Polymer, positive and negative photosensitive resin composition, pattern forming method, cured coating film forming method, interlayer insulating film, surface protection film

Abstract

The invention relates to a polymer, a positive and negative photosensitive resin composition, a pattern forming method, a hardened film forming method, an interlayer insulating film, a surface protective film, and an electronic component. The present invention addresses the problem of providing a polymer which can be dissolved in an aqueous alkali solution, can form a fine pattern, can obtain high resolution, and can use a base resin as a positive and negative photosensitive resin composition, said polymer having good mechanical properties even when cured at low temperature. This problem is solved by a polymer containing a structural unit represented by general formula (1) and / or (2) and a structural unit represented by general formula (3) and / or (4). # imgabs0 # X1 is a tetravalent organic group, R1-R4 are a monovalent organic group or a hydrogen atom, at least one of R1-R4 is a monovalent organic group, and L is a divalent organic group or a divalent atom. # imgabs1 # X2 is a divalent organic group, and R1 to R4 and L are the same as one another. # imgabs2 # X3 is a tetravalent organic group, s is 0 or 1, and Z is a divalent bonding group. # imgabs3 # X4 is a divalent organic group, and s and Z are the same.

Description

Technical Field

[0001] The present invention relates to a polymer, a positive and negative photosensitive resin composition, a pattern forming method, a hardened film forming method, an interlayer insulating film, a surface protective film, and an electronic component. Background Art

[0002] With the miniaturization and high performance of various electronic devices such as personal computers, digital cameras, and mobile phones, the demand for further miniaturization, thinning, and high density of semiconductor components has also increased rapidly. In line with this, the interlayer insulation film and surface protection film of semiconductor components are also required to have excellent electrical properties, heat resistance, mechanical properties, etc.

[0003] In high-density mounting technologies such as three-dimensional lamination, photosensitive insulating materials that can form patterns on substrates have long been used as protective films and insulating layers using polyimide films. Their insulation, mechanical properties, and adhesion to substrates continue to attract attention, and development is still vigorous even now.

[0004] In order to further improve the above required characteristics, various methods have been implemented. For one thing, a photosensitive resin composition using a closed-ring polyimide resin has been proposed for the purpose of lowering the post-curing temperature (Patent Document 1, Patent Document 2). However, it is not easy to take into account the physical properties of the cured film such as resolution, mechanical properties (elongation, tensile strength), and adhesion, and there is still room for improvement.

[0005] In addition, regarding the improvement of the mechanical strength of the cured film, a composition containing a polymer having a structural unit derived from an ester-containing diamine has been proposed (Patent Documents 3 and 4). Patent Document 3 proposes a positive photosensitive resin composition containing a polybenzoxazole precursor containing an ester-containing diamine and a diazonaphthoquinone compound, but only the dissolution contrast and sensitivity are described with respect to the photolithographic properties, and there is no description with respect to the pattern resolution, and there is still room for improvement in the value of the mechanical strength.

[0006] Patent Document 4 proposes a polyamic acid containing a diamine residue and an acid dianhydride residue and a polyimide formed by ring-closing the polyamic acid, wherein the diamine residue is derived from a diamine residue of an ester-containing diamine and a flexible diamine, but there is no description about the photosensitive resin composition, and there is still room for improvement in terms of mechanical strength, especially elongation.

[0007] As chips become more densely packed and highly integrated in the future, the pattern in the redistribution technology of the insulating protective film will inevitably become increasingly miniaturized. Therefore, there is a strong demand for the photosensitive resin composition to have excellent characteristics such as mechanical properties and adhesion of the obtained pattern and protective film without damaging them due to heating, and to have a composition that can achieve a pattern shape with high resolution and excellent rectangularity.

[0008] Prior art literature

[0009] Patent Literature

[0010] [Patent Document 1] Japanese Patent No. 4530284

[0011] [Patent Document 2] Japanese Patent Application Publication No. 2006-313237

[0012] [Patent Document 3] Japanese Patent Application Publication No. 2020-152768

[0013] [Patent Document 4] Japanese Patent Application Publication No. 2021-187934 Summary of the invention

[0014] [Problems to be solved by the invention]

[0015] The present invention is made in view of the above situation, and its purpose is to provide a polymer selected from a base resin of polyamide, polyamideimide, and polyimide which can be used as a positive photosensitive resin composition and a negative photosensitive resin composition that are soluble in an alkaline aqueous solution, can form a fine pattern, can obtain a high resolution, and has good mechanical properties even when cured at a low temperature.

[0016] Another object is to provide a positive photosensitive resin composition and a negative photosensitive resin composition using the above-mentioned polymer which is soluble in an alkaline aqueous solution during pattern formation, has excellent resolution, can form a fine pattern, and has good mechanical properties even when cured at low temperatures.

[0017] [Methods to solve the problem]

[0018] In order to solve the above problems, the present invention provides a polymer comprising a structural unit represented by the following general formula (1) and / or (2) and a structural unit represented by the following general formula (3) and / or (4).

[0019] [Chemistry 1]

[0020]

[0021] In the formula, X1 is a tetravalent organic group, R1 to R4 are monovalent organic groups having 1 to 15 carbon atoms which may be different or the same and may also contain heteroatoms, or hydrogen atoms, and at least one of them is a monovalent organic group having 1 to 15 carbon atoms which may also contain heteroatoms, and L is a divalent organic group or a divalent atom excluding a -OC(=O)- bond or a -C(=O)-O- bond.

[0022] [Chemistry 2]

[0023]

[0024] In the formula, X2 is a divalent organic group, and R1 to R4 and L are the same as described above.

[0025] [Chemistry 3]

[0026]

[0027] In the formula, X3 is a tetravalent organic group which is the same as or different from the aforementioned X1, s is 0 or 1, Z is a divalent bonding group, and when s=0, the two aromatic rings in the formula are directly bonded without a bonding group in between.

[0028] [Chemistry 4]

[0029]

[0030] In the formula, X4 is a divalent organic group which is the same as or different from the above X2, and s and Z are the same as described above.

[0031] If it is such a polymer, the general formula (3) or (4) mentioned above can be dissolved in an alkaline aqueous solution due to the presence of a phenolic hydroxyl group, and can form a fine pattern and obtain a high resolution. The general formula (1) or (2) mentioned above can be used as a base resin of a photosensitive resin composition having good mechanical properties even when cured at a low temperature by promoting appropriate interactions between molecules due to the presence of a substituted phenyl group.

[0032] In the general formulae (1) and (2), any one of R1 and R2 is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom, and the other is a hydrogen atom, and preferably R3 and R4 are hydrogen atoms.

[0033] If a photosensitive resin composition using such a polymer has a substituent at the ortho position of the bonding site, the free rotation of the polymer chain is suppressed due to the steric hindrance of the substituent, and the interaction between molecules becomes appropriate, thereby achieving good mechanical properties even when cured at a low temperature.

[0034] In the general formulae (1) and (2), it is preferred that either one of R1 and R2 is an aromatic group having 6 to 12 carbon atoms, and the other is a hydrogen atom.

[0035] If the photosensitive resin composition uses such a polymer, the mechanical properties are further improved even when it is cured at a low temperature.

[0036] In the general formulae (1) and (2), the L is preferably at least one selected from an oxygen atom, a sulfur atom, a carbonyl group, a linear alkylene group having 1 to 15 carbon atoms, and a branched alkylene group having 3 to 15 carbon atoms.

[0037] When a photosensitive resin composition using such a polymer is used, mechanical properties are improved by imparting flexibility to the polymer chain.

[0038] In the general formulae (3) and (4), the aforementioned Z is preferably at least one bonding group selected from any one of the groups represented by the following formulae (5), (6), (7) and (8).

[0039] [Chemistry 5]

[0040]

[0041] In the formula, dotted lines represent atomic bonds.

[0042] A photosensitive resin composition using such a polymer can improve its solubility in an alkaline aqueous solution, thereby enabling formation of a finer pattern and obtaining a high resolution.

[0043] Furthermore, the present invention provides a positive photosensitive resin composition comprising:

[0044] (A) the above polymer,

[0045] (B) is a photosensitizer that generates acid due to light and increases the dissolution rate in an alkaline aqueous solution, and has a diazoquinone structure, and

[0046] (D) Solvent.

[0047] Thus, by using the photosensitive agent of component (B), in pattern formation, the exposed portion becomes soluble in the developer of the alkaline aqueous solution at a higher dissolution rate, and the unexposed portion does not dissolve due to the alkali dissolution resistance of the photosensitive agent, thereby obtaining a positive image. Since the polymer itself is alkali-soluble, it is difficult to generate residues such as scum at the bottom of the pattern opening, and it is difficult to cause pattern degradation such as tailing, which has a significant effect on fine pattern formation.

[0048] In this case, it is preferable to further contain the following component (C).

[0049] (C) one or more crosslinking agents selected from the group consisting of amino condensates modified with formaldehyde or formaldehyde-alcohol, phenolic compounds having an average of more than two hydroxymethyl or alkoxyhydroxymethyl groups in one molecule, compounds in which the hydrogen atoms of the hydroxyl groups of polyphenols are substituted with glycidyl groups, compounds in which the hydrogen atoms of the hydroxyl groups of polyphenols or polyols are substituted with substituents represented by the following formula (C-1), and compounds containing two or more nitrogen atoms having glycidyl groups represented by the following formula (C-2).

[0050] [Chemistry 6]

[0051]

[0052] In the formula, dotted lines represent atomic bonds, Rc is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.

[0053] After the positive photosensitive resin composition of the present invention is patterned, the component (C) causes a crosslinking reaction during post-curing, thereby further improving the strength of the cured product and forming a more ideal cured film.

[0054] Furthermore, the present invention provides a negative photosensitive resin composition comprising:

[0055] (A) the above polymer,

[0056] (B') a photoacid generator,

[0057] (C) one or more crosslinking agents selected from the group consisting of amino condensates modified with formaldehyde or formaldehyde-alcohol, phenolic compounds having an average of two or more methylol groups or alkoxymethylol groups in one molecule, compounds in which hydrogen atoms of hydroxyl groups of polyphenols are substituted with glycidyl groups, compounds in which hydrogen atoms of hydroxyl groups of polyphenols or polyols are substituted with substituents represented by the following formula (C-1), and compounds containing two or more nitrogen atoms having glycidyl groups represented by the following formula (C-2), and

[0058] [Chemistry 7]

[0059]

[0060] In the formula, dotted lines represent atomic bonds, Rc is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.

[0061] (D) Solvent.

[0062] In this way, by using the photoacid generator of the component (B'), an acid is generated in the exposed area during pattern formation, and the crosslinking groups of the added crosslinking agent of the component (C) are crosslinked with the crosslinking reaction points of the polymer, thereby becoming insoluble in the developer and obtaining a negative image.

[0063] In addition, the present invention provides a pattern forming method, comprising the following steps;

[0064] (1) coating the positive photosensitive resin composition on a substrate to form a photosensitive material film,

[0065] (2) heating the photosensitive material film;

[0066] (3) exposing the photosensitive material film to high-energy radiation or electron beams with a wavelength of 190 to 500 nm through a photomask, and

[0067] (4) Development is performed using an alkaline aqueous solution developer.

[0068] According to such a pattern forming method, by using the positive photosensitive resin composition, it is soluble in an alkaline aqueous solution, does not generate scum, etc., and can form a fine pattern and obtain a high resolution.

[0069] In addition, the present invention provides a pattern forming method, comprising the following steps;

[0070] (I) coating the negative photosensitive resin composition on a substrate to form a photosensitive material film,

[0071] (II) heating the photosensitive material film,

[0072] (III) exposing the photosensitive material film to high energy radiation or electron beam with a wavelength of 190 to 500 nm through a photomask, and

[0073] (IV) After the irradiation, the substrate subjected to the heat treatment is developed using a developer of an alkaline aqueous solution.

[0074] Since the polymer of the base resin of the negative photosensitive resin composition of the present invention contains the structural unit represented by the above general formula (3) and / or (4), it can be alkali developed with an alkali aqueous solution.

[0075] In addition, the present invention provides a method for forming a hardened film, comprising the following steps:

[0076] The patterned film obtained by the above-mentioned pattern forming method is heated at a temperature of 100 to 300° C. and post-cured.

[0077] According to such a cured film forming method, a cured film (pattern) having excellent mechanical properties can be formed even when cured at a low temperature.

[0078] In addition, the present invention provides an interlayer insulating film, which is composed of a cured film formed by curing the positive photosensitive resin composition.

[0079] In addition, the present invention provides an interlayer insulating film, which is composed of a cured film formed by curing the negative photosensitive resin composition.

[0080] In addition, the present invention provides a surface protection film, which is composed of a cured film formed by curing the positive photosensitive resin composition.

[0081] The present invention also provides a surface protection film, which is composed of a cured film formed by curing the negative photosensitive resin composition.

[0082] The cured film formed by curing the positive photosensitive resin composition of the present invention or the negative photosensitive resin composition of the present invention has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength and chemical resistance to alkaline stripping solutions, etc., and the reliability of semiconductor elements using it as a protective film is also excellent. Therefore, it is suitable as a protective film (interlayer insulating film or surface protective film) for electrical and electronic parts, semiconductor elements, etc.

[0083] Furthermore, the present invention provides an electronic component having the above-mentioned interlayer insulating film or the above-mentioned surface protective film.

[0084] Such a protective film (interlayer insulating film or surface protective film) is effective as an insulating film for semiconductor elements including redistribution purposes, an insulating film for multilayer printed circuit boards, etc., due to its heat resistance, chemical resistance, and insulating properties, and can be made into electronic parts with excellent reliability.

[0085] [Effects of the Invention]

[0086] As described above, the present invention can provide a polymer selected from polyamide, polyamideimide, and polyimide that can be used as a base resin for a positive photosensitive resin composition and a negative photosensitive resin composition that is soluble in an alkaline aqueous solution, can form a fine pattern, can obtain a high resolution, and has good mechanical properties even when cured at a low temperature.

[0087] In addition, a positive photosensitive resin composition and a negative photosensitive resin composition using the above polymer can be provided, which are soluble in an alkaline aqueous solution during pattern formation, have excellent resolution, can form a fine pattern, and have good mechanical properties even when cured at a low temperature. DETAILED DESCRIPTION

[0088] As described above, there is a demand for a polymer that can be used as a base resin of a photosensitive resin composition that is soluble in an aqueous alkali solution, can form a fine pattern, can obtain a high resolution, and has excellent mechanical properties even when cured at a low temperature.

[0089] As a result of in-depth studies to achieve the above-mentioned purpose, the present inventors have found that when a polymer containing a structural unit represented by the following general formula (1) and / or (2) and a structural unit represented by the following general formula (3) and / or (4) is used as a base resin of a photosensitive resin composition, the polymer is soluble in an alkaline aqueous developer and can be used in any of a positive photosensitive resin composition that can be developed with an alkaline aqueous solution and a negative photosensitive resin composition that can be developed with an alkaline aqueous solution, and the patterns obtained using these photosensitive resin compositions are fine and have good pattern shapes.

[0090] In addition, it was found that a protective film obtained by heating at a low temperature after pattern formation using a photosensitive resin composition containing a polymer having a structural unit represented by the following general formula (3) and / or (4) as a base resin has excellent mechanical strength and adhesion. That is, a cured film obtained by forming a pattern using a photosensitive resin composition containing a polymer having the above structural unit as a base resin is excellent as an electrical-electronic component protective film or an insulating protective film, and the present invention has been completed. In addition, in this specification, electrical-electronic components are collectively referred to as "electronic components".

