaturated monomer having an acid dissociable group (a-1) can be exemplified by, for example, 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-t-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, 1-ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-t-butoxyethyl acrylate, 1-(2-chloroethoxy)ethyl acrylate, 1-(2- ethylhexyloxy)ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, 1-(2-cyclohexylethoxy)ethyl acrylate, 1-benzyloxyethyl acrylate, 2-tetrahydropyranyl acrylate, 5,6-bis(1-methoxyethoxycarbonyl)-2-norbornene, 5,6-bis(1-(cyclohexyloxy)ethoxycarbonyl)-2-norbornene, 5,6-bis(1-(benzyloxy)ethoxycarbonyl)-2-norbornene, p-1-ethoxyethoxy styrene or m-1-ethoxyethoxy styrene, p-1-methoxyethoxy styrene or m-1-methoxyethoxy styrene, p-1-n-butoxyethoxy styrene or m-1-n-butoxyethoxy styrene, p-1-isobutoxyethoxy styrene or m-1-isobutoxyethoxy styrene, p-1-(1,1-dimethylethoxy)ethoxy styrene or m-1-(1,1-dimethylethoxy)ethoxy styrene, p-1-(2-chloroethoxy)ethoxy styrene or m-1-(2-chloroethoxy)ethoxy styrene, p-1-(2-ethylhexyloxy)ethoxy styrene or m-1-(2-ethylhexyloxy)ethoxy styrene, p-1-n-propoxyethoxy styrene or m-1-n-propoxyethoxy styrene, p-1-cyclohexyloxyethoxy styrene or m-1-cyclohexyloxyethoxy styrene, p-1-(2-cyclohexylethoxy)ethoxy styrene or m-1-(2-cyclohexylethoxy)ethoxy styrene, p-1-benzyloxyethoxy styrene or m-1-benzyloxyethoxy styrene, and the like.

[0069] The unsaturated monomer (a-1) having an acid dissociation group is preferably 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 1-benzyloxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, or 2-tetrahydrofuranyl methacrylate, and more preferably 2-tetrahydropyranyl methacrylate or 2-tetrahydrofuranyl methacrylate.

[0070] The unsaturated monomer (a-1) having an acid dissociation group can be used alone or in a mixture of a plurality of types.

[0071] The unsaturated monomer (a-1) having an acid dissociation group is preferably 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 1-benzyloxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, or 2-tetrahydrofuranyl methacrylate, and more preferably 2-tetrahydropyranyl methacrylate or 2-tetrahydrofuranyl methacrylate.

[0072] [Unsaturated monomer (a-2) having a crosslinking group]

[0073] The unsaturated monomer (a-2) having a crosslinking group refers to a compound that includes a crosslinking group and an unsaturated bond for polymerization. The crosslinking group is not particularly limited as long as it is a group that can undergo a hardening reaction by heat treatment. As specific examples of the unsaturated monomer (a-2) having a crosslinking group, at least one selected from the group consisting of an unsaturated monomer (a-2-1) having an epoxy group, an unsaturated monomer (a-2-2) having an oxetanyl group, an unsaturated monomer (a-2-3) having two alkenyl groups, and an unsaturated monomer (a-2-4) having a group represented by -NH-CH2-O-R (R is a hydrogen atom or an alkyl group having a carbon number of 1 to 20) can be listed. Preferably, at least one selected from the group consisting of an unsaturated monomer (a-2-1) having an epoxy group, an unsaturated monomer (a-2-2) having an oxetanyl group, and an unsaturated monomer (a-2-3) having two alkenyl groups. Among them, in the chemically amplified positive photosensitive resin composition of the present application, as the monomer mixture component of the acid dissociation resin (A), more preferably at least one selected from the group consisting of an unsaturated monomer (a-2-1) having an epoxy group and an unsaturated monomer (a-2-2) having an oxetanyl group is included.

[0074] In the chemically amplified positive photosensitive resin composition of the present application, when the monomer mixture of the acid dissociation resin (A) used includes the unsaturated monomer (a-2) having a crosslinking group, the resulting hardened film has a better long-term chemical resistance.

[0075] The unsaturated monomer (a-2) having a crosslinkable group is used in an amount of 10 to 70 parts by weight, preferably 15 to 60 parts by weight, and more preferably 20 to 50 parts by weight, based on 100 parts by weight of the total amount of monomers in the monomer mixture of the acid-dissociable resin (A).

[0076] [Unsaturated monomers (a-2-1) having an epoxy group and unsaturated monomers (a-2-2) having an oxetanyl group]

[0077] The unsaturated monomers (a-2-1) having an epoxy group and the unsaturated monomers (a-2-2) having an oxetanyl group can have at least one epoxy group or oxetanyl group in one unsaturated monomer, or can have one or more epoxy groups and one or more oxetanyl groups, two or more epoxy groups, or two or more oxetanyl groups. Although there is no particular limitation, it is preferable to have a total of one to three epoxy groups and / or oxetanyl groups, and more preferably to have a total of one or two epoxy groups and / or oxetanyl groups.

[0078] Specific examples of the unsaturated monomers (a-2-1) having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, α-ethyl-3,4-epoxycyclohexylmethyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.

[0079] As specific examples of the unsaturated monomer (a-2-2) having an oxetane group, the following can be preferably exemplified: acrylic acid esters such as 3-(acryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(acryloyloxymethyl)-2-phenyloxetane, 3-(acryloyloxymethyl)-2,2-difluoroxetane, 3-(acryloyloxymethyl)-2,2,4-trifluoroxetane, 3-(acryloyloxymethyl)-2,2,4,4-tetrafluoroxetane, 3-(2-acryloyloxyethyl)oxetane, 3-(2-acryloyloxyethyl)-2-ethyloxetane, 3-(2-acryloyloxyethyl)-3-ethyloxetane, 3-(2-acryloyloxyethyl)-2-trifluoromethyloxetane, 3-(2-acryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-acryloyloxyethyl)-2-phenyloxetane, 3-(2-acryloyloxyethyl)-2,2-difluoroxetane, 3-(2-acryloyloxyethyl)-2,2,4-trifluoroxetane, 3-(2-acryloyloxyethyl)-2,2,4,4-tetrafluoroxetane, and the like;

[0080] 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-2-methyloxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(methacryloyloxymethyl)-2,2-difluoroxetane, 3-(methacryloyloxymethyl)-2,2,4-trifluoroxetane, 3-(methacryloyloxymethyl)-2,2,4,4-tetrafluoroxetane, 3-(2-methacryloyloxyethyl)oxetane, 3-(2-methacryloyloxyethyl)-2-ethyloxetane, 3-(2-methacryloyloxyethyl)-3-ethyloxetane, 3-(2-methacryloyloxyethyl)-2-trifluoromethyloxetane, 3-(2-methacryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-methacryloyloxyethyl)-2-phenyloxetane, 3-(2-methacryloyloxyethyl)-2,2-difluoroxetane, 3-(2-methacryloyloxyethyl)-2,2,4-trifluoroxetane, and 3-(2-methacryloyloxyethyl)-2,2,4,4-tetrafluoroxetane, and the like methacrylic acid esters.

[0081] Among the above monomer compounds, more preferable are glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-(acryloyloxymethyl)-3-ethyloxetane, and 3-(methacryloyloxymethyl)-3-ethyloxetane. The unsaturated monomer having an epoxy group (a-2-1) and the unsaturated monomer having an oxetane group (a-2-2) can be used alone or in combination of two or more.

[0082] When the acid-dissociable resin (A) used in the chemically amplified positive photosensitive resin composition of the present application contains both the unsaturated monomer having an epoxy group (a-2-1) and the unsaturated monomer having an oxetane group (a-2-2) in the monomer mixture, the obtained hardened film has more excellent long-term resistance.

[0083] Based on 100 parts by weight of the total amount of the monomers in the monomer mixture of the acid-dissociable resin (A), the combined amount of the unsaturated monomer having an epoxy group (a-2-1) and the unsaturated monomer having an oxetane group (a-2-2) is preferably 10 to 70 parts by weight, more preferably 12 to 60 parts by weight, and even more preferably 14 to 50 parts by weight.

[0084] [Unsaturated monomer having two alkenyl groups (a-2-3)]

[0085] The unsaturated monomer having two alkenyl groups (a-2-3) has a structure represented by the following formula (a2-3-1) or formula (a2-3-2).

[0086]

[0087] In formula (a2-3-1) and formula (a2-3-2), R1, R2, and R3 each independently represent a hydrogen atom or a linear or branched alkyl group having a carbon number of 1 to 30, preferably a hydrogen atom or a linear or branched alkyl group having a carbon number of 1 to 10, more preferably a hydrogen atom or a linear or branched alkyl group having a carbon number of 1 to 5, and particularly preferably a methyl group.

[0088] In some embodiments, the unsaturated monomer having two alkenyl groups (a-2-3) can include, but is not limited to, the compounds represented by the following formulae.

[0089]

[0090]

[0091] The unsaturated monomer having two alkenyl groups (a-2-3) can be used alone or in combination of two or more.

[0092] The unsaturated monomer (a-2-4) having a group represented by -NH-CH2-O-R (R is a hydrogen atom or an alkyl group having a carbon number of 1 to 20) is preferably further included in the monomer mixture of the acid-dissociable resin (A). By including the unsaturated monomer (a-2-4), a hardening reaction can be induced by mild heat treatment, and a hardening film having excellent properties can be obtained.

[0093] [Unsaturated monomer (a-2-4) having a group represented by -NH-CH2-O-R]

[0094] The unsaturated monomer (a-2-4) having a group represented by -NH-CH2-O-R (R is a hydrogen atom or an alkyl group having a carbon number of 1 to 20) is preferably further included in the monomer mixture of the acid-dissociable resin (A). By including the unsaturated monomer (a-2-4), a hardening reaction can be induced by mild heat treatment, and a hardening film having excellent properties can be obtained.

[0095] R is preferably an alkyl group having a carbon number of 1 to 9, and more preferably an alkyl group having a carbon number of 1 to 4. Furthermore, the alkyl group can be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, and is preferably a linear alkyl group or a branched alkyl group.

[0096] The unsaturated monomer (a-2-4) preferably has a structure represented by the following formula (a2-4).

[0097]

[0098] In formula (a2-4), R1 represents a hydrogen atom or a methyl group, and R2 represents a hydrogen atom or an alkyl group having a carbon number of 1 to 20.

[0099] R2 is preferably an alkyl group having a carbon number of 1 to 9, and more preferably an alkyl group having a carbon number of 1 to 4. Furthermore, the alkyl group can be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, and is preferably a linear alkyl group or a branched alkyl group.

[0100] Specific examples of R2 include a methyl group, an ethyl group, an n-butyl group, an iso-butyl group, a cyclohexyl group, an n-heptyl group, and the like. Among these, a methyl group, an n-butyl group, or an iso-butyl group is preferred.

[0101] The unsaturated monomer (a-2-4) having a group represented by -NH-CH2-O-R (R is a hydrogen atom or an alkyl group having a carbon number of 1 to 20) is preferably further included in the monomer mixture of the acid-dissociable resin (A). By including the unsaturated monomer (a-2-4), a hardening reaction can be induced by mild heat treatment, and a hardening film having excellent properties can be obtained.

[0102] [(Meth)acrylic acid alkyl ester monomer (a-3)]

[0103] Specific examples of the (meth)acrylic acid alkyl ester monomer (a-3) can be (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl ester, (meth)acrylic acid n-butyl ester, (meth)acrylic acid isobutyl ester, (meth)acrylic acid sec-butyl ester, or (meth)acrylic acid t-butyl ester.

[0104] The (meth)acrylic acid alkyl ester monomer (a-3) is used in an amount of 0 to 60 parts by weight, preferably 0.2 to 50 parts by weight, and more preferably 1 to 40 parts by weight, based on 100 parts by weight of the total amount of monomers in the monomer mixture based on the acid dissociable resin (A).

[0105] [Unsaturated monomer (a-4) containing a maleimide group]

[0106] The unsaturated monomer (a-4) containing a maleimide group can have a structure represented by the following formula (a4-1).

[0107]

[0108] In formula (a4-1), R7represents a hydrogen atom, an alkyl group having a carbon number of 1 to 13, a phenyl group substituted or not substituted with a substituent, a benzyl group, or a cycloalkyl group having a carbon number of 3 to 6. The substituent can be an alkyl group having a carbon number of 1 to 5.

[0109] The unsaturated monomer (a-4) containing a maleimide group can include, but is not limited to, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-chlorophenyl)maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmethylmaleimide, N-(2,4,6-tribromophenyl)maleimide, N-[3-(triethoxysilyl)propyl]maleimide, N-stearylmaleimide, N-dodecylmaleimide, N-(2-methoxyphenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, N-(1-hydroxyphenyl)maleimide, and the like, which are nitrogen-substituted or unsubstituted maleimides.

[0110] Among them, the unsaturated monomer (a-4) containing a maleimide group is preferably N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-laurylmaleimide, N-cyclohexylmaleimide, or N-benzylmaleimide, and the like, and more preferably N-phenylmaleimide or N-cyclohexylmaleimide.

[0111] In some embodiments, the unsaturated monomer containing a maleimide group (a-4) can include, but is not limited to, the following compounds.

[0112]

[0113]

[0114] The unsaturated monomer containing a maleimide group (a-4) can be used alone or in a mixture of a plurality of types.

[0115] The unsaturated monomer containing a maleimide group (a-4) is used in an amount of 0 parts by weight to 60 parts by weight, preferably 0.2 parts by weight to 50 parts by weight, and more preferably 1 part by weight to 40 parts by weight, based on 100 parts by weight of the total amount of the monomers of the monomer mixture based on the acid-dissociable resin (A).

[0116] [Unsaturated carboxylic acid monomer (a-5)]

[0117] The unsaturated carboxylic acid monomer (a-5) refers to a compound containing a carboxylic acid group or a carboxylic anhydride and an unsaturated bond for polymerization bonding, and the structure thereof is not particularly limited, and it can include, but is not limited to, an unsaturated monocarboxylic acid compound, an unsaturated dicarboxylic acid compound, an unsaturated dicarboxylic anhydride compound, a polycyclic unsaturated carboxylic acid compound, a polycyclic unsaturated dicarboxylic acid compound, or a polycyclic unsaturated dicarboxylic anhydride compound.

[0118] Specific examples of the unsaturated monocarboxylic acid compound can be, for example, (meth)acrylic acid, crotonic acid, α-chlorocrotonic acid, ethyl acrylate, cinnamic acid, 2-(meth)acryloyloxyethyldisuccinate, 2-(meth)acryloyloxyethylohexahydrophthalate, 2-(meth)acryloyloxyethyldiphenylate, or ω-carboxypolycaprolactone polyol monoacrylate (trade name: ARONIX M-5300, manufactured by Toagosei), and the like.

[0119] Specific examples of the unsaturated dicarboxylic acid compound can be, for example, maleic acid, fumaric acid, methyl fumarate, itaconic acid, citraconic acid, and the like.

[0120] In embodiments of the present application, the unsaturated dicarboxylic anhydride compound can be an anhydride compound of the aforementioned unsaturated dicarboxylic acid compound.

[0121] Specific examples of the polycyclic unsaturated carboxylic acid compound can be, for example, 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, and the like.

[0122] Specific examples of the polycyclic unsaturated dicarboxylic acid compound can be, for example, 5,6-dicarboxylic acid bicyclo[2.2.1]hept-2-ene.

[0123] The polycyclic unsaturated dicarboxylic anhydride compound is an anhydride compound of the aforementioned polycyclic unsaturated dicarboxylic acid compound.

[0124] Preferred specific examples of the unsaturated carboxylic acid monomer (a-5) can be acrylic acid, methacrylic acid, maleic anhydride, 2-methacryloyloxyethyisuccinic acid ester, or 2-methacryloyloxyethyihexahydrophthalic acid.

[0125] The unsaturated carboxylic acid monomer (a-5) can be used alone or in a mixture of a plurality of kinds.

[0126] The unsaturated carboxylic acid monomer (a-5) can be used in an amount of 0 parts by weight to 60 parts by weight, preferably 0.2 parts by weight to 50 parts by weight, and more preferably 1 part by weight to 40 parts by weight, based on 100 parts by weight of the total amount of the monomers in the monomer mixture of the acid-dissociable resin (A).

[0127] [Unsaturated monomer (a-6) containing a lactone structure]

[0128] The unsaturated monomer (a-6) containing a lactone structure can be a compound represented by the following formula (a6-1).

[0129]

[0130] In formula (a6-1), R 11 represents a hydrogen atom or an alkyl group; R 12 represents an alkyl group having a carbon number of 1 to 8, a cycloalkyl group having a carbon number of 3 to 7, an alkoxy group having a carbon number of 1 to 8, an alkoxycarbonyl group having a carbon number of 2 to 8, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid-decomposable group; R 14 represents a single bond or a divalent linking group; R 13 represents a monocyclic or polycyclic structure containing ; b1 represents an integer of 0 or more, and when b1 is greater than 1, a plurality of R 12 may be the same or different.

[0131] R 11 The alkyl group represented by R

[0132] R 12 is preferably an alkyl group having a carbon number of 1 to 4 or a cyano group.

[0133] R 14The divalent linking group of the formula (a-1) may, for example, be a straight-chain alkylen group, a branched alkylen group, a cyclic alkylen group, an aralkylen group, -0-, -COO-, -S-, -NR"-, -CO-, -NR"CO-, or -SO2-, and the like divalent linking group, or a group containing a combination of the aforementioned functional groups, wherein R" may be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom. 14 The divalent linking group of the formula (a-1) preferably contains at least one of -0-, -COO-, -S-, -NH-, and -CO-, or a combination of these groups and -(CH2) d wherein d represents an integer of 1 to 10, preferably an integer of 1 to 6, and more preferably an integer of 1 to 4.

[0134] R 13 is preferably a monocyclic structure. When R 13 represents a monocyclic structure, it is preferably a lactone structure forming a 5-membered ring to a 7-membered ring, and more preferably a lactone structure forming a 5-membered ring or a 6-membered ring. When R 13 represents a polycyclic structure, it is preferably another ring structure, and forms a lactone structure in the form of a bicyclic structure or a spiro structure, and the like. The other ring structure may, for example, be a cyclic hydrocarbon group having 3 to 20 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms, and the like. The heterocyclic group is not particularly limited, and may be exemplified by one in which one or more of the atoms constituting the ring is a hetero atom, 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 is preferably one containing at least one oxygen atom, and may be exemplified by an oxolane ring, an oxane ring, a dioxane ring, and the like.

[0135] b1 is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and particularly preferably 0. When b1 represents an integer of 2 or more, the plurality of R 12 may be the same or different. In addition, the plurality of R 12 may also be bonded to each other to form a ring, but is preferably not bonded to each other to form a ring.

[0136] The unsaturated monomer containing a lactone structure (a-6) is preferably a compound represented by the following formula (a6-2).

[0137]

[0138] In the formula (a6-2), R 11 is a hydrogen atom or an alkyl group; R 12 is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid-decomposable group; b2 represents an integer of 0 or more, and when b2 is greater than 1, the plurality of R 12 may be the same or different; R 14 is a single bond or a divalent linking group; and R13 R R 15 R

[0139] R 11 R

[0140] R 12 R

[0141] R 14 R 14 R d R 14 R

[0142] R 13 R 13 R 13 R

[0143] b2 12 R 12 R R

[0144] R 15 is preferably an oxygen atom. If R 15 is -NR"-, R" can be a hydrogen atom or an alkyl group having a carbon number of 1 to 4, and is preferably a hydrogen atom.