[0091] That is, the present invention is a polymer comprising a structural unit represented by the following general formula (1) and / or (2) and a structural unit represented by the following general formula (3) and / or (4).

[0092] [Chemistry 8]

[0093]

[0094] In the formula, X1 is a tetravalent organic group, R1 to R4 are monovalent organic groups having 1 to 15 carbon atoms which may be different or the same and may also contain heteroatoms, or hydrogen atoms, and at least one of them is a monovalent organic group having 1 to 15 carbon atoms which may also contain heteroatoms, and L is a divalent organic group or a divalent atom excluding a -OC(=O)- bond or a -C(=O)-O- bond.

[0095] [Chemistry 9]

[0096]

[0097] In the formula, X2 is a divalent organic group, and R1 to R4 and L are the same as described above.

[0098] [Chemistry 10]

[0099]

[0100] In the formula, X3 is a tetravalent organic group which is the same as or different from the aforementioned X1, s is 0 or 1, Z is a divalent bonding group, and when s=0, the two aromatic rings in the formula are directly bonded without a bonding group in between.

[0101] [Chemistry 11]

[0102]

[0103] In the formula, X4 is a divalent organic group which is the same as or different from the above X2, and s and Z are the same as described above.

[0104] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0105] [(A) Polymer]

[0106] The polymer of the present invention contains structural units represented by the following general formula (1) and / or (2) (hereinafter also referred to as structural unit (1), structural unit (2)) and structural units represented by the following general formula (3) and / or (4) (hereinafter also referred to as structural unit (3), structural unit (4)).

[0107] [Chemistry 12]

[0108]

[0109] In the formula, X1 is a tetravalent organic group, R1 to R4 are monovalent organic groups having 1 to 15 carbon atoms which may be different or the same and may also contain heteroatoms, or hydrogen atoms, and at least one of them is a monovalent organic group having 1 to 15 carbon atoms which may also contain heteroatoms, and L is a divalent organic group or a divalent atom excluding a -OC(=O)- bond or a -C(=O)-O- bond.

[0110] [Chemistry 13]

[0111]

[0112] In the formula, X2 is a divalent organic group, and R1 to R4 and L are the same as described above.

[0113] [Chemistry 14]

[0114]

[0115] In the formula, X3 is a tetravalent organic group which is the same as or different from the aforementioned X1, s is 0 or 1, Z is a divalent bonding group, and when s=0, the two aromatic rings in the formula are directly bonded without a bonding group in between.

[0116] [Chemistry 15]

[0117]

[0118] In the formula, X4 is a divalent organic group which is the same as or different from the above X2, and s and Z are the same as described above.

[0119] X1 in the above general formula (1) is a tetravalent organic group. If it is a tetravalent organic group, there is no limitation. It is preferably a tetravalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a tetravalent aromatic group having 6 to 40 carbon atoms, and may also contain a siloxane skeleton. It is more preferably a tetravalent organic group represented by the following formula (9). In addition, the structure of X1 may be one or a combination of two or more.

[0120] [Chemistry 16]

[0121]

[0122] In the formula, R a1 , Ra2 Each independently represents a methyl group or a phenyl group, q1 and q2 are integers of 1 to 20, and a dotted line represents an atomic bond.

[0123] In the above general formula (1), any of R1 to R4 is a monovalent organic group having 1 to 15 carbon atoms which may contain a hetero atom, preferably any of R1 and R2 is a monovalent organic group having 1 to 15 carbon atoms which may contain a hetero atom, and the other is a hydrogen atom, and R3 and R4 are hydrogen atoms, any of R1 and R2 is a group selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, a phenoxy group having 6 to 10 carbon atoms, a benzyl group having 7 to 10 carbon atoms, and a benzyloxy group having 7 to 10 carbon atoms, and the other is a hydrogen atom, and R3 and R4 are more preferably hydrogen atoms. Any of R1 and R2 is a monovalent organic group having 1 to 10 carbon atoms which may contain a hetero atom, and the other is a hydrogen atom, and R3 and R4 are more preferably hydrogen atoms.

[0124] Examples of the alkyl group having 1 to 12 carbon atoms include methyl, trifluoromethyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, and hexyl. Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentyloxy. Examples of the aromatic group having 6 to 12 carbon atoms include phenyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, butylphenyl, fluorophenyl, chlorophenyl, bromophenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, diethoxyphenyl, aminophenyl, nitrophenyl, cyanophenyl, phenethyl, phenylpropyl, phenylamino, diphenylamino, biphenyl, and naphthyl. Examples of the phenoxy group having 6 to 10 carbon atoms include methylphenoxy, ethylphenoxy, propylphenoxy, dimethylphenoxy, diethylphenoxy, methoxyphenoxy, ethoxyphenoxy, and dimethoxyphenoxy. Examples of the benzyl group having 7 to 10 carbon atoms include benzyl, methylbenzyl, ethylbenzyl, propylbenzyl, dimethylbenzyl, diethylbenzyl, methoxybenzyl, ethoxybenzyl, dimethoxybenzyl, diethoxybenzyl, aminobenzyl, nitrobenzyl, and cyanobenzyl. Examples of the benzyloxy group having 7 to 10 carbon atoms include benzyloxy, methylbenzyloxy, ethylbenzyloxy, propylbenzyloxy, dimethylbenzyloxy, diethylbenzyloxy, methoxybenzyloxy, and ethoxybenzyloxy.

[0125] Among the above, aromatic groups having 6 to 12 carbon atoms, phenoxy groups having 6 to 10 carbon atoms, benzyl groups having 7 to 10 carbon atoms, and benzyloxy groups having 7 to 10 carbon atoms are preferred, aromatic groups having 6 to 12 carbon atoms are more preferred, and phenyl, methylphenyl, dimethylphenyl, ethylphenyl, and diethylphenyl are even more preferred. If such an organic group is used, it is believed that the free rotation of the polymer chain is suppressed due to its bulkiness, thereby suppressing the intermolecular packing effect, and the interaction between molecules becomes appropriate, thereby improving the mechanical properties of the cured film, especially the elongation at break.

[0126] In the above general formula (1), L is a divalent organic group or a divalent atom excluding a -OC(=O)- bond or a -C(=O)-O- bond, and is not limited. It is preferably an oxygen atom, a sulfur atom, a carbonyl group, a linear alkylene group having 1 to 15 carbon atoms, and a branched alkylene group having 3 to 15 carbon atoms. In view of the ease of obtaining the raw materials, an oxygen atom is more preferred. If it is such an organic group or atom, the mechanical properties become good because flexibility is imparted to the polymer chain.

[0127] X2 in the above general formula (2) is a divalent organic group. There are no restrictions if it is a divalent organic group. It is preferably a divalent organic group of an aliphatic chain length structure with 4 to 40 carbon atoms, a divalent alicyclic aliphatic group with 4 to 40 carbon atoms, or a divalent aromatic group with 6 to 40 carbon atoms. It is more preferably a divalent organic group represented by the following formula (10). In addition, the structure of X2 may be one or a combination of two or more.

[0128] [Chemistry 17]

[0129]

[0130] In the formula, R a3 Each of them is independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, q3 is an integer of 1 to 30, and a dotted line represents an atomic bond.

[0131] In the above general formula (2), R1 to R4 and L are the same as those in the above general formula (1).

[0132] X3 in the above general formula (3) is a tetravalent organic group, which may be the same as or different from the above X1. If it is a tetravalent organic group, there is no limitation. It is preferably a tetravalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a tetravalent aromatic group having 6 to 40 carbon atoms, and may also contain a siloxane skeleton. It is more preferably a tetravalent organic group represented by the above formula (9). In addition, the structure of X3 may be one or a combination of two or more.

[0133] In the general formula (3), s is 0 or 1. When s=0, the two aromatic rings in the general formula (3) are directly bonded without a divalent bonding group Z in between.

[0134] On the other hand, when s=1, the two aromatic rings in the general formula (3) are bonded with a divalent bonding group Z in between. There is no limitation if Z is a divalent group. It is preferably a divalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a divalent aromatic group having 6 to 40 carbon atoms, and is more preferably a divalent bonding group represented by the following formula (11). In addition, the structure of Z may be one or a combination of two or more.

[0135] [Chemistry 18]

[0136]

[0137] In the formula, q4, q5, and q6 represent integers of 1 to 6, and q7 and q8 represent integers of 1 to 10. Dotted lines represent atomic bonds.

[0138] Particularly preferred divalent bonding groups Z are divalent groups represented by the following general formulae (5), (6), (7), and (8). That is, the aforementioned Z in the aforementioned general formulae (3) and (4) is preferably at least one bonding group selected from any one of the groups represented by the following formulae (5), (6), (7), and (8).

[0139] [Chemistry 19]

[0140]

[0141] In the formula, dotted lines represent atomic bonds.

[0142] More preferably, the divalent bonding group Z is a divalent group represented by the above-mentioned general formula (5) or (6).

[0143] With respect to the structural unit represented by the above-mentioned general formula (3), when Z in the above-mentioned general formula (3) is a group represented by the above-mentioned formula (5), it is preferably a structural unit represented by the following general formula (3-1); and when Z in the above-mentioned general formula (3) is a group represented by the above-mentioned formula (6), it is preferably a structural unit represented by the following general formula (3-2).

[0144] [Chemistry 20]

[0145]

[0146] Wherein, X3 is the same as above.

[0147] As shown in the above general formula (3-1), when Z as a divalent bonding group is a hexafluoropropylene group represented by the above formula (5) and is located in the para position of the phenolic hydroxyl group, since the hexafluoropropylene group is an electron-withdrawing group, the acidity of the aforementioned phenolic hydroxyl group will become higher and the solubility in the developer of alkaline aqueous solution will be improved, which is more ideal.

[0148] Similarly, as shown in the above general formula (3-2), when Z as a divalent bonding group is a sulfone group represented by the above formula (6) and is located in the para position of the phenolic hydroxyl group, since the sulfone group is also an electron-withdrawing group, the acidity of the aforementioned phenolic hydroxyl group will become higher and the solubility in the developer of alkaline aqueous solution will be improved, which is more ideal.

[0149] X4 in the above general formula (4) is a divalent organic group, which may be the same as or different from the above X2. If it is a divalent organic group, there is no limitation. It is preferably a divalent organic group of an aliphatic chain length structure having 4 to 40 carbon atoms, a divalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a divalent aromatic group having 6 to 40 carbon atoms. It is more preferably a divalent organic group represented by the above formula (10). In addition, the structure of X4 may be one or a combination of two or more.

[0150] When X4 in the general formula (4) is a divalent organic group having an aliphatic chain length structure, the mechanical strength of the cured film of the negative photosensitive resin composition of the present invention becomes higher, and in particular, the elongation becomes higher, which is preferred.

[0151] In the general formula (4), s and Z are the same as those described above, and Z is preferably the general formula (5) or (6) in view of solubility in an alkaline aqueous developer.

[0152] Furthermore, the polymer of the present invention may contain at least one of the structural units represented by the following general formulae (12) to (15) in addition to the structural units represented by the above general formulae (1), (2), (3), and (4).

[0153] [Chemistry 21]

[0154]

[0155] In the formula, X5 is a tetravalent organic group which is the same as or different from the aforementioned X1, and X6 is a divalent organic group.

[0156] [Chemistry 22]

[0157]

[0158] In the formula, X7 is a divalent organic group which is the same as or different from the aforementioned X2, and X8 is a divalent organic group which is the same as or different from the aforementioned X6.

[0159] [Chemistry 23]

[0160]

[0161] In the formula, X9 is a tetravalent organic group which is the same as or different from the aforementioned X1, 10is a divalent organic group which is the same as or different from the above X6, and Rb may be the same as or different from a hydrogen atom or an organic group having 1 to 10 carbon atoms, which may contain a heteroatom and may have a substituent.

[0162] [Chemistry 24]

[0163]

[0164] Where, X 11 is a divalent organic group which is the same as or different from the aforementioned X2, 12 It is a tetravalent organic group.

[0165] X5 in the above general formula (12) is a tetravalent organic group, which may be the same as or different from the above X1. If it is a tetravalent organic group, there is no limitation. It is preferably a tetravalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a tetravalent aromatic group having 6 to 40 carbon atoms, and may also contain a siloxane skeleton. It is more preferably a tetravalent organic group represented by the above formula (9). In addition, the structure of X5 may be one or a combination of two or more.

[0166] X6 in the above general formula (12) is a divalent organic group. If it is a divalent organic group, there is no restriction. It is preferably a divalent organic group with 6 to 40 carbon atoms, a divalent cyclic organic group containing 1 to 4 aromatic rings or aliphatic rings with substituents, or a divalent aliphatic group without a cyclic structure, or a siloxane group. More ideal X6 can be a structure represented by the following formula (16) or (17). In addition, the structure of X6 can be one or a combination of two or more.

[0167] [Chemistry 25]

[0168]

[0169] In the formula, q9 is an integer of 1 to 20, s1 is an integer of 1 to 40, s2 and s3 are each independently an integer of 0 to 40, and dotted lines represent atomic bonds.

[0170] [Chemistry 26]

[0171]

[0172] In the formula, q 10 is an integer from 1 to 4, R a4 is a fluorine atom, a methyl group, an ethyl group, a propyl group, a n-butyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a trifluoromethyl group, 10 When R is 2 or more, a4 They can be the same or different, q 11 is an integer from 1 to 40, and dotted lines represent atomic bonds.

[0173] A resin composition containing a polymer containing a structural unit represented by the general formula (12) is preferred because the mechanical strength, adhesion to the substrate, and heat resistance of the cured film obtained by patterning can be improved. In addition, the structural unit (12) does not need to undergo a ring-closing reaction during post-curing, and the curing reaction temperature can be relatively lowered, which is preferred.

[0174] X7 in the above general formula (13) is a divalent organic group, which may be the same as or different from the above X2. If it is a divalent organic group, there is no limitation. It is preferably a divalent organic group of an aliphatic chain length structure having 4 to 40 carbon atoms, a divalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a divalent aromatic group having 6 to 40 carbon atoms. It is more preferably a divalent organic group represented by the above formula (10). In addition, the structure of X7 may be one or a combination of two or more.

[0175] X8 in the above general formula (13) is a divalent organic group, which may be the same as or different from the above X6. If it is a divalent organic group, there is no limitation. It is preferably a divalent organic group having 6 to 40 carbon atoms, a divalent cyclic organic group containing 1 to 4 aromatic rings or aliphatic rings having substituents, or a divalent aliphatic group without a cyclic structure, or a siloxane group. The structures represented by the above formula (16) or (17) are more preferred. In addition, the structure of X8 may be one or a combination of two or more.

[0176] A resin composition containing a polymer having a structural unit represented by the general formula (13) is preferred because it can improve mechanical properties such as elongation of a cured film obtained by patterning and adhesion to a substrate.

[0177] X9 in the above general formula (14) is a tetravalent organic group, which may be the same as or different from the above X1. If it is a tetravalent organic group, there is no limitation. It is preferably a tetravalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a tetravalent aromatic group having 6 to 40 carbon atoms, and may also contain a siloxane skeleton. It is more preferably a tetravalent organic group represented by the above formula (9). In addition, the structure of X9 may be one or a combination of two or more.

[0178] In the above general formula (14), X 10 is a divalent organic group, which may be the same as or different from the above X6. If it is a divalent organic group, there is no limitation. It is preferably a divalent organic group having 6 to 40 carbon atoms, a divalent cyclic organic group containing 1 to 4 aromatic rings or aliphatic rings having substituents, or a divalent aliphatic group without a cyclic structure, or a siloxane group. The structure represented by the above formula (16) or (17) is more preferred. 10 The structure may be one kind or a combination of two or more kinds.