[0145] The compound represented by formula (a6-1) preferably contains a structure represented by any one of the following formulae (a6-3-1) to (a6-3-21).

[0146]

[0147]

[0148] In formulae (a6-3-1) to (a6-3-21), R 16 represents an alkyl group having a carbon number of 1 to 8, a cycloalkyl group having a carbon number of 3 to 7, an alkoxy group having a carbon number of 1 to 8, an alkoxycarbonyl group having a carbon number of 2 to 8, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid-decomposable group, and when s is an integer of 2 or more, a plurality of R 16 may be the same or different.

[0149] The structure represented by formulae (a6-3-1) to (a6-3-21) can have or not have R 16 , and is preferably free of R 16 (that is, s is 0). R 16 preferably represents an alkyl group having a carbon number of 1 to 4 or a cyano group.

[0150] s is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and more preferably 0. When s represents an integer of 2 or more, a plurality of R 16 may be the same or different. In addition, a plurality of R 16 may also be bonded to each other to form a ring, but is preferably free of a ring.

[0151] The compound represented by formula (a6-1) preferably contains a structure represented by formula (a6-3-1), formula (a6-3-4), formula (a6-3-5), formula (a6-3-6), formula (a6-3-13), formula (a6-3-14), or formula (a6-3-17), and more preferably contains a structure represented by formula (a6-3-1), formula (a6-3-4), or formula (a6-3-17).

[0152] Specific examples of the compound represented by formula (a6-1) can include the compounds represented by the following formulae (a6-4-1) to (a6-4-21).

[0153]

[0154]

[0155]

[0156] In formula (a6-4-1) to formula (a6-4-2), R 17 is the same as the definition of the aforementioned R 11 , which is not repeated here. In formula (a6-4-18), Me represents a methyl group.

[0157] Specific examples of the lactone structure-containing unsaturated monomer (a-6) can include the compounds represented by the following formula (a6-5-1) to formula (a6-5-11), and preferably the compounds represented by the following formula (a6-5-1) to formula (a6-5-11).

[0158]

[0159]

[0160] The aforementioned lactone structure-containing unsaturated monomer (a-6) can be used alone or in a mixture of a plurality of kinds.

[0161] The amount of use of the lactone structure-containing unsaturated monomer (a-6) is 0 parts by weight to 60 parts by weight, preferably 0.2 parts by weight to 50 parts by weight, and more preferably 1 part by weight to 40 parts by weight, based on 100 parts by weight of the total amount of monomers of the monomer mixture based on the acid-dissociable resin (A).

[0162] [Other unsaturated monomers (a-7)]

[0163] The other unsaturated monomers (a-7) can include (meth)acrylic alicyclic esters, (meth)acrylic aryl esters, unsaturated dicarboxylic acid diesters, (meth)acrylic hydroxyalkyl esters, polyether (meth)acrylates, aromatic vinyl compounds, and other unsaturated monomers other than the aforementioned compounds.

[0164] Specific examples of the (meth)acrylic alicyclic esters can be (meth)acrylic cyclohexyl ester, (meth)acrylic-2-methylcyclohexyl ester, tricyclo[5.2.1.0 2.6 ]dec-8-yl (meth)acrylate (or called bicyclic pentyl (meth)acrylate), dicyclopentyl (meth)acrylate, or isobornyl (meth)acrylate.

[0165] Specific examples of the (meth)acrylic aryl esters can be phenyl (meth)acrylate or benzyl (meth)acrylate.

[0166] Specific examples of the unsaturated dicarboxylic acid diesters can be diethyl maleate, diethyl fumarate, or diethyl itaconate.

[0167] Specific examples of the hydroxyalkyl (meth)acrylate can be (meth)acrylic acid-2-hydroxyethyl ester or (meth)acrylic acid-2-hydroxypropyl ester.

[0168] Specific examples of the polyether of (meth)acrylate can be polyethylene glycol mono(meth)acrylate or polypropylene glycol mono(meth)acrylate.

[0169] Specific examples of the aromatic vinyl compound can be styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene or p-methoxystyrene.

[0170] Specific examples of the other unsaturated compound other than the aforementioned compounds can be acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl 1,3-butadiene, N-cyclohexyl maleimide, N-phenyl maleimide, N-benzyl maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate or N-(9-acridinyl)maleimide.

[0171] The other unsaturated monomer (a-7) can be used alone or in a mixture of a plurality of kinds.

[0172] The other unsaturated monomer (a-7) can be used alone or in a mixture of a plurality of kinds.

[0173] [Other resins]

[0174] The chemically amplified positive photosensitive resin composition of the present application can further contain other resins, and the kind of the other resins is not particularly limited, as long as it is different from the acid-dissociable resin (A).

[0175] [Synthetic method of the acid-dissociable resin (A)]

[0176] The synthesis method of the acid-dissociable resin (A) can be, for example, a method in which the monomers of the monomer mixture are polymerized in a suitable solvent by using a radical polymerization initiator. For example, it is preferable to synthesize by a method in which a solution containing the monomers and the radical polymerization initiator is added dropwise to a solution containing the reaction solvent or the monomers to perform the polymerization reaction, a solution containing the monomers and a solution containing the radical polymerization initiator are added dropwise to a solution containing the reaction solvent or the monomers to perform the polymerization reaction, respectively, or a plurality of solutions containing the respective monomers and a solution containing the radical polymerization initiator are added dropwise to a solution containing the reaction solvent or the monomers to perform the polymerization reaction, respectively, or the like.

[0177] The solvent used for the polymerization reaction of the acid-dissociable resin (A) can be, for example, the same solvent as that described later for the solvent (C) or the like.

[0178] A common radical polymerization initiator can be used as the polymerization initiator for the polymerization reaction, and can be, for example, an azo compound such as 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis- isobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4- dimethylvaleronitrile), 2,2'-azobis(2-methylpropionamide) methyl ester, or the like; an organic peroxide such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy trimethylacetate, 1,1'-bis-(t-butylperoxy) cyclohexane, or the like; or hydrogen peroxide or the like.

[0179] In the polymerization reaction of the acid-dissociable resin (A), a molecular weight adjusting agent can be appropriately used in order to adjust the molecular weight, and can be, for example, chloroform, carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolic acid, 3-mercaptopropionic acid, or the like.

[0180] The weight average molecular weight (Mw) of the acid-dissociable resin (A) can be obtained by gel permeation chromatography (GPC) using polystyrene as a standard. w ) is independently 2000 to 38000, preferably 3000 to 28000, and more preferably 4000 to 18000.

[0181] [Photoacid Generator (B)]

[0182] The photoacid generator (B) of the present application can include an oxime sulfonate-based compound (B-1) and another photoacid generator (B-2).

[0183] [Oxime Sulfonate-Based Compound (B-1)]

[0184] The oxime sulfonate compound (B-1) has a structure represented by the following formula (b-1-1) or formula (b-1-2).

[0185]

[0186] In formula (b-1-1), A1 represents an alkyl group having a carbon number of 1 to 10 or an aryl group, which is substituted or unsubstituted with a substituent; A2 represents an alkyl group having a carbon number of 1 to 10, an aryl group having a carbon number of 1 to 10, or a nitrile group; and A3 to A7 each independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to 10, or an aryl group, wherein the alkyl group having a carbon number of 1 to 10 can be substituted with an ether group (-O-) or a thioether group (-S-), or can be unsubstituted.

[0187] The alkyl group having a carbon number of 1 to 10 represented by A1 can be substituted with a fluorine atom, and the aryl group represented by A1 can be substituted with an alkyl group. Preferably, A1 represents an alkyl group having a carbon number of 1 to 6 or a phenyl group, which is substituted with a substituent.

[0188] Preferably, A2 represents an alkyl group having a carbon number of 1 to 6, a phenyl group, or a nitrile group (-CN).

[0189] The alkyl group having a carbon number of 1 to 10 represented by A3 to A7 can be substituted with an ether group (-O-) or a thioether group (-S-), and the aryl group represented by A3 to A7 can be substituted with an alkyl group. Preferably, A3 to A7 can each independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to 6, which is substituted or unsubstituted with an ether group (-O-) or a thioether group (-S-), or a phenyl group, and at least one of A3 to A7 represents an alkyl group substituted with an ether group (-O-) or a thioether group (-S-).

[0190] Preferably, in formula (b-1-1), A1 represents an alkyl group having a carbon number of 1 to 6 or a phenyl group, which is substituted with a substituent; A2 represents an alkyl group having a carbon number of 1 to 6, a phenyl group, or a nitrile group; and A3 to A7 can each independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to 6, which is substituted or unsubstituted with an ether group (-O-) or a thioether group (-S-), or a phenyl group, and at least one of A3 to A7 represents an alkyl group substituted with an ether group (-O-) or a thioether group (-S-). When this preferable condition is satisfied, the developed adhesion of the obtained hardened film can be further improved.

[0191]

[0192] In formula (b-1-2), R 21 represents a halogenated alkyl group having a carbon number of 1 to 12 or a halogenated aryl group having a carbon number of 6 to 10, R 22 represents an alkyl group having a carbon number of 1 to 6, R 23 represents a halogenated alkyl group having a carbon number of 1 to 8 or an alkyl group having a carbon number of 1 to 8.

[0193] The alkyl group having a carbon number of 1 to 6 can be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a hexyl group.

[0194] The haloalkyl group having a carbon number of 1 to 12, for example, a halo-substituted alkyl group having a carbon number of 1 to 8, an alkyl group having a carbon number of 1 to 6, or an alkyl group having a carbon number of 1 to 4, can be mono- or poly-substituted with a halogen, and the degree of substitution with a halogen can vary from one hydrogen atom to all hydrogen atoms. Examples thereof include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, and a 2-fluoropropyl group, and among them, a trifluoromethyl group or a trichloromethyl group is preferred.

[0195] The haloalkyl group having a carbon number of 1 to 12 can include CF3, 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.

[0196] The haloaryl group having a carbon number of 6 to 10, for example, an aryl group substituted with one or more halogen atoms. Examples thereof include a phenyl group or a naphthyl group substituted with one or more halogen atoms, and the phenyl group is substituted with one to five halogen atoms, or one, two, or three halogen atoms, and among them, one or two halogen atoms are preferred; and the naphthyl group is substituted with one to seven halogen atoms, or one, two, or three halogen atoms, and among them, one or two halogen atoms are preferred.

[0197] The halogen is fluorine, chlorine, bromine, and iodine, and among them, fluorine, chlorine, and bromine are preferred, and fluorine and chlorine are more preferred, and fluorine is further preferred.

[0198] In the production method of the compound represented by formula (b-1-2), the corresponding oxime, sulfonyl halide, and in particular, chloride or anhydride can be produced by a method described in the prior art literature, for example, by reacting with a base or a mixture of bases in an inert solvent, or by reacting in a basic solvent; and the inert solvent can include t-butyl methyl ether, tetrahydrofuran (THF), dimethoxyethane, dimethylacetamide (DMA), or dimethylformamide; the base or the mixture of bases can include trimethylamine, pyridine, or 2,6-lutidine; and the basic solvent can include pyridine. The production method of the compound represented by formula (b-1-2) is described in the following examples:

[0199]

[0200] wherein R 21 , R 22 , and R 23The definition is the same as described above, and a description thereof will not be repeated here. Hal represents a halogen atom, and is preferably chlorine.

[0201] The reaction temperature is not particularly limited, and is, for example, -15°C to 50°C, preferably 0°C to 25°C.

[0202] R 21 R is preferably a halogenated alkyl group having 1 to 12 carbon atoms.

[0203] R 22 R is preferably an alkyl group having 1 to 4 carbon atoms; more preferably a methyl group.

[0204] R 23 R is preferably a halogenated alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, more preferably a n-propyl group, -CH3, or -CF3, and further preferably -CH3or -CF3.

[0205] In some embodiments, the oxime sulfonate-based compound (B-1) can include, but is not limited to, the following compounds.

[0206]

[0207]

[0208]

[0209]

[0210]

[0211] The oxime sulfonate-based compound (B-1) can be used alone or in a mixture of two or more.

[0212] The content of the oxime sulfonate-based compound (B-1) is 0.5% by weight to 20% by weight, preferably 1% by weight to 15% by weight, and more preferably 1.5% by weight to 10% by weight, based on the total weight of the solid components of the chemically amplified positive photosensitive resin composition being 100% by weight.

[0213] [Other photo acid generators (B-2)]

[0214] The other photo acid generators (B-2) can include other oxime sulfonate-based compounds, N-sulfonyloxy imide compounds, onium salts, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylate compounds, and the like, other than the aforementioned oxime sulfonate-based compounds (B-1).

[0215] The other oxime sulfonate-based compounds can include oxime sulfonate compounds having the following formula (b-2-1) to formula (b-2-3), and the like.

[0216]

[0217] In formula (b-2-1) to formula (b-2-3), A8may represent a substituted or unsubstituted alkyl group, alicyclic hydrocarbon group, or an aryl group having a carbon number of 1 to 20. In formula (b-2-1) and formula (b-2-2), A9may represent an alkyl group having a carbon number of 1 to 12 or a fluoroalkyl group having a carbon number of 1 to 12. In formula (b-2-3), A 10 represents an alkyl group, an alkoxy group, or a halogen atom. i is an integer of 0 to 3, and when i is 2 or 3, a plurality of A 10 may be the same or different from each other.

[0218] A 10 The alkyl group represented by A 10 The alkoxy group represented by A 10 The halogen atom represented by A

[0219] The oxime sulfonate compound represented by formula (b-2-3) may, for example, be a compound represented by formula (b-2-4) to formula (b-2-8) below, or the like.

[0220]

[0221]

[0222] The oxime sulfonate compound represented by formula (b-2-3) may, for example, be (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, 4-methylphenylsulfonyloxyimino-α-(4-methoxyphenyl)acetonitrile, and a commercially available product of the above-mentioned compounds can be used.

[0223] The N-sulfonyloxy imide compound may, for example, be: N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, (4-methylphenylsulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(phenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(nonafluorobutylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyimide,1] heptane-5, 6-oxyl-2, 3-dicarboxylic imide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5, 6-oxyl-2, 3-dicarboxylic imide, N- (trifluoromethylsulfonyloxy) naphthalene dicarboxylic imide, N- (camphorsulfonyloxy) naphthalene dicarboxylic imide, N- (4-methylphenylsulfonyloxy) naphthalene dicarboxylic imide, N- (phenylsulfonyloxy) naphthalene dicarboxylic imide, N- (2-trifluoromethylphenylsulfonyloxy) naphthalene dicarboxylic imide, N- (4-fluorophenylsulfonyloxy) naphthalene dicarboxylic imide, N- (pentafluoroethylsulfonyloxy) naphthalene dicarboxylic imide, N- (heptafluoropropylsulfonyloxy) naphthalene dicarboxylic imide, N- (nonafluorobutylsulfonyloxy) naphthalene dicarboxylic imide, N- (ethylsulfonyloxy) naphthalene dicarboxylic imide, N- (propylsulfonyloxy) naphthalene dicarboxylic imide, N- (butylsulfonyloxy) naphthalene dicarboxylic imide, N- (pentylsulfonyloxy) naphthalene dicarboxylic imide, N- (hexylsulfonyloxy) naphthalene dicarboxylic imide, N- (heptylsulfonyloxy) naphthalene dicarboxylic imide, N- (octylsulfonyloxy) naphthalene dicarboxylic imide, or N- (nonylsulfonyloxy) naphthalene dicarboxylic imide, and the like.

[0224] Onium salts, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and the like can use the compounds described in Japanese Patent Application Publication No. 2011-232632. For example, benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate.

[0225] The content of the other photoacid generator (B-2) is 0 to 19.5% by weight, preferably 1 to 15% by weight, and more preferably 1.5 to 10% by weight, based on 100% by weight of the total weight of the solid components of the chemically amplified positive photosensitive resin composition.

[0226] The photoacid generator (B) can be used alone or in a mixture of a plurality of kinds.

[0227] The content of the photoacid generator (B) is 0.5 to 20% by weight, preferably 1 to 15% by weight, and more preferably 1.5 to 10% by weight, based on 100% by weight of the total weight of the solid components of the chemically amplified positive photosensitive resin composition.

[0228] [Solvent (C)]

[0229] The solvent (C) of the present application is not particularly limited. Specific examples of the solvent (C) can be alcoholichydroxy-containing compounds, carbonyl group-containing cyclic compounds, and the like.

[0230] Specific examples of the compound containing an alcoholic hydroxyl group are acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (also known as diacetone alcohol (DAA)), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether (PGEE), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, or a combination thereof. Preferably, the compound containing an alcoholic hydroxyl group can be diacetone alcohol, ethyl lactate, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, or a combination thereof. The aforementioned compound containing an alcoholic hydroxyl group can be used alone or in a mixture of a plurality of kinds.

[0231] Specific examples of the cyclic compound containing a carbonyl group are γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methyl pyrrolidone, cyclohexanone, cycloheptanone, and the like. Preferably, the cyclic compound containing a carbonyl group can be γ-butyrolactone, N-methyl pyrrolidone, cyclohexanone, or a combination thereof. The aforementioned cyclic compound containing a carbonyl group can be used alone or in a mixture of a plurality of kinds.

[0232] The compound containing an alcoholic hydroxyl group can be used in combination with the cyclic compound containing a carbonyl group, and the weight ratio thereof is not particularly limited. The weight ratio of the compound containing an alcoholic hydroxyl group to the cyclic compound containing a carbonyl group is preferably 99 / 1 to 50 / 50, more preferably 95 / 5 to 60 / 40.

[0233] The solvent (C) can also include other solvents within a range not impairing the effects of the present application. Specific examples of the other solvents can be: (1) esters: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol methyl ether acetate, 3-methoxy-l-butyl acetate, or 3-methyl-3-methoxy-l-butyl acetate, and the like; (2) ketones: methyl isobutyl ketone, diisopropyl ketone, or diisobutyl ketone, and the like; or (3) ethers: diethyl ether, diisopropyl ether, di-n-butyl ether, or diphenyl ether, and the like.

[0234] The solvent (C) can be used alone or in a mixture of a plurality of kinds.

[0235] The content of the solvent (C) is 10% by weight to 99% by weight, preferably 15% by weight to 97% by weight, more preferably 20% by weight to 95% by weight, based on the total weight of the chemically amplified positive photosensitive resin composition being 100% by weight.

[0236] [Blocked isocyanate silane compound (D)]

[0237] The blocked isocyanate silane compound (D) in the present application refers to a compound having a blocked isocyanate group and a silane structure.

[0238] The blocked isocyanate group in the present application refers to a group in which an isocyanate group is blocked (protected), for example, a group represented by AC(=O)-NH- (A is a protective group).

[0239] The silane structure in the present application is represented by -Si(R a ) 3-n (OR b )n R a and R b each is a hydrocarbon group, preferably an alkyl group, more preferably a methyl group or an ethyl group.

[0240] In the blocked isocyanate silane compound (D) in the present application, one or more blocked isocyanate groups and one or more silane structures are included. In the blocked isocyanate silane compound (D), the upper limit of the number of the blocked isocyanate groups is not particularly limited, for example, 5 or less, preferably 3 or less. The upper limit of the number of the silane structures is not particularly limited, for example, 5 or less, preferably 3 or less.