[0179] In the general formula (14), the organic group having 1 to 10 carbon atoms of Rb is not particularly limited, and may be, for example, an organic group containing an acryloyl group or a methacryloyl group.

[0180] A resin composition containing a polymer containing a structural unit represented by the general formula (14) is preferred because the mechanical strength of the cured film and the adhesion to the substrate are improved.

[0181] In the above general formula (15), X 11 is a divalent organic group, which may be the same as or different from the above X2. If it is a divalent organic group, there is no limitation. It is preferably a divalent organic group of an aliphatic chain length structure having 4 to 40 carbon atoms, a divalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a divalent aromatic group having 6 to 40 carbon atoms. It is more preferably a divalent organic group represented by the above formula (10). 11 The structure may be one kind or a combination of two or more kinds.

[0182] In the above general formula (15), X 12 It is a tetravalent organic group. If it is a tetravalent organic group, there is no limitation. It is preferably a tetravalent organic group having 6 to 40 carbon atoms, a tetravalent cyclic organic group containing 1 to 4 aromatic rings or aliphatic rings having substituents, a tetravalent aliphatic group without a ring structure, or a siloxane group. More preferably, X 12 The structure represented by the following formula (18) can be cited. 12 The structure may be one kind or a combination of two or more kinds.

[0183] [Chemistry 27]

[0184]

[0185] In the formula, q 12 ,q 13 , and q 14 is an integer from 1 to 10, q 15 is an integer from 1 to 20, and dotted lines represent atomic bonds.

[0186] A resin composition containing a polymer having a structural unit represented by the general formula (15) is preferred because the mechanical strength, adhesion to the substrate, and heat resistance of the cured film obtained by patterning can be improved. In addition, when the structure represented by the general formula (15) is contained, a ring-closing reaction is not required in post-curing, and the curing reaction temperature can be relatively lowered, which is preferred.

[0187] In the polymer, the ratio of the structural unit represented by the above general formula (1) and / or (2) to the structural unit represented by the above general formula (3) and / or (4) is not particularly limited. For example, the structural unit represented by the general formula (1) and / or (2) may be 1 to 99 mol%, preferably 2 to 50 mol%, more preferably 3 to 20 mol%, and even more preferably 5 to 15 mol%, relative to 100 mol% of the total of the structural units of the general formulae (1) to (4).

[0188] Furthermore, the polymer may contain only the structural units represented by the above general formulae (1) to (4) (excluding the terminal portion), or may contain other structural units (e.g., structural units represented by the above general formulae (12) to (15)) in addition to the structural units represented by the above general formulae (1) to (4) as described above. The ratio of the structural units represented by the above general formulae (1) to (4) contained in the polymer is not particularly limited, and may be, for example, 60 to 100 mol%, preferably 80 to 100 mol%, relative to 100 mol% of the total of the structural units contained in the polymer.

[0189] [Method for producing polymer]

[0190] The polymer of the present invention contains structural units represented by the following general formula (1) and / or (2) and structural units represented by the following general formula (3) and / or (4). These structural units are hereinafter also referred to as structural units (1) to (4).

[0191] [Chemistry 28]

[0192]

[0193] In the formula, X1, R1 to R4, and L are the same as those described above.

[0194] [Chemistry 29]

[0195]

[0196] In the formula, X2, R1 to R4, and L are the same as those described above.

[0197] [Chemistry 30]

[0198]

[0199] Wherein, X3, Z, and s are the same as above.

[0200] [Chemistry 31]

[0201]

[0202] In the formula, X4, Z, and s are the same as above.

[0203] A polymer containing a structural unit represented by the general formula (1) can be obtained by reacting a tetracarboxylic dianhydride represented by the general formula (19) with a diamine represented by the general formula (20). First, a polymer containing a structural unit (1) can be obtained by reacting a tetracarboxylic dianhydride represented by the general formula (19) with a diamine represented by the general formula (20). A polymer containing a structural unit (1) can be obtained by synthesizing an amic acid by heating and dehydrating the amic acid to form an imide ring.

[0204] The production of the structural unit (1) can be carried out by dissolving a diamine in a solvent having a high boiling point and high polarity such as γ-butyrolactone or N-methyl-2-pyrrolidone, adding an acid anhydride and reacting the diamine at 0 to 80°C, preferably 10 to 50°C to convert the diamine into an amic acid, adding a non-polar solvent such as xylene, heating the diamine to 100 to 200°C, preferably 130 to 180°C, and carrying out an imidization reaction while removing water from the reaction system.

[0205] [Chemistry 32]

[0206]

[0207] Wherein, X1 is the same as above.

[0208] [Chemistry 33]

[0209]

[0210] In the formula, R1 to R4 and L are the same as described above.

[0211] Preferred examples of the tetracarboxylic dianhydride represented by the general formula (19) include aromatic acid dianhydrides, alicyclic acid dianhydrides, aliphatic acid dianhydrides, and siloxane skeleton-containing acid dianhydrides.

[0212] Examples of the aromatic acid dianhydride include pyromellitic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3,2',3'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-terphenyltetracarboxylic acid dianhydride, 3,3',4,4'-oxyphthalic acid dianhydride, 2,3,3',4'-oxyphthalic acid dianhydride, 2,3,2',3'-oxyphthalic acid dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride, -tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1,4-(3,4-dicarboxyphenoxy)phthalic dianhydride, p-phenylenebis(trimellitic acid monoester anhydride), bis(1,3-dioxo-1,3-dihydroisobenzofuran-5- -carboxylic acid) 1,4-phenylene ester, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis(4-(3,4-dicarboxyphenoxy)phenyl)fluorene dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxyphenyl) The invention also includes, but is not limited to, 1,6-difluoropyromellitic acid dianhydride, 1-trifluoromethylpyromellitic acid dianhydride, 1,6-bis(trifluoromethyl)pyromellitic acid dianhydride, 2,2'-bis(trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, or acid dianhydride compounds in which the aromatic rings thereof are substituted with alkyl groups, alkoxy groups, halogen atoms, etc.

[0213] Examples of the alicyclic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cycloheptanetetracarboxylic dianhydride, 2,3,4,5-tetrahydro Furantetracarboxylic acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid dianhydride, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic acid dianhydride, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic acid dianhydride, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic acid dianhydride, tricyclo[6,3,0,0 2,6 ] undecane-3,5,9,11-tetracarboxylic dianhydride, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,1]heptanetetracarboxylic dianhydride, bicyclo[2,2,1]heptane-5-carboxymethyl-2,3,6-tricarboxylic dianhydride, 7-oxabicyclo[2,2,1]heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecahydroanthracene-1,2 ,8,9-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride, 3,3',4,4'-oxydicyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furan)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and "RIKACID" (registered trademark) BT-100 (above, trade names, manufactured by Shin Nippon Chemical Co., Ltd.) and their derivatives, or acid dianhydride compounds in which their alicyclic rings are substituted with alkyl groups, alkoxy groups, halogen atoms, etc., but are not limited thereto.

[0214] Examples of the aliphatic acid dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and derivatives thereof, but are not limited thereto.

[0215] Examples of the siloxane skeleton-containing acid dianhydride include, but are not limited to, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 3,3′-((1,1,3,3-tetramethyl-1,3-disiloxanediyl)di-3,1-propanediyl)bis(dihydro-2,5-furandione), and derivatives thereof.

[0216] These aromatic acid dianhydrides, alicyclic acid dianhydrides, aliphatic acid dianhydrides, and siloxane skeleton-containing acid dianhydrides may be used alone or in combination of two or more.

[0217] Examples of desirable diamines represented by the general formula (20) include 4-(4-aminophenoxy)-3-methylaniline, 4-(4-aminophenoxy)-2-methylaniline, 4-(4-aminophenoxy)-3-ethylaniline, 4-(4-aminophenoxy)-2-ethylaniline, 4-(4-aminophenoxy)-3-propylaniline, 4-(4-aminophenoxy)-2-propylaniline, 4-(4-aminophenoxy)-3-isopropylaniline, 4-(4-aminophenoxy)-2-isopropylaniline, 4-(4-aminophenoxy)-3-butylaniline, 4-(4-aminophenoxy)-2-butylaniline, 4-(4-aminophenoxy)-3-isobutylaniline, 4-(4-aminophenoxy) 4-(4-aminophenoxy)-2-(trifluoromethyl)aniline, 4-(4-aminophenoxy)-3-methoxyaniline, 4-(4-aminophenoxy)-2-methoxyaniline, 4-(4-aminophenoxy)-3-ethoxyaniline, 4-(4-aminophenoxy)-2-ethoxyaniline, 4-(4-aminophenoxy)-3-propoxyaniline, 4-(4-aminophenoxy)-2-propoxyaniline 4-(4-aminophenoxy)-3-butyloxyaniline, 4-(4-aminophenoxy)-2-butyloxyaniline, 4-(4-aminophenoxy)-3-phenylaniline, 4-(4-aminophenoxy)-2-phenylaniline, 4-(4-aminophenoxy)-3-tolylaniline, 4-(4-aminophenoxy)-2-tolylaniline, 4-(4-aminophenoxy)-3-ethylphenylaniline, 4-(4-aminophenoxy)-2-ethylphenylaniline, 4-(4-aminophenoxy)-3-propylphenylaniline, 4-(4-aminophenoxy)-2-propylphenylaniline, 4-(4-aminophenoxy)-3-butylphenylaniline, 4-(4-aminophenoxy)-2-butylphenylaniline, 4-(4-aminophenoxy)-3-butylphenylaniline 4-(4-aminophenoxy)-3-fluorophenylaniline, 4-(4-aminophenoxy)-2-fluorophenylaniline, 4-(4-aminophenoxy)-3-chlorophenylaniline, 4-(4-aminophenoxy)-2-chlorophenylaniline, 4-(4-aminophenoxy)-3-bromophenylaniline, 4-(4-aminophenoxy)-2-bromophenylaniline, 4-(4-aminophenoxy)-3-methoxyphenylaniline, 4-(4-aminophenoxy)-2-methoxyphenylaniline, 4-(4-aminophenoxy)-3-ethoxyphenylaniline, 4-(4-aminophenoxy)-2-ethoxyphenylaniline, 4-(4-aminophenoxy)-3-(phenethyl)phenylaniline, 4-(4-aminophenoxy)-2-(phenethyl)phenylaniline,4-(4-aminophenoxy)-3-naphthylphenylaniline, 4-(4-aminophenoxy)-2-naphthylphenylaniline, 4-(4-aminophenoxy)-3-benzylphenylaniline, 4-(4-aminophenoxy)-2-benzylphenylaniline, 4-((4-aminophenyl)thio)-3-methylaniline, 4-((4-aminophenyl)thio)-2-methylaniline, 4-((4-aminophenyl)thio)-3-ethylaniline, 4-((4-aminophenyl)thio)-2-ethylaniline, 4-((4-aminophenyl)thio)-3-propylaniline, 4-((4-aminophenyl)thio)-2-propylaniline, 4-((4-aminophenyl)thio)-3-isopropylaniline, 4-((4-aminophenyl)thio)- 4-((4-aminophenyl)thio)-2-isopropylaniline, 4-((4-aminophenyl)thio)-3-butylaniline, 4-((4-aminophenyl)thio)-2-butylaniline, 4-((4-aminophenyl)thio)-3-isobutylaniline, 4-((4-aminophenyl)thio)-2-isobutylaniline, 4-((4-aminophenyl)thio)-3-(trifluoromethyl)aniline, 4-((4-aminophenyl)thio)-2-(trifluoromethyl)aniline, 4-((4-aminophenyl)thio)-3-methoxyaniline, 4-((4-aminophenyl)thio)-2-methoxyaniline, 4-((4-aminophenyl)thio)-3-ethoxyaniline, 4-((4-aminophenyl)thio)-2-ethoxyaniline, 4-( (4-aminophenyl)thio)-3-propoxyaniline, 4-((4-aminophenyl)thio)-2-propoxyaniline, 4-((4-aminophenyl)thio)-3-isopropoxyaniline, 4-((4-aminophenyl)thio)-2-isopropoxyaniline, 4-((4-aminophenyl)thio)-3-butoxyaniline, 4-((4-aminophenyl)thio)-2-butoxyaniline, 4-((4-aminophenyl)thio)-3-phenylaniline, 4-((4-aminophenyl)thio)-2-phenylaniline, 4-((4-aminophenyl)thio)-3-naphthylaniline, 4-((4-aminophenyl)thio)-2-naphthylaniline, 4-((4-aminophenyl)thio)-3-methoxyphenylaniline amine, 4-((4-aminophenyl)thio)-2-methoxyphenylaniline, 4-((4-aminophenyl)methyl)-3-methylaniline, 4-((4-aminophenyl)methyl)-2-methylaniline, 4-((4-aminophenyl)methyl)-3-ethylaniline, 4-((4-aminophenyl)methyl)-2-ethylaniline, 4-((4-aminophenyl)methyl)-3-propylaniline, 4-((4-aminophenyl)methyl)-2-propylaniline, 4-((4-aminophenyl)methyl)-3-isopropylaniline, 4-((4-aminophenyl)methyl)-2-isopropylaniline, 4-((4-aminophenyl)methyl)-3-butylaniline, 4-((4-aminophenyl)methyl)-2-butylaniline,4-((4-aminophenyl)methyl)-3-isobutylaniline, 4-((4-aminophenyl)methyl)-2-isobutylaniline, 4-((4-aminophenyl)methyl)-3-(trifluoromethyl)aniline, 4-((4-aminophenyl)methyl)-2-(trifluoromethyl)aniline, 4-((4-aminophenyl)methyl)-3-methoxyaniline, 4-((4-aminophenyl)methyl)-2-methoxyaniline, 4-((4-aminophenyl)methyl)-3-ethoxyaniline, 4-((4-aminophenyl)methyl )-2-ethoxyaniline, 4-((4-aminophenyl)methyl)-3-propoxyaniline, 4-((4-aminophenyl)methyl)-2-propoxyaniline, 4-((4-aminophenyl)methyl)-3-isopropoxyaniline, 4-((4-aminophenyl)methyl)-2-isopropoxyaniline, 4-((4-aminophenyl)methyl)-3-butoxyaniline, 4-((4-aminophenyl)methyl)-2-butoxyaniline, 4-((4-aminophenyl)methyl)-3-phenylaniline, 4-((4-aminophenyl)methyl phenyl)methyl)-2-phenylaniline, 4-((4-aminophenyl)methyl)-3-naphthylaniline, 4-((4-aminophenyl)methyl)-2-naphthylaniline, 4-((4-aminophenyl)methyl)-3-methoxyphenylaniline, 4-((4-aminophenyl)methyl)-2-methoxyphenylaniline, (4-amino-2-methylphenyl)(4-aminophenyl)methanone, (4-amino-2-ethylphenyl)(4-aminophenyl)methanone, (4-amino-2-propylphenyl)(4-aminophenyl)methanone, (4-amino 1-aminophenyl) ketone, (4-amino-2-isopropylphenyl) (4-aminophenyl) ketone, (4-amino-2-butylphenyl) (4-aminophenyl) ketone, (4-amino-2-(trifluoromethyl) phenyl) (4-aminophenyl) ketone, 4-amino-2-methoxyphenyl) (4-aminophenyl) ketone, 4-amino-2-ethoxyphenyl) (4-aminophenyl) ketone, (4-amino-2-(phenyl) phenyl) (4-aminophenyl) ketone, (4-amino-2-(methoxyphenyl) phenyl) (4-aminophenyl) ketone, but not limited thereto.