[0241] In the blocked isocyanate silane compound (D) used in the present application, the blocked isocyanate group and the silane structure are preferably bonded via a divalent linking group. As the divalent linking group, an alkylene group, -0-, -S-, -NR-, -CO-, -COO-, -NRCO-, -SO2- or a combination of these divalent linking groups can be exemplified. Here, R represents a hydrogen atom or an alkyl group having a carbon number of 1 to 4, preferably a hydrogen atom. As the divalent linking group, an alkylene group is preferred, and more preferably an alkylene group represented by -(CH2) m a group represented by -(CH2) m a group containing one or more -0-, -S-, -NH-, -CO- or -COO- in a group represented by -(CH2)

[0242] The molecular weight of the blocked isocyanate silane compound (D) is preferably 200 to 800, more preferably 250 to 600.

[0243] When the blocked isocyanate silane compound (D) is not included in the chemically amplified positive photosensitive resin composition of the present application, the long-term durability and the high-temperature high-humidity reliability of the obtained hardened film are not good.

[0244] The blocked isocyanate silane compound (D) has a structure represented by the following formula (D-1):

[0245]

[0246] In formula (D-1), R 1 and R 2 each independently represents an alkyl group; n represents an integer of 1 to 3; L represents a divalent linking group; X represents -0-, -NR'-; R' represents a hydrogen atom, an alkyl group or a group capable of forming a cyclic structure in combination with Y; Y represents a hydrogen atom or a monovalent organic group.

[0247] In formula (D-1), R 1 and R 2each independently represents an alkyl group. As the alkyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbons is preferable, an unsubstituted alkyl group having 1 to 6 carbons is more preferable, and an alkyl group having 1 to 4 carbons is further preferable, and a methyl group or an ethyl group is particularly preferable.

[0248] In formula (D-1), L represents a divalent linking group. As the divalent linking group, a divalent linking group such as an alkylene group, -0-, -S-, -NR-, -CO-, -COO-, -NRCO-, and -S02-, or a combination of these divalent linking groups can be exemplified. Here, R represents a hydrogen atom or an alkyl group having 1 to 4 carbons, and a hydrogen atom is preferable. As the divalent linking group, a group represented by -(CH2) m - (m is an integer of 1 to 10, preferably an integer of 1 to 6, and more preferably an integer of 1 to 4) or a group in which one or more -0-, -S-, -NH-, -CO-, or -COO- is contained in a group represented by -(CH2) m - (m is an integer of 1 to 10, preferably an integer of 1 to 6, and more preferably an integer of 1 to 4) or a group in which one or more -0-, -S-, -NH-, -CO-, or -COO- is contained in a group represented by -(CH2)

[0249] In formula (D-1), X represents -0-, -NR'-. X in formula (D-1) is a group that is a part of a protective group of the blocked isocyanate silane compound (D), and is not particularly limited because it is to be detached by heating.

[0250] In -NR'-, R' represents a hydrogen atom, an alkyl group, or a group that can form a cyclic structure in combination with Y. When R' represents an alkyl group, R' is preferably a linear or branched alkyl group having 1 to 5 carbons, and more preferably a methyl group or an ethyl group.

[0251] When R' in -NR'- represents a group that can form a cyclic structure in combination with Y, -NR'- represents a group that can form a heterocyclic structure in combination with X in formula (D-1). As the heteroatom in this heterocyclic structure, two or more nitrogen atoms are preferable, and two nitrogen atoms are more preferable. The heterocyclic structure is preferably a 5-membered ring or a 6-membered ring structure, and more preferably a 5-membered ring structure.

[0252] In formula (D-1), Y represents a hydrogen atom or a monovalent organic group. Y in formula (D-1) is a group that is a part of a protective group of the blocked isocyanate silane compound (D), and is not particularly limited because it is to be detached by heating.

[0253] As the monovalent organic group, a hydrogen atom and a hydrocarbon group can be exemplified. As the hydrocarbon group, an alkyl group having 1 to 20 carbons, an aryl group having 6 to 20 carbons, or a combination of these groups is preferable.

[0254] As the alkyl group having 1 to 20 carbons, a linear, branched or cyclic alkyl group having 1 to 20 carbons, an -OH group, -N=R" or a combination of these groups is preferable. R" is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbons.

[0255] As the aryl group having 6 to 20 carbons, a phenyl group substituted with a carboxyl group, a phenyl group or -N=R'" is preferable. R'" is preferably an aryl group having 6 to 10 carbons or a group combined from an aryl group having 6 to 10 carbons and an alkyl group having 1 to 10 carbons.

[0256] Since X and Y in formula (D-1) correspond to so-called protecting groups in the blocked isocyanate silane compound (D), they are detached by heating. The smaller the molecular weight of the detached protecting group, the less the waste components in the final hardened film.

[0257] When the blocked isocyanate silane compound (D) having the structure shown in formula (D-1) is included in the chemically amplified positive photosensitive resin composition of the present application, the resulting hardened film has better high-temperature high-humidity reliability.

[0258] As the blocked isocyanate silane compound (D), one having the structure shown in the following formula (D-1-1) is preferable:

[0259]

[0260] In formula (D-1-1), R 1 and R 2 each independently represent an alkyl group; n represents an integer of 1 to 3; L represents a divalent linking group; and Z represents a monovalent linking group.

[0261] In formula (D-1-1), R 1 and R 2 correspond to R 1 and R 2 in formula (D-1), respectively, and the preferable ranges are the same.

[0262] In formula (D-1-1), L corresponds to L in formula (D-1), and the preferable range is the same.

[0263] In formula (D-1-1), Z corresponds to Y in formula (D-1), and the preferable range is the same.

[0264] As the blocked isocyanate silane compound (D), one having at least one selected from the group consisting of the structures shown in the following formula (D-2) and formula (D-3) is more preferable:

[0265]

[0266] In formula (D-2) and formula (D-3), R 1 and R 2 each independently represents an alkyl group; R 3 to R 6 each independently represents a hydrogen atom, a monovalent organic group, R 3 and R 4 or R 5 and R 6 may be linked to each other to form a cyclic structure; n represents an integer of 1 to 3; and L represents a divalent linking group.

[0267] In formula (D-2) and formula (D-3), R 1 and R 2 correspond to R 1 and R 2 in formula (D-1), respectively. The preferable ranges thereof are also the same.

[0268] In formula (D-2), R 3 and R 4 are preferably an alkyl group, an aryl group, or a heteroaryl group, and more preferably an alkyl group having a carbon number of 1 to 20, an aryl group having a carbon number of 6 to 20, or a heteroaryl group having a carbon number of 6 to 20. R 3 and R 4 may be linked to each other to form a cyclic structure. These hydrocarbon groups can have a substituent, and as the substituent, a carboxyl group, a hydroxyl group, an ester group, and the like can be exemplified.

[0269] In formula (D-3), R 5 and R 6 are preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or R 5 and R 6 are linked to each other to form a heterocyclic structure.

[0270] As the alkyl group, a linear alkyl group or a branched alkyl group having a carbon number of 1 to 5, or -N=R”” is preferable. R”” is a linear alkyl group or a branched alkyl group having a carbon number of 1 to 5. As the aryl group, an aryl group having a carbon number of 6 to 10, and more preferably a phenyl group is preferable. R 5 and R 6 may be linked to each other to form a cyclic structure. These hydrocarbon groups can have a substituent, and as the substituent, a carboxyl group, a hydroxyl group, an ester group, and the like can be exemplified.

[0271] When R 5 and R 6 are linked to each other to form a heterocyclic structure, as the heteroatom in this heterocyclic structure, two or more nitrogen atoms are preferable, and two nitrogen atoms are more preferable. The heterocyclic structure is preferably a 5-membered ring structure or a 6-membered ring structure, and more preferably a 5-membered ring structure.

[0272] In formula (D-2) and formula (D-3), L corresponds to L in formula (D-1), and the preferable range thereof is also the same.

[0273] When the chemical amplification positive photosensitive resin composition of the present application includes the blocked isocyanate silane compound (D) having at least one selected from the group consisting of the structures represented by Formula (D-2) and Formula (D-3), the obtained hardened film has better high-temperature high-humidity reliability.

[0274] When the chemical amplification positive photosensitive resin composition of the present application includes the blocked isocyanate silane compound (D) having the structure represented by Formula (D-2), the obtained hardened film has even better high-temperature high-humidity reliability.

[0275] The blocked isocyanate silane compound (D) can include, but is not limited to, the compound represented by Formula (D-2) below.

[0276]

[0277]

[0278]

[0279] The blocked isocyanate silane compound (D) can be used alone or in a mixture of a plurality of types.

[0280] The content of the blocked isocyanate silane compound (D) is 0.01 to 10% by weight, preferably 0.05 to 5% by weight, and more preferably 0.1 to 1% by weight, based on the total weight of the solid components of the chemical amplification positive photosensitive resin composition being 100% by weight.

[0281] When the content of the blocked isocyanate silane compound (D) in the chemical amplification positive photosensitive resin composition of the present application is within the above range, the obtained hardened film has better high-temperature high-humidity reliability.

[0282] [Photosensitizer (E)]

[0283] The chemical amplification positive photosensitive resin composition of the present application can optionally include a photosensitizer (E) represented by Formula (E-1) below.

[0284]

[0285] In Formula (E-1), X1and X2independently represent an alkyl group, an aralkyl group, an alkoxyalkyl group, an aryloxyalkyl group, or a glycidyl group; X3and X4independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, or a halogen atom; r1and r2independently represent an integer of 0 to 2, and the sum of r1and r2is 0 to 2, wherein the plurality of X3and X4are the same or different.

[0286] Specific examples of the alkyl group represented by X1and X2in formula (E-1) can include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, an n-pentyl group, an n-hexyl group, a 2-ethylhexyl group, an n-decyl group, or an n-dodecyl group. Specific examples of the aralkyl group represented by X1and X2can include a benzyl group or a phenethyl group. Specific examples of the alkoxyalkyl group represented by X1and X2can include a 2-methoxyethyl group or a 2-ethoxyethyl group. Specific examples of the aryloxyalkyl group represented by X1and X2can include a 2-phenoxyethyl group or a 2-naphthoxyethyl group. Specific examples of the glycidyl group represented by X1and X2can include a glycidyl group or a 2-methylglycidyl group.