[0218] On the other hand, a polymer containing a structural unit represented by the above general formula (2) can be obtained by reacting a dicarboxylic acid compound represented by the following general formula (21) with a diamine represented by the above general formula (20).

[0219] [Chemistry 34]

[0220]

[0221] Wherein, X2 is the same as above.

[0222] Here, the polymer containing the structural unit (2) can be obtained, for example, by reacting a dicarboxylic acid compound represented by the general formula (21) and a diamine represented by the general formula (20) in the presence of a dehydration condensation agent. That is, the dicarboxylic acid compound represented by the general formula (21) is used for the reaction in a state dissolved in a reaction solvent, and a known dehydration condensation agent (e.g., dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc.) is added to the reaction solution under ice cooling and mixed, and the dicarboxylic acid compound represented by the general formula (21) is converted into an acid anhydride, and then the diamine represented by the general formula (20) is separately dissolved or dispersed in a solvent and added dropwise thereto, and the mixture is subjected to polycondensation, thereby obtaining a polymer containing the structural unit (2).

[0223] Another method for obtaining a polymer containing the structural unit (2) by reacting a dicarboxylic acid compound represented by the general formula (21) with a diamine (diamine compound) represented by the general formula (20) is as follows: a method for synthesizing by converting the dicarboxylic acid compound represented by the general formula (21) into an acid chloride using a chlorinating agent such as thionyl chloride or dichlorooxalic acid, and then reacting the resulting mixture with the diamine represented by the general formula (20).

[0224] In the reaction of converting the dicarboxylic acid compound into an acid chloride using a chlorinating agent, a basic compound may be used, such as pyridine, N,N-dimethyl-4-aminopyridine, triethylamine, etc.

[0225] Then, by reacting the obtained acid chloride of the dicarboxylic acid compound with the diamine represented by the above general formula (20) in the presence of a basic catalyst, the target polymer containing the structural unit (2) can be obtained. In this case, the basic catalyst includes pyridine, N,N-dimethyl-4-aminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, etc. These basic catalysts can be used alone or in combination of two or more.

[0226] Among the methods for producing the polymer of the present invention, the solvent used in the method via the acid chloride is preferably one that can dissolve the above-mentioned dicarboxylic acid compound and its acid chloride well, and the polymer obtained by the polycondensation reaction with diamines. Specifically, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric acid triamide, γ-butyrolactone, etc. In addition, in addition to polar solvents, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. can also be used. For example, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, etc. These organic solvents may be used alone or in combination of two or more.

[0227] Preferred examples of X2 in the dicarboxylic acid compound represented by the general formula (21) include the same examples as those mentioned above.

[0228] Examples of the dicarboxylic acid compound represented by the general formula (21) include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2, 6,6-Tetramethyl pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid Alkanedioic acid, hexadecanedioic acid, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, heptacosanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, hexadecanedioic acid, triacontanedioic acid, 3-oxoglutaric acid, etc.

[0229] Examples of dicarboxylic acid compounds having an aromatic ring include phthalic acid, isophthalic acid, terephthalic acid, 4,4'-diphenyl ether dicarboxylic acid, 3,4'-diphenyl ether dicarboxylic acid, 3,3'-diphenyl ether dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 3,4'-biphenyl dicarboxylic acid, 3,3'-biphenyl dicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylic acid, 3,3'-benzophenone dicarboxylic acid, 4,4'-hexafluoroisopropylidene dibenzoic acid, 4,4'-dicarboxy diphenylamide, and 1 , 4-phenylene diethanedioxane acid, bis(4-carboxyphenyl) sulfide, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-carboxyphenyl)tetraphenyldisiloxane, bis(4-carboxyphenyl)tetramethyldisiloxane, bis(4-carboxyphenyl)sulfone, bis(4-carboxyphenyl)methane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,2-bis-(p-carboxyphenyl)propane, 2,6-naphthalene dicarboxylic acid, etc., but not limited thereto. Again, they can be used alone or in combination.

[0230] On the other hand, the polymer containing the structural unit (3) can be obtained by implementing the same reaction procedure as the structural unit (1). That is, it can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (22) with a diamine represented by the following general formula (23). First, after synthesizing an amic acid by reacting a tetracarboxylic dianhydride represented by the following general formula (22) with a diamine represented by the following general formula (23), heating and dehydration are then used to form an imide ring, thereby obtaining a polymer containing the structural unit (3).

[0231] [Chemistry 35]

[0232]

[0233] Wherein, X3 is the same as above.

[0234] [Chemistry 36]

[0235]

[0236] Wherein, s and Z are the same as above.

[0237] Preferred examples of the tetracarboxylic dianhydride represented by the general formula (22) include the examples exemplified by the tetracarboxylic dianhydride represented by the general formula (19).

[0238] On the other hand, s in the general formula (23) represents 0 or 1. When s=0, the two aromatic rings in the general formula (23) are directly bonded without a divalent bonding group Z interposed therebetween.

[0239] Furthermore, when s in the general formula (23) is 1, there is no limitation on Z in the general formula (23) as long as it is a divalent group. It is preferably a divalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a divalent aromatic group having 6 to 40 carbon atoms as described above, and is more preferably a divalent bonding group represented by the formula (11). Furthermore, the structure of Z may be one or a combination of two or more.

[0240] Furthermore, preferred examples of the diamine represented by the general formula (23) are compounds represented by the following formulas (24), (25), (26) and (27).

[0241] [Chemistry 37]

[0242]

[0243] Particularly preferred examples of the diamine represented by the general formula (23) are compounds represented by the formulas (24) and (25).

[0244] The polymer obtained by reacting the diamine represented by the above formula (24) with the tetracarboxylic dianhydride represented by the above general formula (22) is preferably a polymer containing the structural unit represented by the above general formula (3-1) as a structural unit.

[0245] On the other hand, the polymer obtained by reacting the diamine represented by the above formula (25) with the tetracarboxylic dianhydride represented by the above general formula (22) is preferably a polymer containing the structural unit represented by the above general formula (3-2) as a structural unit.

[0246] On the other hand, the polymer containing the structural unit (4) can be obtained by carrying out the same reaction procedure as the structural unit (2). That is, it can be obtained by reacting a dicarboxylic acid compound represented by the following general formula (28) in the presence of a dehydrating condensation agent or by using a chlorinating agent to convert it into an acid chloride, and then reacting it with a diamine represented by the above general formula (23).

[0247] [Chemistry 38]

[0248]

[0249] Wherein, X4 is the same as above.

[0250] Preferred examples of the dicarboxylic acid compound represented by the general formula (28) include the dicarboxylic acid compounds represented by the general formula (21).

[0251] Furthermore, as described above, the polymer of the present invention may contain a structural unit represented by the following general formula (12) in addition to the structural units represented by the above general formulas (1), (2), (3) and (4).

[0252] [Chemistry 39]

[0253]

[0254] In the formula, X5 and X6 are the same as above.

[0255] The polymer containing the structural unit represented by the general formula (12) can be obtained by carrying out the same reaction procedure as the structural unit (1). That is, by reacting the tetracarboxylic dianhydride represented by the general formula (29) below with the diamine represented by the general formula (30) below to synthesize the amic acid, and then forming the imide ring through a heating dehydration step, thereby obtaining the polymer containing the structural unit represented by the general formula (12).

[0256] [Chemistry 40]

[0257]

[0258] Wherein, X5 is the same as above.

[0259] [Chemistry 41]

[0260] NH2-X6-NH2 (30)

[0261] Wherein, X6 is the same as above.

[0262] As the tetracarboxylic dianhydride represented by the above general formula (29), the examples exemplified by the tetracarboxylic dianhydride represented by the above general formula (19) are mentioned as preferable examples.

[0263] Examples of the diamine represented by the general formula (30) include aromatic diamines, alicyclic diamines, aliphatic diamines, and polyether diamines.

[0264] Preferred aromatic diamines include, for example, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzidine, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2'-3,3'-tetramethylbenzidine, 2,2'-dichlorobenzidine, 3,3'-dichlorobenzidine, 2,2 '3,3'-tetrachlorobenzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)fluorene, 2,2'-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminobenzanilide, or diamine compounds in which the aromatic rings thereof are substituted with alkyl groups, alkoxy groups, halogen atoms, etc., but are not limited thereto.

[0265] Examples of the alicyclic diamine include cyclobutanediamine, isophoronediamine, bicyclo[2,2,1]heptanedimethylamine, tricyclo[3,3,1,1 3,7]Decane-1,3-diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-diaminocyclohexane, trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3', 5,5'-Tetramethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-Tetraethyl-4,4'-diaminodicyclohexylmethane, 3,5-Diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, 3,3'-Dimethyl-4,4'-diaminodicyclohexyl ether, 3,3'-Diethyl-4,4'-diamino Dicyclohexyl ether, 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexyl ether, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexyl ether, 3,5-diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexyl ether, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(3-methyl-4-aminocyclohexyl)propane, 2,2-bis(3-ethyl The invention also includes, but is not limited to, diamine compounds in which the alicyclic rings thereof are substituted with alkyl groups, alkoxy groups, halogen atoms, etc.

[0266] Examples of the aliphatic diamine include, but are not limited to, alkylenediamines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane, bis(aminomethyl)ether, bis(2-aminoethyl)ether, and siloxanediamines such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, and α,ω-bis(3-aminopropyl)polydimethylsiloxane.

[0267] Examples of the polyether diamine include, but are not limited to, 1,2-bis(aminoethoxy)ethane, HK-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-230, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009, RT-1000, HE-1000, and HT-1700 (all trade names, manufactured by HUNTSMAN Co., Ltd.). These may be used alone or in combination.

[0268] These aromatic diamines, alicyclic diamines, aliphatic diamines, and polyether diamines can be used alone or in combination of two or more.

[0269] Furthermore, siloxane diamines can also be preferably used.

[0270] Furthermore, as described above, the polymer of the present invention may contain a structural unit represented by the following general formula (13) in addition to the structural units represented by the above general formulas (1), (2), (3) and (4).

[0271] [Chemistry 42]

[0272]

[0273] In the formula, X7 and X8 are the same as above.

[0274] The polymer containing the structural unit represented by the general formula (13) can be obtained by carrying out the same reaction procedure as the structural unit (2). That is, it can be obtained by reacting a dicarboxylic acid compound represented by the general formula (31) in the presence of a dehydrating condensation agent or by converting it into an acid chloride using a chlorinating agent, and then reacting it with a diamine represented by the general formula (32).

[0275] [Chemistry 43]

[0276]

[0277] Wherein, X7 is the same as above.

[0278] [Chemistry 44]

[0279] NH2-X8-NH2 (32)

[0280] Wherein, X8 is the same as above.

[0281] Preferred examples of the dicarboxylic acid compound represented by the general formula (31) include the dicarboxylic acid compounds represented by the general formula (21).

[0282] Moreover, as the diamine represented by the above-mentioned general formula (32), the examples exemplified for the diamine represented by the above-mentioned general formula (30) are mentioned as preferable examples.

[0283] Furthermore, as described above, the polymer of the present invention may contain a structural unit represented by the following general formula (14) in addition to the structural units represented by the above general formulas (1), (2), (3) and (4).

[0284] [Chemistry 45]

[0285]

[0286] In the formula, X9, X 10 , and R b Same as above.

[0287] The polymer containing the structural unit represented by the general formula (14) can be obtained by carrying out the same reaction procedure as the structural unit (2). That is, it can be obtained by reacting a tetracarboxylic acid diester compound represented by the general formula (33) in the presence of a dehydrating condensation agent or by converting it into an acid chloride using a chlorinating agent, and then reacting it with a diamine represented by the general formula (34).

[0288] [Chemistry 46]

[0289]

[0290] In the formula, R b and X9 is the same as above.

[0291] [Chemistry 47]

[0292] H2N-X 10 NH2 (344

[0293] Where, X 10 Same as above.

[0294] The method for producing the tetracarboxylic acid diester compound represented by the general formula (33) can be exemplified by reacting a tetracarboxylic acid dianhydride represented by the general formula (35) below with a compound having a hydroxyl group at the terminal represented by the general formula (36) below in the presence of a basic catalyst such as pyridine to introduce R b Here, the tetracarboxylic dianhydride represented by the following general formula (35) becomes the basis of X9 (for example, the tetravalent organic group represented by the above formula (9)) in the above general formula (14).

[0295] [Chemistry 48]

[0296]

[0297] Wherein, X9 is the same as above.

[0298] [Chemistry 49]

[0299] HO-Rb (36)

[0300] In the formula, R b Same as above.

[0301] Preferred examples of the tetracarboxylic dianhydride represented by the general formula (35) include the examples exemplified by the tetracarboxylic dianhydride represented by the general formula (19).

[0302] The reaction of the tetracarboxylic dianhydride represented by the general formula (35) and the compound having a hydroxyl group at the terminal represented by the general formula (36) can be carried out by stirring, dissolving and mixing the tetracarboxylic dianhydride represented by the general formula (35) and the compound having a hydroxyl group at the terminal represented by the general formula (36) in the presence of a basic catalyst such as pyridine in a reaction solvent at a reaction temperature of 20 to 50°C for 4 to 10 hours to carry out a half-esterification reaction of the acid dianhydride, and obtaining the desired tetracarboxylic acid diester compound represented by the general formula (33) in the form of a solution dissolved in the reaction solvent.

[0303] The obtained tetracarboxylic acid diester compound may be isolated, or the obtained solution may be used directly in the reaction of the diamine in the above-mentioned subsequent step.

[0304] The reaction solvent is preferably one that can dissolve the tetracarboxylic acid diester compound and the polymer having the structural unit of the polyimide precursor obtained by the subsequent polycondensation reaction of the tetracarboxylic acid diester compound and the diamines, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, etc. In addition, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. can also be used, and specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. can be used. These may be used alone or in combination of two or more types as needed.

[0305] Furthermore, as the diamine represented by the general formula (34), the diamines represented by the general formula (30) mentioned above can be exemplified as preferred examples.

[0306] Furthermore, as described above, the polymer of the present invention may contain a structural unit represented by the following general formula (15) in addition to the structural units represented by the above general formulas (1), (2), (3) and (4).

[0307] [Chemistry 50]

[0308]

[0309] Where, X 11 and X 12 Same as above.

[0310] A polymer containing the structural unit represented by the general formula (15) can be obtained by reacting a dicarboxylic acid compound represented by the general formula (37) in the presence of a dehydrating condensation agent or converting it into an acid chloride using a chlorinating agent, and then reacting it with a dihydroxydiamine compound represented by the general formula (38) to synthesize a hydroxyamide (polyoxazole precursor), and then subjecting it to a heating dehydration step to form an oxazole ring, thereby obtaining a polymer containing the structural unit represented by the general formula (15).

[0311] [Chemistry 51]

[0312]

[0313] Where, X 11 Same as above.

[0314] [Chemistry 52]

[0315]

[0316] Where, X 12 Same as above.

[0317] Preferred examples of the dicarboxylic acid compound represented by the general formula (37) include the dicarboxylic acid compounds represented by the general formula (21).

[0318] Examples of the dihydroxydiamine compound represented by the general formula (38) include 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxybiphenyl ether, 2,2'-bis(3-amino-4-hydroxyphenyl)sulfide, 2,2'-bis(3-amino-4-hydroxyphenyl)ketone, 3,3'-diamino-4,4'-dihydroxyphenylmethane, 1,2-bis(3-amino-4-hydroxyphenyl)ethane, 2,2'-bis(3-amino-4-hydroxyphenyl)difluoromethane, 4,4' ... -(1,1,2,2,3,3-hexafluoro-1,3-propanediyl)bis(2-aminophenol), 2,2'-bis(3-amino-4-hydroxyphenyl)propane, 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxyphenyl)sulfone, 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane, 4,4'-(1,4-phenylenebis(oxy))bis(2-aminophenol), 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, etc., but not limited thereto. Moreover, these can be used alone or in combination.