[0287] Specific examples of the alkyl group represented by X3and X4in formula (E-1) can include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, or a 4-methylpentyl group. Specific examples of the alkoxy group represented by X3and X4can include a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. Specific examples of the aryloxy group represented by X3and X4can include a phenoxy group. Specific examples of the halogen atom represented by X3and X4can include a chlorine atom, a bromine atom, or an iodine atom.

[0288] Specific examples of sensitizers (E) as shown in formula (E-1) may be 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-di(n-propoxy)anthracene, 9,10-di(isopropoxy)anthracene, 9,10-di(n-butoxy)anthracene, 9,10-di(isobutoxy)anthracene, 9,10-di(n-pentoxy)anthracene, 9,10-di(n-hexyloxy)anthracene, 9,10-di(2-ethylhexyloxy)anthracene, 9,10-di(dodecyloxy)anthracene, 9,10-di(allyloxy)anthracene, 9,10-di(2-methylallyloxy)anthracene, 9,10-di(benzyloxy)anthracene, 9,10-di(phenethoxy)anthracene, 9,10-bis(2-phenoxyethoxy)anthracene, 9,10-diglycidyloxy Anthracene, 2-methyl-9,10-dimethoxyanthracene, 2-methyl-9,10-diethoxyanthracene, 2-methyl-9,10-di(n-propoxy)anthracene, 2-methyl-9,10-di(isopropoxy)anthracene, 2-methyl-9,10-di(n-butoxy)anthracene, 2-methyl-9,10-di(isobutoxy)anthracene, 2-methyl-9,10-di(n-pentoxy)anthracene, 2-methyl-9,10-di(n-hexyloxy)anthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-ethyl-9,10-di(n-propoxy)anthracene, 2-ethyl-9,10-di(isopropoxy)anthracene, 2-ethyl-9,10-di(n-butoxy)anthracene, 2-ethyl-9,10-di (Isobutoxy)anthracene, 2-ethyl-9,10-di(n-pentoxy)anthracene, 2-ethyl-9,10-di(n-hexyloxy)anthracene, 2-tert-butyl-9,10-dimethoxyanthracene, 2-tert-butyl-9,10-diethoxyanthracene, 2-tert-butyl-9,10-di(n-propoxy)anthracene, 2-tert-butyl-9,10-di(isopropoxy)anthracene, 2-tert-butyl-9,10-di(n-butoxy)anthracene, 2-tert-butyl-9,10-di(isobutoxy)anthracene, 2-tert-butyl-9,10-di(n-pentoxy)anthracene, 2-tert-butyl-9,10-di(n-hexyloxy)anthracene, 2-(4-methylpentyl)-9,10-dimethoxyanthracene, 2-(4-methylpentyl)-9,10-diethoxyanthracene, 2-(4- 2-(4-methylpentyl)-9,10-di(n-propoxy)anthracene, 2-tert-butyl-9,10-di(isopropoxy)anthracene, 2-(4-methylpentyl)-9,10-di(n-butoxy)anthracene, 2-(4-methylpentyl)-9,10-di(isobutoxy)anthracene, 2-(4-methylpentyl)-9,10-di(n-pentyloxy)anthracene, 2-(4-methylpentyl)-9,10-di(n-hexyloxy)anthracene, 2-chloro-9,10-dimethoxyanthracene, 2-chloro-9,10-diethoxyanthracene, 2-chloro-9,10-di(n-propoxy)anthracene, 2-chloro-9,10-di(isopropoxy)anthracene, 2-chloro-9,10-di(n-butoxy)anthracene, 2-chloro-9,10-di(isobutoxy)anthracene, 2-chloro-9,10-di(isobutoxy)anthracene, 2-chloro-9,10-di(isobutoxy)anthracene, 2-chloro-9,10-di(n-pentoxy)anthracene, 2-chloro-9,10-di(n-hexyloxy)anthracene, 2-phenoxy-9,10-dimethoxyanthracene, 2-phenoxy-9,10-diethoxyanthracene, 2-phenoxy-9,10-di(n-propoxy)anthracene, 2-phenoxy-9,10-di(i-propoxy)anthracene, 2-phenoxy-9,10-di(n-butoxy)anthracene, 2-phenoxy-9,10-di(i-butoxy)anthracene, 2-phenoxy-9,10-di(n-pentoxy)anthracene, 2-phenoxy-9,10-di(n-hexyloxy)anthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-diethoxyanthracene, 2,3-dimethyl-9,10-di(n-propoxy)anthracene, 2,3-dimethyl-9,10-di(i-propoxy)anthracene, 2,3-dimethyl-9,10-di(n-butoxy)anthracene, 2,3-dimethyl-9,10-di(i-butoxy)anthracene, 2,3-dimethyl-9,10-di(n-pentoxy)anthracene, or 2,3-dimethyl-9,10-di(n-hexyloxy)anthracene, and the like.

[0289] The sensitizer (E) represented by Formula (E-1) is preferably 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-di(n-propoxy)anthracene, 9,10-di(n-butoxy)anthracene, 2-methyl-9,10-di(n-butoxy)anthracene, 2-phenoxy-9,10-diethoxyanthracene, 2-chloro-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, or 9,10-diglycidyloxyanthracene.

[0290] The sensitizer (E) can be used alone or in a mixture of a plurality of kinds.

[0291] The content of the sensitizer (E) is 0% by weight to 20% by weight, preferably 0.005% by weight to 17% by weight, and more preferably 0.01% by weight to 15% by weight, based on the total weight of the solid components of the chemically amplified positive photosensitive resin composition as 100% by weight.

[0292] [Additive (F)]

[0293] The chemically amplified positive photosensitive resin composition of the present application can optionally contain an additive (F) within the scope of the efficacy of the present application. Specific examples of the additive (F) can be, for example, an adhesion auxiliary agent, a surfactant, a solubility promoter, a defoamer, or a combination thereof.

[0294] Specific examples of the adhesion auxiliary agent can be a melamine compound, a silane-based compound, and the like.

[0295] Specific examples of the melamine can be commercially available products manufactured by Mitsui Chemicals, Inc., and having trade names of Cymel-300 or Cymel-303, or commercially available products manufactured by Sanwa Chemical Co., Ltd., and having trade names of MW-30MH, MW-30, MS-11, MS-001, MX-750, or MX-706.

[0296] Specific examples of the silane compound can be vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, or commercially available products manufactured by Shin-Etsu Chemical Co., Ltd. (trade names such as KBM403), or the like.

[0297] Specific examples of the surfactant are anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane surfactants, fluorine-based surfactants, or combinations thereof.

[0298] Specific examples of the surfactant can include (1) polyoxyethylene alkyl ethers: polyoxyethylene lauryl ether, or the like; (2) polyoxyethylene alkyl phenyl ethers: polyoxyethylene octyl phenyl ether, or polyoxyethylene nonyl phenyl ether, or the like; (3) polyethylene glycol diesters: polyethylene glycol dilaurate, or polyethylene glycol dihardened acid ester, or the like; (4) sorbitan fatty acid esters; (5) fatty acid modified polyesters; and (6) tertiary amine modified polyurethanes, or the like. Specific examples of commercially available products of the surfactant can be KP (manufactured by Shin-Etsu Chemical), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow (manufactured by Sanyu Chemical Industries), F-Top (manufactured by Tochem Products Co., Ltd.), Megaface (manufactured by DIC), Fluorade (manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Asahi Glass), SINOPOL E8008 (manufactured by Nippon Soda), F-475 (manufactured by DIC), or any combination of the above compounds.

[0299] Specific examples of the dissolution promoter can include N-hydroxydicarboxylic imide compounds or phenolic hydroxyl-containing compounds.

[0300] Specific examples of the defoaming agent can include Surfynol MD-20, Surfynol MD-30, EnviroGem AD01, EnviroGem AE01, EnviroGem AE02, Surfynol DF110D, Surfynol 104E, Surfynol 420, Surfynol DF37, Surfynol DF58, Surfynol DF66, Surfynol DF70, and Surfynol DF210 (manufactured by Air Products and Chemicals, Inc.), and the like.

[0301] The aforementioned adhesion aid, surfactant, dissolution promoter, and defoaming agent can be used singly or in a mixture of a plurality of kinds.

[0302] The content of the additive (F) is 0 to 20% by weight, preferably 0.005 to 17% by weight, and more preferably 0.01 to 15% by weight, based on the total weight of the solid components of the chemically amplified positive photosensitive resin composition as 100% by weight.

[0303] <Method for producing chemically amplified positive photosensitive resin composition>

[0304] The chemically amplified positive photosensitive resin composition of the present application can be produced by placing the acid-dissociable resin (A), the photoacid generator (B), the solvent (C), and the blocked isocyanate silane compound (D) in a stirrer, stirring them to uniformly mix them into a solution state, and, if necessary, adding the sensitizer (E) and / or the additive (F).

[0305] <Method for producing hardened film and element>

[0306] The present application also provides a hardened film formed by applying the aforementioned chemically amplified positive photosensitive resin composition to a substrate, and then performing a pre-baking, exposure, development, and post-baking process.

[0307] The present application also provides an element having a hardened film, which includes a substrate and the aforementioned hardened film, and the hardened film is provided on the substrate.

[0308] In some embodiments, the chemically amplified positive photosensitive resin composition of the present application can be used as a material for forming a hardened film of a display element. In addition, the present application also includes a hardened film for a display element formed from a chemically amplified positive photosensitive resin composition.

[0309] The method for forming a hardened film includes the following steps:

[0310] A process of forming a coating film on a substrate using a chemically amplified positive photosensitive resin composition (hereinafter referred to as process (1));

[0311] A process of irradiating at least a part of the coating film with radiation (hereinafter referred to as process (2));

[0312] A process of developing the coating film after the radiation (hereinafter referred to as process (3)); and

[0313] A process of heating the coating film after the development (hereinafter referred to as process (4)).

[0314] According to this forming method, a hardened film for a display element having excellent high-temperature high-humidity reliability and long-time resistance can be formed. In addition, by using a chemically amplified positive photosensitive resin composition having excellent high-temperature high-humidity reliability and long-time resistance, a hardened film for a display element having a fine and delicate pattern can be easily formed. Therefore, the hardened film for a display element formed is suitable for a display element such as a liquid crystal display element or an organic EL display element.

[0315] Process (1): In this process, a chemically amplified positive photosensitive resin composition is applied to a substrate to form a coating film. Preferably, the coating film is pre-baked to remove the solvent. The substrate may, for example, be glass, quartz, a silicon substrate, or a resin, etc. The resin may, for example, be polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof, etc. The conditions of the pre-baking also vary depending on the type, blending ratio, etc. of each component, and can be set to 70°C to 120°C for 1 minute to 10 minutes.

[0316] Process (2): In this process, exposure is performed by irradiating at least a part of the coating film formed in the aforementioned process with radiation. At the time of the exposure, exposure is usually performed through a mask having a predetermined pattern. The radiation used for the exposure is preferably radiation having a wavelength in the range of 190 nm to 450 nm, and more preferably radiation including ultraviolet rays of 365 nm. The exposure dose is a value obtained by measuring the intensity of radiation having a wavelength of 365 nm using an illuminometer (manufactured by OAI Optical Associates, and model number OAI model 356), and is preferably 500 J / m 2 to 6,000 J / m 2 , more preferably 1,500 J / m 2 to 3,000 J / m 2 .

[0317] Process (3): In this process, the coating film after irradiation of the radiation is subjected to development. By developing the coating film after exposure, the unnecessary portion (irradiation portion of the radiation) is removed to form a predetermined pattern. The developing solution used in the development process is preferably an aqueous alkali solution. The alkali can be, for example, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, or amine; a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide.

[0318] In the aqueous alkali solution, a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added in an appropriate amount. From the viewpoint of obtaining appropriate developability, the concentration of the alkali in the aqueous alkali solution is preferably 0.1% by mass or more and 5% by mass or less. The developing method can be, for example, puddle method, dip method, shake-dip method, or spray method. The developing time varies depending on the composition of the chemically amplified positive photosensitive resin composition, and can be, for example, 1 second to 180 seconds. After the development treatment, for example, water washing is performed for 10 seconds to 90 seconds, and then the coating film is air-dried using, for example, compressed air or compressed nitrogen to form a desired pattern.

[0319] Process (4): In this process, the developed coating film is subjected to heating. At the time of heating, the patterned film is heated using a heating device such as a hot plate or an oven to promote the hardening reaction of the acid-dissociable resin (A) and obtain a hardened product. The heating temperature is, for example, 120°C to 250°C. The heating time varies depending on the type of the heating machine, and is, for example, 5 minutes to 30 minutes on a hot plate and 30 minutes to 90 minutes in an oven. Alternatively, a stage baking method in which the heating process is performed two or more times, or the like can be used.

[0320] In addition, before the post-baking treatment, the entire surface of the patterned substrate can be exposed to actinic rays again (post-exposure), and by the post-baking treatment, the photoacid generator present in the unexposed area generates acid and can function as a catalyst to accelerate the hardening reaction of the film during the cross-linking process. When the post-exposure process is included in the production method of the hardened film, the preferred exposure amount is 100 to 3,000 mJ / cm 2 , and particularly preferably 100 to 500 mJ / cm 2 .

[0321] In this way, a patterned film corresponding to the hardened film for a display element targeted can be formed on the surface of the substrate. Furthermore, the use of the hardened film is not limited to the hardened film for a display element, and can be utilized as a spacer or an interlayer insulating film.

[0322] The film thickness of the hardened film for a display element formed is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and particularly preferably 0.1 μm to 4 μm.

[0323] The following examples are presented to illustrate the application and are not intended to limit the scope of the application. Various modifications can be made by those skilled in the art, without departing from the spirit and scope of the application.

[0324] <Example>

[0325] [Synthesis Example of Acid-Dissociable Resin (A)]

[0326] Synthesis Example A-1

[0327] A four-necked flask with a capacity of 1000 ml was equipped with a nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer. After introducing nitrogen, 30 parts by weight of 1-ethoxyethyl methacrylate (MAEVE, hereinafter referred to as a-1-1), 40 parts by weight of glycidyl methacrylate (GMA, hereinafter referred to as a-2-1-1), 10 parts by weight of 3-(methacryloyloxymethyl)-3-ethyloxetane (OXMA, hereinafter referred to as a-2-2-1), 2 parts by weight of a compound represented by the formula (a2-3-1-1) (hereinafter referred to as a-2-3-1), 10 parts by weight of methyl methacrylate (MMA, hereinafter referred to as a-3-1), 2 parts by weight of a compound represented by the formula (a4-1-3) (hereinafter referred to as a-4-1), 2 parts by weight of methacrylic acid (MAA, hereinafter referred to as a-5-1), 2 parts by weight of a compound represented by the formula (a6-5-1) (hereinafter referred to as a-6-1), 2 parts by weight of 2-hydroxyethyl methacrylate (HEMA, hereinafter referred to as a-7-1), 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN), and 200 parts by weight of diglyme were introduced. Then, the above ingredients were slowly stirred to warm the solution to 70°C, and polymerization was carried out at this temperature for 6 hours. After the solvent was distilled off, the acid-dissociable resin (A-1) of Synthesis Example A-1 was obtained.

[0328] Synthesis Examples A-2 to A-9 and Comparative Synthesis Examples A'-1 to A'-3

[0329] Synthesis Examples A-2 to A-9 and Comparative Synthesis Examples A'-1 to A'-3 were produced by the same method as that used in the production of the acid-dissociable resin (A-1) of Synthesis Example A-1, except that the kind and amount of the monomer used in the resin were changed in Synthesis Examples A-2 to A-9 and Comparative Synthesis Examples A'-1 to A'-3. The formulations are shown in Tables 1 and 2, and further description is omitted.

[0330] In addition, the compounds corresponding to the abbreviations in Tables 1 and 2 are shown below.

[0331]

[0332]

[0333]

[0334]

[0335] [Table 1]

[0336]

[0337] [Table 2]

[0338]

[0339] [Synthesis Example of Enclosed Isocyanate Silane Compound (D)]

[0340] Synthesis Example D-1

[0341] A 10 liter pressurized reaction vessel was equipped with a nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer. After introducing nitrogen, 961.3 g of 3,5-dimethylpyrazole (10 mol) was added as a reactant 1. While stirring the suspension, 2473.6 g of (3-isocyanatopropyl)triethoxysilane (10 mol) was added dropwise as a reactant 2 over a period of 1 hour. The internal temperature was 20 to 160°C. Then, stirring was continued for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. Then, after solvent devolatilization, a compound represented by formula (D-3-1) of Synthesis Example D-1 was obtained.

[0342] Synthesis Example D-2

[0343] The same synthesis procedure as Synthesis Example D-1 was performed except that the reactant 1 was changed to aniline (Aniline) in an equimolar amount, and a compound represented by formula (D-3-2) of Synthesis Example D-2 was obtained.

[0344] Synthesis Example D-3

[0345] The same synthesis procedure as Synthesis Example D-1 was performed except that the reactant 1 was changed to methyl ethyl ketoxime in an equimolar amount, and the reactant 2 was changed to (3-isocyanatopropyl)triethoxysilane in an equimolar amount, and a compound represented by formula (D-2-1) of Synthesis Example D-3 was obtained.

[0346] Synthesis Example D-4

[0347] The same synthetic procedure as Synthetic Example D-1 was conducted except that the reactant 1 was changed to an equimolar amount of 4-methyl-2-pentanone oxime and the reactant 2 was changed to an equimolar amount of (5-isocyanatopentyl)triethoxysilane, whereby the compound represented by the formula (D-2-3) of Synthetic Example D-4 was obtained.

[0348] Synthesis Example D-5

[0349] The same synthetic procedure as Synthetic Example D-1 was conducted except that the reactant 1 was changed to an equimolar amount of phenol and the reactant 2 was changed to an equimolar amount of (3-isocyanatopropyl)triethoxysilane, whereby the compound represented by the formula (D-4-2) of Synthetic Example D-5 was obtained.

[0350] Synthesis Example D-6

[0351] The same synthetic procedure as Synthetic Example D-1 was conducted except that the reactant 1 was changed to an equimolar amount of 1,2-butanediol and the reactant 2 was changed to an equimolar amount of (3-isocyanatopropyl)triethoxysilane, whereby the compound represented by the formula (D-4-5) of Synthetic Example D-6 was obtained.

[0352] Synthesis Example D'-1

[0353] The same synthetic procedure as Synthetic Example D-1 was conducted except that the reactant 1 was changed to an equimolar amount of n-butylamine and the reactant 2 was changed to an equimolar amount of (3-isothiocyanatopropyl)trimethoxysilane, whereby the blocked isothiocyanate silane compound of Synthetic Example D'-1 was obtained.

[0354] [Examples of the chemically amplified positive photosensitive resin composition]

[0355] Examples of the chemically amplified positive photosensitive resin composition are described below.