[0319] (Polymer molecular weight and introduction of terminal capping agent)

[0320] The ideal molecular weight of the polymer is preferably 5,000 to 100,000, more preferably 7,000 to 50,000. If the molecular weight is 5,000 or more, the positive and negative photosensitive resin compositions of the present invention using the polymer can be easily formed into a desired film thickness on a substrate. If the molecular weight is 100,000 or less, the viscosity of the positive and negative photosensitive resin compositions will not be significantly high, and there will be no doubt that the film cannot be formed. In addition, in the present invention, the weight average molecular weight is a polystyrene conversion value obtained by gel permeation chromatography (GPC).

[0321] In order to control the molecular weight in the polycondensation reaction and suppress the change of the molecular weight of the obtained polymer over time, that is, to suppress gelation, the above-mentioned polymer can also be sealed at both ends by using an end-capping agent. The end-capping agent that reacts with the acid dianhydride can be exemplified by monoamine, monohydric alcohol, etc. In addition, the end-capping agent that reacts with the diamine compound can be exemplified by anhydride, unit carboxylic acid, monoacyl chloride compound, monoactive ester compound, dicarbonate, vinyl ether, etc. In addition, by reacting the end-capping agent, various organic groups can be introduced as terminal groups.

[0322] Examples of monoamines that can be used as an end-capping agent for the acid anhydride group terminal include aniline, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy 4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 6-amino-2,4-dihydroxy-1,3,5-triazine (ammelide), 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4 ,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol , 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-aminonaphthalene, 3,5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7-diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-aminonaphthalene, 4,8-diethynyl-2-aminonaphthalene, 4-fluoroaniline, 3-fluoroaniline, 2-fluoroaniline, 2,4-difluoroaniline, 3,4-difluoroaniline, 2,4,6-trifluoroaniline, 2,3,4-trifluoroaniline, pentafluoroaniline, etc., but not limited thereto. They may be used alone or in combination of two or more.

[0323] On the other hand, examples of monohydric alcohols that can be used as an end-capping agent for the acid anhydride groups include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, 2-nonanol, 1-decanol, 2-decanol, 1-undecanol, 2-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 2-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 2-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2-heptadecanol, 1-octadecanol, 2-octadecanol, 1-nonadecanol, 2-nonadecanol, 1-eicosyl alcohol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-propyl-1-pentanol, 2-ethyl-1-hexanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,4,4-trimethyl-1-hexanol, 2,6-dimethyl-4-heptanol, isononyl alcohol, 3,7-dimethyl-3-octanol, 2,4-dimethyl-1-heptanol, 2-heptylundecanol, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol 1-methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, cyclopentanol, cyclohexanol, cyclopentane monomethylol, dicyclopentane monomethylol, tricyclodecane monomethylol, norborneol, terpineol, etc., but are not limited thereto. These may be used alone or in combination of two or more.

[0324] Examples of acid anhydrides, monocarboxylic acids, monoacyl chloride compounds, and monoactive ester compounds that can be used as an amino terminal blocking agent include phthalic anhydride, maleic anhydride, anhydrous nadic acid, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride and the like, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy- 2-Carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl- Monocarboxylic acids such as 1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid, 8-ethynyl-2-naphthoic acid, and monocarboxylic acid compounds obtained by chlorinating their carboxyl groups, and terephthalic acid, phthalic acid, malic acid The invention also includes monoacyl chloride compounds obtained by chlorinating only a single carboxyl group of dicarboxylic acids such as naphthalene, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene and 2,7-dicarboxynaphthalene; and monoactive ester compounds obtained by reacting the monoacyl chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxyimide.

[0325] Examples of the dicarbonate compound that can be used as the amino terminal blocking agent include di(tert-butyl) dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.

[0326] Examples of the vinyl ether compound that can be used as the amino terminal blocking agent include butyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, tert-butyl vinyl ether, and benzyl vinyl ether.

[0327] Other compounds that can be used as the amino terminal blocking agent include: chloroformates such as benzoyl chloride, fluorenylmethyl chloroformate, 2,2,2-trichloroethyl chloroformate, tert-butyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, benzyl chloroformate, allyl chloroformate, ethyl chloroformate, and isopropyl chloroformate, isocyanate compounds such as butyl isocyanate, 1-naphthyl isocyanate, octadecyl isocyanate, and phenyl isocyanate, methanesulfonyl chloride, and p-toluenesulfonyl chloride.

[0328] The introduction ratio of the end-capping agent at the end of the acid anhydride group is preferably in the range of 0.1 to 60 mol %, preferably 5 to 50 mol %, and more preferably 5 to 20 mol % relative to the total amount of the tetracarboxylic dianhydride component and the dicarboxylic acid component. In addition, the introduction ratio of the end-capping agent at the amino terminal is preferably in the range of 0.1 to 100 mol %, preferably 5 to 90 mol %, relative to the diamine component. In addition, by reacting a plurality of end-capping agents, a plurality of different terminal groups can also be introduced.

[0329] [Photosensitive resin composition]

[0330] Next, a photosensitive resin composition using the polymer of the present invention as a base resin will be described. The present invention can obtain a positive photosensitive resin composition or a negative photosensitive resin composition by using the polymer of the present invention as a base resin.

[0331] [Positive photosensitive resin composition]

[0332] First, among the photosensitive resin compositions using the polymer of the present invention as a base resin, a positive photosensitive resin composition that can be alkali developed will be described. The positive photosensitive resin composition of the present invention can be prepared into the following two forms, for example, but is not limited thereto.

[0333] The first embodiment of the positive photosensitive resin composition of the present invention comprises:

[0334] (A) A polymer comprising the structural unit (1) and / or the structural unit (2) and the structural unit (3) and / or the structural unit (4)

[0335] (B) is a photosensitizer that generates acid due to light and increases the dissolution rate in an alkaline aqueous solution, and has a diazoquinone structure, and

[0336] (D) Solvent.

[0337] The component (A) in the positive photosensitive resin composition of the present invention uses the above-mentioned polymer. The amount of the component (A) added is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 30 parts by mass relative to 100 parts by mass of the total amount of the composition. In addition, one kind of the component (A) may be used or two or more kinds may be used in combination.

[0338] The structural unit (3) or structural unit (4) in the positive photosensitive resin composition of the present invention has a phenolic hydroxyl group, so that a desired alkali dissolution rate can be obtained in a developer which is an alkali aqueous solution, and a fine pattern can be formed with high resolution.

[0339] The component (B) in the positive photosensitive resin composition of the present invention is a photosensitive agent that generates acid by light and increases the dissolution rate in an alkaline aqueous solution, and has a diazoquinone structure. Examples of the component (B) include compounds having a 1,2-diazonaphthoquinonesulfonyl group in the molecule.

[0340] Examples of the compound having a 1,2-diazonaphthoquinonesulfonyl group in the molecule include compounds having a 1,2-diazonaphthoquinonesulfonyl group in the molecule represented by the following general formula (39) or (40).

[0341] [Chemistry 53]

[0342]

[0343] The compound into which the 1,2-diazonaphthoquinonesulfonyl group is introduced is preferably trihydroxybenzophenone or tetrahydroxybenzophenone, a ballast molecule represented by the following general formula (41) having a phenolic hydroxyl group, or a novolac resin having a repeating unit represented by the formula (46) described later and having a weight average molecular weight of 2,000 to 20,000, preferably 3,000 to 10,000. That is, the resin having a phenolic hydroxyl group listed below, or a compound in which the hydrogen atom of the phenolic hydroxyl group is substituted by the 1,2-diazonaphthoquinonesulfonyl group can be preferably used as the component (B).

[0344] [Chemistry 54]

[0345]

[0346] Here, R 101 ~R 106Each of E and E is independently a hydrogen atom, a methyl group, a group represented by the following formula (42), or a group represented by the following formula (43). w is an integer of 0 to 2, and z is an integer of 0 to 2. When z is 0, w is 1 or 2. When z is 0 and w is 1, E is a hydrogen atom, a methyl group, or a group represented by the following formula (42). When z is 0 and w is 2, one of E is a methylene group or a group represented by the following formula (44), and the other is a hydrogen atom, a methyl group, or a group represented by the following formula (42). When z is 1, E is a methylene group or a group represented by the following formula (44). When z is 2 and w is 1, E is a methine group or a group represented by the following formula (45). When w is 2, one of E is a methylene group or a group represented by the following formula (44), and the other is a methine group or a group represented by the following formula (45).

[0347] [Chemistry 55]

[0348]

[0349] In the formula, a1, a2, a3, a4, a5, a6, and a7 are integers of 0 to 3, respectively, but a1+a2≤5, a3+a4≤4, a6+a7≤3.

[0350] In this case, in the ballast molecule of the formula (41), the number of benzene rings is 2 to 20, preferably 2 to 10, and more preferably 3 to 6, and the number of phenolic hydroxyl groups is

[0351] The ratio of the number of benzene rings is 0.5 to 2.5, more preferably 0.7 to 2.0, and even more preferably 0.8 to 1.5.

[0352] Specific examples of such ballast molecules include the following (B-1) to (B-44).

[0353] [Chemistry 56]

[0354]

[0355] [Chemistry 57]

[0356]

[0357] [Chemistry 58]

[0358]

[0359] [Chemistry 59]

[0360]

[0361] [Chemistry 60]

[0362]

[0363] [Chemistry 61]

[0364]

[0365] [Chemistry 62]

[0366]

[0367] Among the ballast molecules exemplified above, (B-3), (B-29), (B-33), (B-38) and the like are preferably used. Compounds in which the hydrogen atoms of the phenolic hydroxyl groups of these ballast molecules are substituted with 1,2-diazonaphthoquinonesulfonyl groups are preferably used as the component (B) of the positive photosensitive resin composition of the present invention.

[0368] [Chemistry 63]

[0369]

[0370] In the formula, mm is an integer from 0 to 3.

[0371] The novolac resin having a repeating unit represented by the above formula (46) can be synthesized by condensing at least one phenol represented by the following formula (47), specifically, o-cresol, m-cresol, p-cresol, 3,5-dimethylphenol, etc., with an aldehyde by a conventional method.

[0372] [Chemistry 64]

[0373]

[0374] In the formula, mm is an integer from 0 to 3.

[0375] In this case, examples of the aldehyde include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and the like, and formaldehyde is preferred.

[0376] The ratio of the phenols represented by the above formula (47) to the aldehydes is 0.2 to 2 in terms of molar ratio, and particularly preferably 0.3 to 2.

[0377] The method for introducing 1,2-diazonaphthoquinonesulfonyl groups into the above-mentioned compound into which 1,2-diazonaphthoquinonesulfonyl groups have been introduced is preferably a dehydrogenation condensation reaction of 1,2-diazonaphthoquinonesulfonyl chloride with a phenolic hydroxyl group using a base catalyst. In the case of the stabilizing agent molecule represented by the above-mentioned formula (41), trihydroxybenzophenone or tetrahydroxybenzophenone, the proportion of the hydrogen atoms of the phenolic hydroxyl group being replaced by 1,2-diazonaphthoquinonesulfonyl groups is 10 to 100 mol%, preferably 50 to 100 mol%. In the case of the novolac resin having a repeating unit represented by the above-mentioned formula (46), the proportion of the hydrogen atoms of the phenolic hydroxyl group being replaced by 1,2-diazonaphthoquinonesulfonyl groups is 2 to 50 mol%, preferably 3 to 27 mol%.

[0378] The amount of the component (B) added is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the component (A).

[0379] By mixing such a component (B), before exposure, the solubility in the alkaline aqueous solution is suppressed due to the dissolution inhibition of the component (B), and the system becomes alkali-insoluble. During exposure, the photosensitizer of the component (B) generates acid due to light, and the dissolution rate in the alkaline aqueous solution is increased, and the system becomes alkali-soluble. That is, when the developer uses an alkaline aqueous solution, the unexposed part will not dissolve in the developer, and the exposed part will dissolve in the developer, so a positive pattern can be formed.

[0380] Then, the component (D) in the first embodiment of the positive photosensitive resin composition is a solvent. The solvent of the component (D) is not limited as long as it can dissolve the components (A) and (B). Examples of the solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, and γ-butyrolactone, and one or more of these can be used. Ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, or a mixed solvent thereof is particularly preferred.

[0381] The amount of the component (D) to be added is preferably 50 to 2,000 parts by mass, particularly preferably 100 to 1,000 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (B).

[0382] Next, a second embodiment of the positive photosensitive resin composition of the present invention will be described.

[0383] The second aspect of the positive photosensitive resin composition of the present invention contains, in addition to the above-mentioned components (A), (B), and (D), one or more crosslinking agents (C) selected from amino condensates modified by formaldehyde or formaldehyde-alcohol, phenol compounds having an average of more than two hydroxymethyl or alkoxyhydroxymethyl groups in one molecule, compounds in which the hydrogen atoms of the hydroxyl groups of polyphenols are substituted with glycidyl groups, compounds in which the hydrogen atoms of the hydroxyl groups of polyphenols or polyols are substituted with substituents represented by the following formula (C-1), and compounds containing two or more nitrogen atoms having glycidyl groups represented by the following formula (C-2).

[0384] [Chemistry 65]

[0385]

[0386] In the formula, dotted lines represent atomic bonds, Rc is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.

[0387] The component (A) and the component (B) of the second embodiment of the positive photosensitive resin composition of the present invention may preferably be the same as those of the first embodiment of the positive photosensitive resin composition.

[0388] The component (C) in the second aspect of the positive photosensitive resin composition of the present invention is one or more crosslinking agents selected from amino condensates modified with formaldehyde or formaldehyde-alcohol, phenol compounds having an average of more than two methylol groups or alkoxymethylol groups in one molecule, compounds in which the hydrogen atoms of the hydroxyl groups of polyphenols are substituted with glycidyl groups, compounds in which the hydrogen atoms of the hydroxyl groups of polyphenols or polyols are substituted with substituents represented by the following formula (C-1), and compounds containing two or more nitrogen atoms having glycidyl groups represented by the following formula (C-2).

[0389] [Chemistry 66]

[0390]

[0391] In the formula, a dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v represents 1 or 2.

[0392] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include melamine condensate modified with formaldehyde or formaldehyde-alcohol, and urea condensate modified with formaldehyde or formaldehyde-alcohol.

[0393] The preparation of the formaldehyde or formaldehyde-alcohol modified melamine condensate is, for example, firstly modifying the melamine monomer by hydroxymethylation with formaldehyde or further modifying it by alkoxylation with an alcohol according to a known method to prepare a modified melamine represented by the following general formula (48). The alcohol is preferably a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms.

[0394] [Chemistry 67]

[0395]

[0396] In the formula, R5 may be the same or different and may be a hydroxymethyl group, an alkoxymethyl group containing an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, but at least one of them is a hydroxymethyl group or the above alkoxymethyl group.

[0397] Examples of R5 include alkoxymethyl groups such as hydroxymethyl groups, methoxymethyl groups, and ethoxymethyl groups, and hydrogen atoms.