[0356] Example 1

[0357] After 95 parts by weight of the acid-dissociable resin (A-1) obtained in Synthesis Example A-1 (hereinafter referred to as A-1), 4 parts by weight of a compound represented by the formula (b-1-2-3) (hereinafter referred to as B-1), 120 parts by weight of propylene glycol methyl ether acetate (hereinafter referred to as C-1), 0.8 parts by weight of a compound represented by the formula (D-3-1) (hereinafter referred to as D-1), and 0.2 parts by weight of 9, 10-dimethoxyanthracene (hereinafter referred to as E-1) were weighed, the mixture was stirred at room temperature until dissolved. Thus, a positive chemically amplified photosensitive resin composition of Example 1 was obtained, and the formulation thereof is shown in Table 3.

[0358] Examples 2 to 13 and Comparative Examples 1 to 8

[0359] Examples 2 to 13 and Comparative Examples 1 to 8 were produced using the same production method as the positive chemically amplified photosensitive resin composition of Example 1, except that the kind and amount of the raw material used in the positive chemically amplified photosensitive resin composition were changed, and the formulation and evaluation results thereof are shown in Table 3 and Table 4, respectively, which are not described here.

[0360] In addition, the compounds corresponding to the abbreviations in Table 3 and Table 4 are shown below.

[0361]

[0362]

[0363]

[0364]

[0365] [Table 3]

[0366]

[0367] [Table 4]

[0368]

[0369] [Method of Evaluation]

[0370] High-temperature high-humidity reliability

[0371] The chemically amplified positive photosensitive resin composition prepared in Examples 1 to 16 and Comparative Examples 1 to 6 was applied to a 0.7 mm glass substrate (100 mm x 100 mm) by spin coating. Subsequently, a coating film having a film thickness of 3 μm was formed under heating conditions of 110°C for 2 minutes. Then, the coating film was subjected to a 70 second rinse with a 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution at 23°C, followed by a 15 second rinse with pure water. Subsequently, the coating film was irradiated with 200 mJ / cm2of ultraviolet rays from a mercury lamp. Thereafter, the coating film was heated in an oven at 230°C for 30 minutes to form a hardened film. 2

[0001] The hardened film was placed in an oven at a temperature of 85°C and a relative humidity of 85%. After 24 hours, the hardened film was cut into 100 checkers with a small knife. The checkers were observed for the presence of residual checkers after being adhered with a tape and peeled off, and the high temperature and high humidity reliability of the hardened film was evaluated according to the following criteria. The fewer checkers that fell off, the better the high temperature and high humidity reliability of the hardened film. *: No checkers fell off.

[0002] ◎: 0% < number of checkers that fell off ≦ 5%.

[0003] O: 5% < number of checkers that fell off ≦ 10%.

[0004] Δ: 10% < number of checkers that fell off ≦ 15%.

[0005] ╳: 15% < number of checkers that fell off.

[0006] Long-term resistance

[0007] The hardened film prepared in the evaluation method "high temperature and high humidity reliability" was measured for the initial film thickness (S0, unit: μm) of the hardened film. Then, the hardened film was immersed in TOK 106 resist stripper (main components: 70% monoethanolamine and 30% dimethyl sulfoxide, manufactured by Tokyo Ohka Kogyo) heated to 60°C for 30 minutes, and then taken out and the surface was wiped dry. Subsequently, the hardened film was immersed in N-methylpyrrolidone (NMP) solvent heated to 80°C for 30 minutes, and then taken out and the surface was wiped dry. The film thickness of the hardened film after immersion in the two solvents was measured to obtain another film thickness (S1, unit: μm), and the film thickness change rate was expressed as a percentage to serve as an index of long-term resistance. The smaller the film thickness change rate, the better the long-term resistance of the hardened film.

[0008] Film thickness change rate (%) = (S1 - S0) / S0 x 100%

[0009] *: Film thickness change rate < 102%

[0010] ​◎: 102% ≦ film thickness change rate < 103%

[0383] O: 103% ≦ film thickness change rate < 104%

[0384] △: 104% ≦ film thickness change rate < 105%

[0385] X: 105% ≦ film thickness change rate

[0386] It is to be noted that, unlike the known chemical resistance test method, the present application is tested for chemical resistance in a short time contact environment with only a single drug in the hardened film, and in the present examples and comparative examples, it is difficult to observe differences, so it cannot be used as a basis for evaluation. In addition, the known test method also lags behind the current situation of the present application, which is caused by the increasingly diverse and long-time drug contact process, resulting in long-term chemical resistance variation, so it is difficult to produce a link.

[0387] [Results of evaluation]

[0388] As shown in Tables 3 and 4, the long-term chemical resistance and high-temperature high-humidity reliability evaluation of the hardened film prepared from the chemical amplification positive photosensitive resin composition of Comparative Examples 1, 5-7, which does not include the acid dissociation resin (A), is not good compared to the hardened film prepared from the chemical amplification positive photosensitive resin composition including the specific acid dissociation resin (A) and the blocked isocyanate silane compound (D) (Examples 1-13).

[0389] Furthermore, although the chemical amplification positive photosensitive resin composition of Comparative Examples 2-4 includes an acid dissociation resin, the internal stress of the hardened film formed is greater than 40 MPa. Therefore, the long-term chemical resistance and high-temperature high-humidity reliability evaluation of the hardened film prepared from the chemical amplification positive photosensitive resin composition of Comparative Examples 2-4 is not good.

[0390] In addition, when the chemical amplification positive photosensitive resin composition does not include the blocked isocyanate silane compound (D) (Comparative Example 8), the long-term chemical resistance and high-temperature high-humidity reliability evaluation of the hardened film prepared is not good.

[0391] In addition, when the internal stress of the hardened film formed is 35 MPa or less (Examples 1-3, 8-11), the hardened film formed has good long-term chemical resistance.

[0392] In addition, when the internal stress of the hardened film formed is 30 MPa or less (Examples 1-3), the hardened film formed has better long-term chemical resistance.

[0393] Further, when the acid-dissociable resin (A) includes the repeating unit having an epoxy group (A-2-1) and the repeating unit having an oxetane group (A-2-2) (Examples 1-3, 8-11), the formed hardened film has better long-term chemical resistance.

[0394] Further, when the monomer mixture for preparing the acid-dissociable resin (A) includes the unsaturated monomer (a-1) having an acid-dissociable group, the unsaturated monomer (a-2) having a cross-linkable group, and the (meth)acrylic alkyl ester monomer (a-3) (Example 1-3), the formed hardened film has better long-term chemical resistance.

[0395] In addition, when the blocked isocyanate silane compound (D) has at least one selected from the group consisting of the structures represented by Formula (D-2) and Formula (D-3) (Examples 1-5, 8-9), the formed hardened film has better high-temperature and high-humidity reliability.

[0396] In summary, the chemically amplified positive photosensitive resin composition of the present application includes a specific blocked isocyanate silane compound (D), and the internal stress of the formed hardened film is 40 MPa or less, so the chemically amplified positive photosensitive resin composition can improve the technical problems of poor long-term chemical resistance and high-temperature and high-humidity reliability in the prior art.

[0397] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that they can still modify the technical solutions described in the foregoing examples, or make equivalent substitutions for part or all of the technical features; and these modifications or substitutions do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A chemically amplified positive photosensitive resin composition, comprising: Acid-dissociable resin (A); Photoacid generator (B); Solvent (C); as well as Blocked isocyanate silane compounds (D), in which The hardened film formed from the chemically amplified positive photosensitive resin composition has an internal stress of less than 40 MPa.

2. The chemically amplified positive photosensitive resin composition according to claim 1, wherein, The hardened film formed from the chemically amplified positive photosensitive resin composition has an internal stress of less than 35 MPa.

3. The chemically amplified positive photosensitive resin composition according to claim 1, wherein, The hardened film formed from the chemically amplified positive photosensitive resin composition has an internal stress of less than 30 MPa.

4. The chemically amplified positive photosensitive resin composition according to claim 1, wherein, The blocked isocyanate silane compound (D) has a structure as shown in the following formula (D-1): In equation (D-1), R 1 and R 2 Each can be independently represented as an alkyl group; n represents an integer from 1 to 3; L represents a divalent linker; X represents -O-, -NR'-; R' represents a hydrogen atom, an alkyl group, or a group that can combine with Y to form a cyclic structure; Y represents a hydrogen atom or a monovalent organic group.

5. The chemically amplified positive photosensitive resin composition according to claim 1, wherein, The blocked isocyanate silane compound (D) has at least one of the structures selected from the group consisting of the structures shown in formulas (D-2) and (D-3) below: In equations (D-2) and (D-3), R 1 and R 2 Each can be independently represented as an alkyl group; R 3 To R 6 Each independently represents a hydrogen atom and a monovalent organic group, R 3 and R 4 or R 5 and R 6 They can connect to each other to form a ring structure; n represents an integer from 1 to 3; L represents a divalent linker.

6. The chemically amplified positive photosensitive resin composition according to claim 5, wherein, The blocked isocyanate silane compound (D) has a structure as shown in formula (D-2).

7. The chemically amplified positive photosensitive resin composition according to claim 1, wherein, The acid-dissociative resin (A) comprises repeating units (A-2) having crosslinking groups.

8. The chemically amplified positive photosensitive resin composition according to claim 7, wherein, The repeating unit (A-2) with crosslinking groups includes repeating units (A-2-1) with epoxy groups and repeating units (A-2-2) with oxybutyl groups.

9. The chemically amplified positive photosensitive resin composition according to claim 1, wherein, The acid-dissociable resin (A) is formed by copolymerization of a monomer mixture. The monomer mixture includes an unsaturated monomer (a-1) having an acid-dissociable group, an unsaturated monomer (a-2) having a crosslinking group, and an alkyl (meth)acrylate monomer (a-3).

10. The chemically amplified positive photosensitive resin composition according to claim 1, wherein, The total weight of the solids content of the chemically amplified positive photosensitive resin composition is 100% by weight. The content of the blocked isocyanate silane compound (D) is from 0.01% to 10% by weight.

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

12. An element having a hardened film, comprising: Substrate; as well as The hardened film as described in claim 11 is disposed on the substrate.

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