[0398] Specific examples of the modified melamine represented by the general formula (48) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethylol melamine, etc. Then, the modified melamine represented by the general formula (48) or its polymer (e.g., oligomer such as dimer and trimer) is subjected to addition condensation polymerization with formaldehyde according to a conventional method until the desired molecular weight is reached, thereby obtaining a melamine condensate modified by formaldehyde or formaldehyde-alcohol.

[0399] The above-mentioned urea condensate modified with formaldehyde or formaldehyde-alcohol can be prepared, for example, by modifying a urea condensate of a desired molecular weight by hydroxymethylation with formaldehyde, or further modifying it by alkoxylation with an alcohol according to a known method.

[0400] Specific examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, propoxymethylated urea condensate, and the like.

[0401] Moreover, these modified melamine condensates and modified urea condensates may be used alone or in combination of two or more.

[0402] Examples of the phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and compounds represented by the following formulae (C-3) to (C-7).

[0403] [Chemistry 68]

[0404]

[0405] The above cross-linking agents may be used alone or in combination of two or more.

[0406] On the other hand, examples of compounds in which the hydrogen atoms of the hydroxyl groups of polyphenols are substituted with glycidyl groups include compounds obtained by reacting the hydroxyl groups of bisphenol A, tris(4-hydroxyphenyl)methane, and 1,1,1-tris(4-hydroxyphenyl)ethane with epichlorohydrin in the presence of a base. Preferred examples of compounds in which the hydrogen atoms of the hydroxyl groups of polyphenols are substituted with glycidyl groups include compounds represented by the following formulae (C-8) to (C-14).

[0407] [Chemistry 69]

[0408]

[0409] In the formula, t is 2≤t≤3.

[0410] As the crosslinking agent, one or two of the compounds in which the hydroxyl group of the polyphenol is substituted with a glycidoxy group (the compounds in which the hydrogen atom of the hydroxyl group of the polyphenol is substituted with a glycidyl group) can be used.

[0411] Examples of the compound in which the hydrogen atom of the hydroxyl group of the polyphenol is substituted with a substituent represented by the following formula (C-1) include compounds having two or more of the substituents and represented by the following formula (C-15).

[0412] [Chemistry 70]

[0413]

[0414] In the formula, dotted lines represent bonds.

[0415] [Chemistry 71]

[0416]

[0417] In the formula, 1≤u≤3.

[0418] On the other hand, examples of the compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2) include compounds represented by the following formula (C-16).

[0419] [Chemistry 72]

[0420]

[0421] In the formula, a dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v represents 1 or 2.

[0422] [Chemistry 73]

[0423]

[0424] In the formula, U represents a linear, branched or cyclic alkylene group having 2 to 12 carbon atoms, or a divalent aromatic group.

[0425] Examples of the compound represented by the above formula (C-16) include compounds represented by the following formulae (C-17) to (C-20).

[0426] [Chemistry 74]

[0427]

[0428] On the other hand, as the compound containing two or more nitrogen atoms having glycidyl groups represented by the above formula (C-2), a compound represented by the following formula (C-21) can be preferably used.

[0429] [Chemistry 75]

[0430]

[0431] One or two of the compounds containing two or more nitrogen atoms having a glycidyl group represented by the above formula (C-2) can be used as a crosslinking agent.

[0432] The component (C) is a component that causes a crosslinking reaction during post-curing after pattern formation of the positive photosensitive resin composition using the polymer of the present invention, and further improves the strength of the cured product. The weight average molecular weight of the component (C) is preferably 150 to 10,000, and particularly preferably 200 to 3,000, from the perspective of light curing and heat resistance.

[0433] In the positive photosensitive resin composition of the second embodiment of the present invention, the content of the component (C) is preferably 0.5 to 50 parts by mass, particularly preferably 1 to 30 parts by mass, based on 100 parts by mass of the component (A).

[0434] In addition, as the solvent of the component (D) in the second embodiment of the positive photosensitive resin composition of the present invention, the same solvents as those described in the first embodiment of the positive photosensitive resin composition can be preferably used.

[0435] The positive photosensitive resin composition of the present invention may further contain (E) a compound that generates an acid by heat. The compound that generates an acid by heat as the component (E) may be added to thermally accelerate the crosslinking reaction with the component (A) in the step of post-curing by heating at a temperature of 100 to 300° C. applied after the pattern formation.

[0436] In particular, the component (E) is preferably one that does not promote the hardening of the film before patterning by development, and does not hinder pattern formation. In order to achieve this purpose, the component (E) is preferably one that does not generate acid at the temperature of the solvent removal and drying steps after coating the photosensitive resin composition, and promotes the hardening of the pattern and film of the positive photosensitive resin composition by first generating acid by heat treatment after pattern formation. Specifically, it is preferably a compound that decomposes and generates acid by heat treatment at 100°C to 300°C, preferably 150°C to 300°C. By containing such a component (E), the pattern and film of the positive photosensitive resin composition can be changed into a pattern and film that further undergoes crosslinking and hardening reaction in the step of heating and post-hardening at a temperature of 100 to 300°C applied after pattern formation. By further crosslinking and hardening reaction, the component (E) can further improve the mechanical strength, chemical resistance, adhesion, etc. of the obtained pattern or film.

[0437] The compound that generates an acid by heat is not particularly limited, and for example, the compounds described in paragraphs

[0061] to

[0085] of JP-A-2007-199653 can be used.

[0438] The amount of the compound generating an acid by heat is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the component (A) in the positive photosensitive resin composition of the present invention.

[0439] Furthermore, the positive photosensitive resin composition of the present invention may contain, in addition to component (A), component (B), component (C), component (D), and component (E), at least one selected from the group consisting of (F) a protective amine compound, (G) an antioxidant, (H) a silane compound, (I) a surfactant, and (J) a solubility inhibitor.

[0440] The positive photosensitive resin composition of the present invention may contain a protected amine compound (F) in addition to the above-mentioned components (A), (B), (C), and (D). The protected amine compound of the component (F) may be any nitrogen-containing organic compound in which a group deprotected by heat or acid is bonded to a nitrogen atom. In particular, there is no particular limitation if it has a carbamate structure represented by the following general formula (49) or (50).

[0441] [Chemistry 76]

[0442]

[0443] Here, in the formula, R 1 , R 2 , R 3 and R 4each independently represents hydrogen, an alkyl group having 1 to 8 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent, an alkoxy group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, an alkynyl group having 2 to 8 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and R 5 and R 6 Each independently represents hydrogen, an alkyl group having 1 to 8 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent, an alkoxy group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, an alkynyl group having 2 to 8 carbon atoms which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a monocyclic group which may have a substituent formed by bonding to each other, or a polycyclic group which may have a substituent formed by bonding to each other. (However, the total number of carbon atoms in the formula is preferably 10 or less.

[0444] Again, R 7 represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 12 carbon atoms which may have a substituent, an alkynyl group having 2 to 12 carbon atoms which may have a substituent, an aryl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, an aralkyl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, or a heterocyclic group which may have a substituent. (However, the group constituting R 7 The total number of carbon atoms is 12 or less). The substituents that the above groups may have may be any substituents as long as they do not violate the concept of the present invention.

[0445] [Chemistry 77]

[0446]

[0447] Specific examples of the above formulas (49) and (50) include the following. For example, N-(isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(isopropoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(isopropoxycarbonyl)diisopropylamine, N-(isopropoxycarbonyl)pyrrolidine, N-(isopropoxycarbonyl)-2,5-dimethylpyrrolidine, N-(isopropoxycarbonyl)azetidine, N-(1-ethylpropoxycarbonyl)-2,6-dimethylpiperidine, N-(1-ethylpropoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(1-ethylpropoxycarbonyl)diisopropylamine, N-(1-ethylpropoxycarbonyl)pyrrolidine, N-(1-ethylpropoxycarbonyl)-2 ,5-dimethylpyrrolidine, N-(1-ethylpropoxycarbonyl)azetidine, N-(1-propylbutoxycarbonyl)-2,6-dimethylpiperidine, N-(1-propylbutoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(1-propylbutoxycarbonyl)diisopropylamine, N-(1-propylbutoxycarbonyl)pyrrolidine, N-(1-propylbutoxycarbonyl)-2,5-dimethylpyrrolidine, N-(1-propylbutoxycarbonyl)azetidine, N-(cyclopentyloxycarbonyl)-2,6-dimethylpiperidine, N-(cyclopentyloxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(cyclopentyloxycarbonyl)diisopropylamine Propylamine, N-(cyclopentyloxycarbonyl)pyrrolidine, N-(cyclopentyloxycarbonyl)-2,5-dimethylpyrrolidine, N-(cyclopentyloxycarbonyl)azetidine, N-(cyclohexylcarbonyl)-2,6-dimethylpiperidine, N-(cyclohexylcarbonyl)-2,2,6,6-tetramethylpiperidine, N-(cyclohexylcarbonyl)diisopropylamine, N-(cyclohexylcarbonyl)pyrrolidine, N-(cyclohexylcarbonyl)-2,5-dimethylpyrrolidine, N-(cyclohexylcarbonyl)azetidine, N-(tert-butoxycarbonyl)-2,6-dimethylpiperidine, N-(tert-butoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(tert-butoxycarbonyl) diisopropylamine, N-(tert-butoxycarbonyl)pyrrolidine, N-(tert-butoxycarbonyl)-2,5-dimethylpyrrolidine, N-(tert-butoxycarbonyl)azetidine, N-(benzyloxycarbonyl)-2,6-dimethylpiperidine, N-(benzyloxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(benzyloxycarbonyl)diisopropylamine, N-(benzyloxycarbonyl)pyrrolidine, N-(benzyloxycarbonyl)-2,5-dimethylpyrrolidine, N-(benzyloxycarbonyl)azetidine, 1,4-bis(N,N'-diisopropylaminocarbonyloxy)cyclohexane, imidazole compounds described in Japanese Patent No. 5609815, and the like.

[0448] The protected amine compound of this embodiment is particularly preferably one that decomposes 100% below 200°C. This allows the base compound to be generated more efficiently, and promotes the imidization of the polyimide precursor or the cross-linking reaction between the thermal cross-linking agent and the resin. The base and other decomposition products obtained by heating the protected amine compound preferably have a boiling point of 200°C or less at 1 atmosphere (0.1 GPa). The temperature is set to be below 200°C so that the decomposition products can be volatilized from the coating film by low temperature treatment. There is no particular limit to the lower limit of the boiling point of the decomposition product at 1 atmosphere. Considering the simplicity of the synthesis of the protected amine compound, it is preferable to use one above -150°C.

[0449] When the amine compound is directly added to the photosensitive resin composition of the present invention, there is a concern that the crosslinking agent of the component (C) reacts with the amine compound at room temperature, and the viscosity of the composition increases over time, which may deteriorate the storage stability. On the other hand, if the basic amine compound is protected by a protecting group, it will not react with the component (C) at room temperature as when it is not heated, so the storage stability of the photosensitive resin composition over time can be improved. In addition, since the base is first generated when heated, it can be a catalyst for the imide ring-closing reaction and the reaction between the polymer of the component (A) and the crosslinking agent of the component (C), and can effectively promote the crosslinking reaction.

[0450] In addition, the protective amine compound can be used alone or in combination of two or more, and the amount thereof is 0 to 10 parts by mass relative to 100 parts by mass of the polymer (alkali-soluble resin) of the component (A), preferably 0.01 to 10 parts by mass, and particularly preferably 0.01 to 5 parts by mass. When the amount is 10 parts by mass or less, the alkali solubility of the composition is sufficient and the photolithography patterning properties are good.

[0451] The positive photosensitive resin composition of the present invention may further contain (G) an antioxidant. The antioxidant containing the component (G) can suppress oxidative degradation of the aliphatic group and phenolic hydroxyl group of the component (A). In addition, by utilizing the rust-proofing effect on metal materials, metal oxidation caused by external moisture, photoacid generators, thermal acid generators, etc., or the resulting decrease in adhesion and peeling can be suppressed.

[0452] Specific examples of the (G) antioxidant that can be used here include preferably hindered phenol antioxidants, phosphorus antioxidants, and sulfur antioxidants. However, it is not limited thereto. Moreover, these (G) antioxidants can be used alone or in combination of two or more.

[0453] Among the specific examples of the antioxidant (G), if hindered phenol antioxidants are further illustrated, pentaerythritol tetrakis[3-(3,5-di(tert-butyl)-4-hydroxyphenyl)propionate] (BASF Japan Co., Ltd., IRGANOX 1010 (trade name)), thiodiethylenebis[3-(3,5-di(tert-butyl)-4-hydroxyphenyl)propionate] (BASF Japan Co., Ltd., IRGANOX 1035 (trade name)), octadecyl[3-(3,5-di(tert-butyl)-4-hydroxyphenyl)propionate] (BASF Japan Co., Ltd., IRGANOX 1076 (trade name)), octyl-1-3,5-di(tert-butyl)-4-hydroxy-hydrocinnamic acid (BASF Japan Co., Ltd., IRGANOX 1135 (trade name)), 4,6-bis(octylthiomethyl o-cresol) (BASF Japan (Co., Ltd., IRGANOX 1520L), Sumilizer GA80 (Sumitomo Chemical Co., Ltd., trade name), ADK STAB AO-20 (ADEKA Co., Ltd., trade name), ADK STAB AO-30 (ADEKA Co., Ltd., trade name), ADK STAB AO-40 (ADEKA Co., Ltd., trade name), ADK STAB AO-50 (ADEKA Co., Ltd., trade name), ADK STAB AO-60 (ADEKA Co., Ltd., trade name), ADK STAB AO-80 (ADEKA Co., Ltd., trade name), ADK STAB AO-330 (ADEKA Co., Ltd., trade name), hindered phenol-based antioxidants described in International Publication No. 2017 / 188153, and the like.

[0454] Among the specific examples of the above-mentioned (G) antioxidants, further examples of phosphorus-based antioxidants include triphenyl phosphite, tri(methylphenyl)phosphite, triisooctyl phosphite, tridecyl phosphite, tri(2-ethylhexyl)phosphite, tri(nonylphenyl)phosphite, tri(octylphenyl)phosphite, tri[decylpoly(oxyethylene)phosphite, tri(cyclohexylphenyl)phosphite, tricyclohexyl phosphite, tridecylthiophosphite, triisodecylthiophosphite, phenyl-bis(2-ethylhexyl)phosphite, tris(nonylphenyl)phosphite, tris(octylphenyl)phosphite, tris[decylpoly(oxyethylene)phosphite, tris(cyclohexylphenyl)phosphite, tricyclohexyl phosphite, tridecylthiophosphite, triisodecylthiophosphite, phenyl-bis(2-ethylhexyl)phosphite, tris(2-ethylhexyl)phosphite, tris(2-ethylhexyl)phosphite, tris(2-octylphenyl)phosphite, tris[decylpoly(oxyethylene)phosphite, tris(2-ethylhexyl)phosphite, tris(2-ethylhexyl)phosphite, tris(2-octylphenyl)phosphite, tris(2-dec ... -ethylhexyl) phosphite, phenyl-diisodecyl phosphite, tetradecyl poly(oxyethylene)-bis(ethylphenyl) phosphite, phenyl-dicyclohexyl phosphite, phenyl-diisooctyl phosphite, phenyl-di(tridecyl) phosphite, diphenyl-cyclohexyl phosphite, diphenyl-isooctyl phosphite, diphenyl-2-ethylhexyl phosphite, diphenyl-isodecyl phosphite, diphenyl-cyclohexyl phenyl phosphite, diphenyl-(tridecyl) thiophosphite, and the like.

[0455] Specific examples of the above-mentioned (G) antioxidant include sulfur-based antioxidants such as ADK STABAO-412S (trade name, manufactured by ADEKA Co., Ltd.), AO-503S (trade name, manufactured by ADEKA Co., Ltd.), and Sumilizer TP-D (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

[0456] Sulfur-based antioxidants and phosphorus-based antioxidants are expected to have the effect of decomposing peroxides.

[0457] The content of the antioxidant (G) is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, relative to 100 parts by mass of the polymer of the component (A). When the content is 0.1 parts by mass or more, the adhesion to the metal material is improved and peeling is suppressed. When the content is 10 parts by mass or less, the alkali developability of the composition and the toughness of the cured film are not deteriorated.

[0458] The positive photosensitive resin composition of the present invention may further contain a silane compound (H). By containing the silane compound (H), not only the adhesion to metal materials can be improved, but also the peeling of the cured film in reliability tests such as thermal shock tests and high temperature and high humidity tests can be suppressed.

[0459] The (H) silane compound that can be used here is not particularly limited, and it is preferably one having an alkoxysilyl group. In addition, ideal specific examples are shown below. Examples include: γ-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, bis(2-hydroxyethyl)-3-aminopropyl-triethoxysilane, γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, γ-acryloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, bis(2-hydroxyethyl)-3-aminopropyl triethoxysilane, Silane, triethoxysilylpropylethylcarbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, silane compounds containing acylamino groups described in Japanese Patent No. 6414060, silane compounds containing thiourea groups described in International Publication No. 2016 / 140024 and Japanese Patent No. 5987984, silane compounds containing thiol groups described in Japanese Patent Publication No. 2017-044964, etc. However, it is not limited thereto. In addition, these (H) silane compounds can be used alone or in combination of two or more.

[0460] In addition, the content of the silane compound (H) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 3 to 6 parts by mass relative to 100 parts by mass of the polymer of the component (A). If it is 0.1 parts by mass or more, it can provide more sufficient adhesion to the substrate, and if it is 20 parts by mass or less, it can further suppress the increase in viscosity during storage at room temperature. In addition, when the content is 10 parts by mass or less, the alkali developability of the composition will not deteriorate and will not cause development residues.

[0461] The positive photosensitive resin composition of the present invention may further contain (I) a surfactant. (I) The surfactant is preferably nonionic, and examples thereof include fluorine-based surfactants, and specifically include perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkyl amine oxides, fluorinated organosiloxane compounds, and non-fluorinated organosiloxane compounds.

[0462] As these (I) surfactants, commercially available ones can be used, and examples thereof include FLUORAD FC-4430 (trade name, manufactured by Sumitomo 3M Co., Ltd.), PF-6320 (trade name, manufactured by OMNOVA Co., Ltd.), PF-636 (trade name, manufactured by OMNOVA Co., Ltd.), SURFLONS-141 and S-145 (these are trade names, manufactured by Asahi Glass Co., Ltd.), UNIDYNE DS-401, DS-4031 and DS-451 (these are trade names, manufactured by Daikin Industries, Ltd.), MEGAFACE F-8151 (trade name, manufactured by DIC Co., Ltd.), X-70-093 and KP-341 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. Among them, FLUORAD FC-4430 (trade name, manufactured by Sumitomo 3M Co., Ltd.), PF-6320 (trade name, manufactured by OMNOVA Co., Ltd.), PF-636 (trade name, manufactured by OMNOVA Co., Ltd.), and KP-341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0463] The amount of the surfactant (I) to be added is preferably 0.01 to 0.05 parts by mass based on 100 parts by mass of the polymer (A). Within this range, the coating properties on the substrate can be improved without impairing the patterning performance or the properties of the cured film.

[0464] The positive photosensitive resin composition of the present invention may further contain (J) a dissolution inhibitor. The (J) dissolution inhibitor may be a compound having a weight average molecular weight of 100 to 1,000, preferably 150 to 800, wherein the hydrogen atoms of the phenolic hydroxyl groups in the compound having two or more phenolic hydroxyl groups in the molecule are substituted by acid-labile groups at an average ratio of 0 to 100 mol %, or a compound having a carboxyl group in the molecule wherein the hydrogen atoms of the carboxyl groups are substituted by acid-labile groups at an average ratio of 50 to 100 mol %.

[0465] In addition, the substitution rate that the hydrogen atom of phenolic hydroxyl group is replaced by acid labile group, to be averaged as more than 0 mol % of the overall phenolic hydroxyl group, preferably more than 30 mol %, and its upper limit is 100 mol %, and 80 mol % is better. The substitution rate that the hydrogen atom of carboxyl is replaced by acid labile group, to be averaged as more than 50 mol % of the overall carboxyl group, preferably more than 70 mol %, and its upper limit is 100 mol %.

[0466] In this case, the compound having two or more phenolic hydroxyl groups or the compound having a carboxyl group is preferably represented by the following formulas (J1) to (J14).

[0467] [Chemistry 78]

[0468]

[0469] However, R 201 , R 202 R represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms. 203 R represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms. 204 Represents -(CH2) i1 -(i1=2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. 205 R represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. 206 R represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or a phenyl group or naphthyl group substituted with a hydroxyl group. 207 represents a hydrogen atom or a hydroxyl group. v1 is an integer of 0 to 2, and v2 is 0 or 1. w1 and h1 are 0 or 1. t1, u1, t2, u2, t3, and u3 satisfy t1+u1=8, t2+u2=5, and t3+u3=4, respectively, and are numbers such that each phenyl skeleton has at least one hydroxyl group. aa is a number such that the molecular weight of the compound of formula (J8) or (J9) is 100 to 1,000.

[0470] The amount of the dissolution inhibitor (J) to be added is more than 0 and less than 50 parts by mass, preferably 5 to 50 parts by mass, more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the polymer of the component (A). The dissolution inhibitor may be used alone or in combination of two or more. By adding the component (J), the resolution is improved. By setting the amount to less than 50 parts by mass, the film loss of the pattern does not occur and the resolution does not decrease.

[0471] [Negative photosensitive resin composition]

[0472] Among the photosensitive resin compositions using the polymer of the present invention as a base resin, a negative photosensitive resin composition that can be alkali developed will be described. The negative photosensitive resin composition of the present invention can be, for example, in the form described below, but is not limited thereto.

[0473] The negative photosensitive resin composition of the present invention contains:

[0474] (A) A polymer comprising the structural unit (1) and / or the structural unit (2) and the structural unit (3) and / or the structural unit (4)

[0475] (B') a photoacid generator,

[0476] (C) one or more crosslinking agents selected from the group consisting of amino condensates modified with formaldehyde or formaldehyde-alcohol, phenolic compounds having an average of two or more methylol groups or alkoxymethylol groups in one molecule, compounds in which hydrogen atoms of hydroxyl groups of polyphenols are substituted with glycidyl groups, compounds in which hydrogen atoms of hydroxyl groups of polyphenols or polyols are substituted with substituents represented by the following formula (C-1), and compounds containing two or more nitrogen atoms having glycidyl groups represented by the following formula (C-2), and

[0477] [Chemistry 79]

[0478]

[0479] In the formula, dotted lines represent atomic bonds, Rc is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.

[0480] (D) Solvent.

[0481] The component (A) of the negative photosensitive resin composition is a polymer containing the structural unit (1) and / or the structural unit (2) and the structural unit (3) and / or the structural unit (4). The amount of the component (A) added is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, and even more preferably 10 to 30 parts by weight, relative to 100 parts by weight of the total amount of the composition. In addition, one kind of the component (A) may be used or two or more kinds may be used in combination.

[0482] The negative photosensitive resin composition can be made into a negative photosensitive resin composition by using the acid generated from the component (B') as a catalyst to crosslink the crosslinking group of the component (C) with the polymer of the component (A).

[0483] The (B') component of the negative photosensitive resin composition is a photoacid generator. The (B') photoacid generator contained in the negative photosensitive resin composition of the present invention is not particularly limited, and can be a photoacid generator that generates acid by irradiation with a wavelength of 190 to 500 nm, and the acid acts as a curing catalyst. Examples thereof include: onium salts, diazomethane derivatives, glyoxal dioxime derivatives, oxime sulfonate derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonate derivatives, imidosulfonate derivatives, iminosulfonate derivatives, triazine derivatives, etc. They are described in detail below, and they can be used alone or in combination of two or more.

[0484] Examples of the onium salt include compounds represented by the following general formula (51).

[0485] (R6) j M + K - (51)

[0486] In the formula, R6 may be a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, which may also have a substituent. + is an iodonium ion or a sulfonium ion, K - It is a non-nucleophilic relative ion, and j is 2 or 3.

[0487] In the above R6, examples of the linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, cyclohexyl, 2-oxocyclohexyl, norbornyl, and adamantyl. Examples of the aryl group having 6 to 12 carbon atoms include phenyl; alkoxyphenyl groups such as o-, m-, or p-methoxyphenyl, ethoxyphenyl, and m- or p-tert-butyloxyphenyl; and alkylphenyl groups such as 2-, 3-, or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl. Examples of the aralkyl group having 7 to 12 carbon atoms include various groups such as benzyl and phenethyl.

[0488] K - Examples of the non-nucleophilic counter ions include halide ions such as chloride ion and bromide ion; fluoroalkyl sulfonates such as trifluoromethanesulfonate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; aryl sulfonates such as toluenesulfonate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; alkyl sulfonates such as methanesulfonate and butanesulfonate, and the like.

[0489] Examples of the diazomethane derivative include compounds represented by the following general formula (52).

[0490] [Chemistry 80]

[0491]

[0492] In the formula, R7 may be the same or different and represent a linear, branched or cyclic alkyl group or a halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or a halogenated aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

[0493] In the above R7, examples of the linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Examples of the linear, branched, or cyclic halogenated alkyl group having 1 to 12 carbon atoms include trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, and nonafluorobutyl. Examples of the aryl group having 6 to 12 carbon atoms include phenyl; alkoxyphenyl groups such as o-, m-, or p-methoxyphenyl, ethoxyphenyl, and m- or p-tert-butyloxyphenyl; and alkylphenyl groups such as 2-, 3-, or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl. Examples of the halogenated aryl group having 6 to 12 carbon atoms include fluorophenyl, chlorophenyl, and 1,2,3,4,5-pentafluorophenyl. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl and phenethyl.

[0494] Specific examples of such photoacid generators include diphenyl iodine trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyl iodine trifluoromethanesulfonate, diphenyl iodine p-toluenesulfonate, (p-tert-butoxyphenyl)phenyl iodine p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, sulfonium, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tri(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, onium salts such as dicyclohexylphenylsulfonium benzenesulfonate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate; bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis( Diazomethane derivatives such as bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, and 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane;Bis-o-(p-toluenesulfonyl)-α-dimethylglyoxal dioxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxal dioxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxal dioxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxal dioxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glyoxal dioxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxal dioxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxal dioxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxal dioxime, bis-o-(n-butanesulfonyl)-2,3 -pentanedione glyoxal dioxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxal dioxime, bis-o-(methanesulfonyl)-α-dimethylglyoxal dioxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxal dioxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxal dioxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxal dioxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxal dioxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxal dioxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxal dioxime, bis- Glyoxal dioxime derivatives such as o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxal dioxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxal dioxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxal dioxime, and bis-o-(camphorsulfonyl)-α-dimethylglyoxal dioxime; oxime sulfonate derivatives such as α-(phenylsulfonyloxyimino)-4-methylphenylacetonitrile; β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane; disulfone derivatives such as diphenyl disulfone and dicyclohexyl disulfone; 2,6-dinitrobenzyl p-toluenesulfonate , nitrobenzyl sulfonate derivatives such as 2,4-dinitrobenzyl p-toluenesulfonate; sulfonate derivatives such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3-tris(p-toluenesulfonyloxy)benzene; phthalimido trifluoromethanesulfonate, phthalimido toluenesulfonate, 5-norbornene-2,3-dicarboxyimido trifluoromethanesulfonate, 5-norbornene-2,3-dicarboxyimido toluenesulfonate, 5-norbornene-2,3-dicarboxyimido n-butylsulfonate, n-trifluoromethylsulfonyloxynaphthyl imide and other imide sulfonate derivatives;Imidosulfonate derivatives such as (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophene-2-ylidene)-(2-methylphenyl)-acetonitrile, and 2-methyl-2[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane. Among them, imidosulfonate derivatives, iminosulfonate derivatives, oximesulfonate derivatives, etc. can be preferably used. The above-mentioned photoacid generator can be used alone or in combination. ;

[0495] The amount of the photoacid generator of the above-mentioned component (B') is preferably 0.05 to 20 parts by mass, and particularly preferably 0.2 to 5 parts by mass, relative to 100 parts by mass of component (A) in the negative photosensitive resin composition of the present invention, taking into account the light absorption of the photoacid generator itself and the photocurability of the thick film.

[0496] As the component (C) of the negative photosensitive resin composition of the present invention, the same crosslinking agent as the component (C) explained in the second embodiment of the positive photosensitive resin composition can be preferably used.

[0497] As described above, the component (C) of the negative photosensitive resin composition of the present invention is a component that forms a negative pattern by crosslinking the crosslinking groups of the component (C) with the polymer of the component (A) using the acid generated from the component (B') as a catalyst. After the pattern is formed, a crosslinking reaction is induced during post-curing to further improve the strength of the cured product. The weight average molecular weight of the component (C) is preferably 150 to 10,000, and particularly preferably 200 to 3,000, from the viewpoint of light curing and heat resistance.

[0498] The amount of the component (C) in the negative photosensitive resin composition of the present invention is preferably 0.5 to 50 parts by mass, particularly preferably 1 to 30 parts by mass, based on 100 parts by mass of the component (A).

[0499] As the solvent of the component (D), the solvents exemplified in the above-mentioned positive photosensitive resin composition can be preferably used.

[0500] The amount of the component (D) is preferably 50 to 2,000 parts by mass, particularly preferably 100 to 1,000 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (B′).

[0501] In the negative photosensitive resin composition of the present invention, in addition to the components (A), (B'), (C), and (D), a basic compound may be added as the component (K) as needed. The basic compound is preferably a compound that can inhibit the diffusion rate of the acid generated from the photoacid generator when it diffuses in the resist film. In addition, by adding the above-mentioned basic compound, the resolution can be improved, the sensitivity change after exposure can be suppressed, the substrate and environmental dependence can be reduced, and the exposure latitude and pattern shape can be improved.

[0502] The above-mentioned basic compounds can be listed as: ammonia, primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, and compounds represented by the following general formula (53), etc.

[0503] N(α) q (β) 3-q (53)

[0504] In the formula, q=1, 2, or 3. The side chains α may be identical or different and may be any substituent represented by the following general formulae (54) to (56). The side chains β may be identical or different and may represent a hydrogen atom, or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and may also contain an ether bond or a hydroxyl group. In addition, the side chains α may be bonded to each other to form a ring.

[0505] [Chemistry 81]

[0506]

[0507] Here, R 300 , R 302 , R 305 is a linear or branched alkylene group having 1 to 4 carbon atoms, R 301 , R 304 It is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain one or more hydroxyl groups, ether bonds, ester bonds or lactone rings. 303 is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, R 306 It is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms and may contain one or more hydroxyl groups, ether bonds, ester bonds or lactone rings. In addition, * indicates a bonding terminal.

[0508] Examples of the primary aliphatic amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, methylenediamine, ethylenediamine, and tetraethylenepentamine.

[0509] Examples of the secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di(sec-butyl)amine, diamylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, didhexadecylamine, N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, and N,N-dimethyltetraethylenepentamine.

[0510] Examples of tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri(sec-butyl)amine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tri(dodecyl)amine, tri(hexadecyl)amine, N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyltetraethylenepentamine, etc.

[0511] Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine.

[0512] Examples of aromatic amines and heterocyclic amines include aniline derivatives (e.g., aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, etc.), diphenyl(p-tolyl)amine, methyldiphenylamine, Phenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (e.g., oxazole, isoxazole, etc.), thiazole derivatives (e.g., thiazole, isothiazole, etc.), imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazolidone derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl 1-butylpentyl)pyridine, methylpyridine, methylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinylpyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoleline derivatives, quinoline derivatives (e.g., quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, phenanthroline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, etc.

[0513] Examples of the nitrogen-containing compound having a carboxyl group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (e.g., nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.), and the like.

[0514] Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid and pyridine p-toluenesulfonate.

[0515] Examples of nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-( [2-hydroxyethoxy)ethyl] piperazine, piperidineethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidone, 3-piperidinyl-1,2-propanediol, 3-pyrrolidinyl-1,2-propanediol, 8-hydroxyjulolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N-(2-hydroxyethyl)phthalimide, N-(2-hydroxyethyl)isonicotinamide, etc.

[0516] Examples of the amide derivatives include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, etc. Examples of the imide derivatives include phthalimide, succinimide, maleimide, etc.

[0517] Examples of the compound represented by the general formula (53) include tris[2-(methoxymethoxy)ethyl]amine, tris[2-(2-methoxyethoxy)ethyl]amine, tris[2-(2-methoxyethoxymethoxy)ethyl]amine, tris[2-(1-methoxyethoxy)ethyl]amine, tris[2-(1-ethoxyethoxy)ethyl]amine, tris[2-(1-ethoxypropoxy)ethyl]amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane, 1,4,10,13- Tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris(2-formyloxyethyl)amine, tris(2-acetoxyethyl)amine, tris(2-propionyloxyethyl)amine, tris(2-butyryloxyethyl)amine, tris(2-isobutyryloxyethyl)amine, tris(2-pentanoyloxyethyl)amine, tris(2-trimethylacetyloxyethyl)amine, N,N-bis(2-acetoxyethyl)2-(acetoxyacetoxy)ethylamine, tris(2-methoxycarbonyloxyethyl)amine, tris(2-tert-butoxycarbonyloxyethyl)amine, tris[2-(2-oxopropoxy)ethyl]amine, tris[2-(methoxycarbonylmethyl)oxyethyl ]amine, tris[2-(tert-butoxycarbonylmethyloxy)ethyl]amine, tris[2-(cyclohexyloxycarbonylmethyloxy)ethyl]amine, tris(2-methoxycarbonylethyl)amine, tris(2-ethoxycarbonylethyl)amine, N,N-bis(2-hydroxyethyl)2-(methoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)2-(methoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)2-(ethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)2-(ethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2 -hydroxyethyl) 2-(2-hydroxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl) 2-(2-acetoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl) 2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl) 2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl) 2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl) 2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl) 2-(tetrahydrofuranylmethyloxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl) 2-(tetrahydrofuranylmethyloxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl)2-(4-hydroxybutoxycarbonyl)ethylamine, N,N-bis(2-formyloxyethyl)2-(4-formyloxybutoxycarbonyl)ethylamine, N,N-bis(2-formyloxyethyl)2-(4-formyloxybutoxycarbonyl)ethylamine, 2-(methoxycarbonyl)ethylamine, N,N-bis(2-methoxyethyl)2-(methoxycarbonyl)ethylamine, N-(2-hydroxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-hydroxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(3-hydroxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(3-acetoxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-methoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-butylbis[2-(methoxycarbonyl)ethyl]amine, N-butylbis[2-(2-methoxyethoxycarbonyl)ethyl]amine, N-methylbis(2-acetoxyethyl)amine, N-ethylbis (2-acetoxyethyl) amine, N-methylbis(2-trimethylacetyloxyethyl) amine, N-ethylbis[2-(methoxycarbonyloxy)ethyl] amine, N-ethylbis[2-(tert-butoxycarbonyloxy)ethyl] amine, tris(methoxycarbonylmethyl) amine, tris(ethoxycarbonylmethyl) amine, N-butylbis(methoxycarbonylmethyl) amine, N-hexylbis(methoxycarbonylmethyl) amine, β-(diethylamino)-δ-valerolactone, but not limited thereto. ,

[0518] The above-mentioned basic compounds may be used alone or in combination of two or more.

[0519] The amount of the basic compound blended in the negative photosensitive resin composition of the present invention is preferably 0 to 3 parts by mass, particularly preferably 0.01 to 1 part by mass, based on 100 parts by mass of the component (A), from the viewpoint of sensitivity.

[0520] The negative photosensitive resin composition of the present invention may further contain other components other than the components (A), (B'), (C), (D) and (K). The other components may contain one or more selected from (E) a thermal acid generator, (F) a protective amine compound, (G) an antioxidant, (H) a silane compound, (I) a surfactant, (J) a dissolution inhibitor, etc., and preferably, the same examples as those described in the positive photosensitive resin composition can be used.

[0521] (Pattern Formation Method)

[0522] Next, a pattern forming method using the positive photosensitive resin composition and the negative photosensitive resin composition of the present invention will be described.

[0523] The present invention provides a pattern forming method, comprising the following steps:

[0524] (1) coating the positive photosensitive resin composition on a substrate to form a photosensitive material film,

[0525] (2) heating the photosensitive material film;

[0526] (3) exposing the photosensitive material film to high-energy radiation or electron beams with a wavelength of 190 to 500 nm through a photomask, and

[0527] (4) Development is performed using an alkaline aqueous solution developer.

[0528] Furthermore, the present invention provides a pattern forming method, comprising the following steps:

[0529] (I) coating the negative photosensitive resin composition on a substrate to form a photosensitive material film,

[0530] (II) heating the photosensitive material film,

[0531] (III) exposing the photosensitive material film to high energy radiation or electron beam with a wavelength of 190 to 500 nm through a photomask, and

[0532] (IV) After the irradiation, the substrate subjected to the heat treatment is developed using a developer of an alkaline aqueous solution.

[0533] Regardless of whether it is the positive photosensitive resin composition or the negative photosensitive resin composition of the present invention, the pattern formation can be implemented by using known photolithography technology. For example, the photosensitive resin composition is applied to a silicon wafer or a SiO2 substrate, a SiN substrate, or a substrate having a pattern of copper wiring, etc. by a spin coating method (spin coating method), and pre-baked at about 80 to 130°C for 50 to 600 seconds to form a photosensitive material film with a thickness of 1 to 50 μm, preferably 1 to 30 μm, and more preferably 5 to 20 μm.

[0534] The spin coating method can be applied to the substrate by dispensing about 5 mL of the photosensitive resin composition onto the silicon substrate and then rotating the substrate. At this time, the thickness of the photosensitive material film on the substrate can be easily adjusted by adjusting the rotation speed. Afterwards, the residual solvent can be removed by pre-baking.

[0535] Then, a mask for forming a target pattern is placed on the photosensitive material film, and high-energy rays such as i-rays and g-rays with a wavelength of 190 to 500 nm or electron beams are exposed to the photosensitive material at an exposure dose of about 1 to 5,000 mJ / cm 2 It is preferably about 100 to 2,000 mJ / cm 2 way of irradiation.

[0536] Then, if necessary, a post-exposure heat treatment (post-exposure bake (PEB)) may be performed on a hot plate at 60-150° C. for 1-10 minutes, preferably 80-120° C. for 1-5 minutes, between the exposure step and the development step.

[0537] The positive photosensitive resin composition and the negative photosensitive resin composition of the present invention can be developed using an alkali aqueous solution.

[0538] On the other hand, an ideal alkaline aqueous solution that can be used for alkali development is a 2.38% tetramethylammonium hydroxyl (TMAH) aqueous solution. Development can be carried out by conventional methods such as spraying, dipping, etc., or by immersion in a developer. Thereafter, cleaning, rinsing, drying, etc. can be carried out as needed to obtain a resist film having a desired pattern.

[0539] (Method for forming hardened film)

[0540] Furthermore, the present invention provides a method for forming a hardened film, comprising the following steps:

[0541] The patterned film obtained by the above-mentioned pattern forming method is heated at a temperature of 100 to 300° C. and post-cured.

[0542] The patterned film obtained by the above-mentioned pattern forming method is heated and post-cured at a temperature of 100 to 300° C., preferably 150 to 300° C., and more preferably 180 to 250° C. using an oven, a hot plate, etc. to form a hardened film. If the post-curing temperature is 100 to 300° C., the cross-linking density of the film of the photosensitive resin composition can be increased, and the remaining volatile components can be removed, which is more ideal from the perspective of adhesion to the substrate, heat resistance, strength, and electrical properties. In addition, the post-curing time can be set to 10 minutes to 10 hours.

[0543] The patterns formed as described above are used to form protective films covering wiring, circuits, substrates, etc. The patterns and protective films formed by them not only have excellent insulation properties, but also exhibit excellent adhesion to metal layers such as Cu in the covered wiring and circuits, metal electrodes on the substrate, or insulating substrates such as SiN in the covered wiring and circuits. They also have suitable mechanical strength as a protective film and can greatly improve the resolution capability for forming fine patterns.

[0544] (hardened film)

[0545] The cured film obtained in this manner has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength and chemical resistance to alkaline stripping solutions, and the reliability of semiconductor elements using it as a protective film is also excellent. In particular, it can prevent the occurrence of cracks during temperature cycle tests and can be ideally used as a protective film (interlayer insulating film or surface protective film) for electrical and electronic parts, semiconductor elements, etc.

[0546] That is, the present invention provides an interlayer insulating film or a surface protective film composed of a cured film formed by curing the positive photosensitive resin composition or the negative photosensitive resin composition.

[0547] The protective film is effective for applications such as insulating films for semiconductor elements including redistribution applications, insulating films for multilayer printed circuit boards, solder resist masks, and cover films due to its heat resistance, chemical resistance, and insulating properties.

[0548] Furthermore, the present invention provides an electronic component having the above interlayer insulating film or the above surface protective film.

[0549] Such electronic components have excellent reliability because they have a protective film (interlayer insulating film or surface protective film) having heat resistance, chemical resistance, and insulating properties.

[0550] Example

[0551] Hereinafter, the present invention will be specifically described with reference to synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples.

[0552] I. Synthesis of polymers

[0553] In the following synthesis examples, the chemical structural formulas and names of the compounds used are shown below.

[0554] [Chemistry 82]

[0555]

[0556] [Chemistry 83]

[0557]

[0558] DA-1: 4-(4-aminophenoxy)-3-methylaniline

[0559] DA-2: 2-phenyl-4,4'-diaminodiphenyl ether

[0560] DA-3: 4-(4-aminophenoxy)-3-(trifluoromethyl)aniline

[0561] DA-4: 4-((4-aminophenyl)thio)-3-phenylaniline

[0562] DA-5: (4-amino-2-(phenyl)phenyl)(4-aminophenyl)methanone

[0563] DA-6: 4-((4-aminophenyl)methyl)-3-phenylaniline

[0564] 6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0565] BPS: Bis(3-amino-4-hydroxyphenyl)sulfone

[0566] BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane

[0567] BAHF: 9,9-bis(3-amino-4-hydroxyphenyl)fluorene

[0568] ODA: 4,4'-diaminodiphenyl ether

[0569] APB: 1,3-bis(3-aminophenoxy)benzene

[0570] s-ODPA: 3,3',4,4'-oxydiphthalic anhydride

[0571] s-BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

[0572] DC-1: Sebacoyl dichloride

[0573] PAP: 4-aminophenol

[0574] D-400 and RT-1000 are diamines manufactured by HUNTSMAN Co., Ltd.

[0575] [Synthesis Example 1] Synthesis of polyimide resin (A-1)

[0576] In a 1L flask equipped with a stirrer and a thermometer, 2.1g (9.6mmol) of (DA-1), 30.0g (81.9mmol) of (6FAP), 1.0g (9.6mmol) of (PAP), and 132g of N-methyl-2-pyrrolidone were added, and dissolved by stirring at room temperature. Then, a solution prepared by dissolving 29.9g (96.4mmol) of (s-ODPA) in 269g of N-methyl-2-pyrrolidone was added dropwise at room temperature, and after the addition was completed, the mixture was stirred at room temperature for 1 hour. Thereafter, 20g of xylene was added to the reaction solution, and the mixture was heated and refluxed at 170°C for 3 hours while the generated water was discharged to the outside of the system. After cooling to room temperature, the reaction solution was added dropwise to 2L of ultrapure water under stirring, and the precipitate was filtered and washed with water appropriately, and then dried under reduced pressure at 40°C for 48 hours to obtain a polyimide resin (A-1). The molecular weight of the polymer was measured by GPC and found to be a weight average molecular weight of 34,000 in terms of polystyrene.

[0577] [Synthesis Example 11] Synthesis of polyamide-imide resin (A-11)

[0578] In a 1L flask equipped with a stirrer and a thermometer, 2.1g (9.6mmol) of (DA-1), 30.0g (81.9mmol) of (6FAP), 1.0g (9.6mmol) of (PAP), and 132g of N-methyl-2-pyrrolidone were added and dissolved by stirring at room temperature. Then, a solution prepared by dissolving 23.9g (77.1mmol) of (s-ODPA) in 215g of N-methyl-2-pyrrolidone at room temperature was added dropwise and stirred at room temperature for 1 hour. Thereafter, 20g of xylene was added to the reaction solution, and the solution was heated under reflux at 170°C for 3 hours while removing the generated water from the system. After cooling to room temperature, 3.1g (38.6mmol) of pyridine was added, and 4.6g (19.3mmol) of (DC-1) was added dropwise while maintaining the solution at 20°C or below. After the addition was completed, the reaction solution was added dropwise to 2 L of ultrapure water under stirring, and the precipitate was filtered and washed with water appropriately, and then dried under reduced pressure at 40° C. for 48 hours to obtain a polyamide-imide resin (A-11). The molecular weight of the polymer was measured by GPC, and the weight average molecular weight was 33,000 in terms of polystyrene.

[0579] [Synthesis Example 17] Synthesis of polyamide resin (A-17)

[0580] In a 1L flask equipped with a stirrer and a thermometer, 2.7g (9.6mmol) of (DA-2), 30.0g (81.9mmol) of (6FAP), 1.0g (9.6mmol) of (PAP), and 135g of N-methyl-2-pyrrolidone were added and dissolved by stirring at room temperature. Then, 15.3g (192.8mmol) of pyridine was added, and 23.1g (96.4mmol) of (DC-1) was added dropwise while maintaining the mixture at 20°C or below. After the addition was completed, the reaction solution was added dropwise to 2L of ultrapure water under stirring, and the precipitate was filtered and washed with water appropriately, and then dried under reduced pressure at 40°C for 48 hours to obtain a polyamide resin (A-17). When the molecular weight of the polymer was measured by GPC, it was a weight average molecular weight of 38,000 in terms of polystyrene.

[0581] [Synthesis Example 18] Synthesis of Tetracarboxylic Acid Diester Compound (X-1)

[0582] In a 3L flask equipped with a stirrer and a thermometer, 100g (322mmol) of (s-ODPA), 65.2g (644mmol) of triethylamine, 39.3g (322mmol) of N,N-dimethyl-4-aminopyridine, and 400g of γ-butyrolactone were added, and 83.8g (644mmol) of hydroxyethyl methacrylate (HEMA) was added dropwise while stirring at room temperature, and then stirred at room temperature for 24 hours. Thereafter, 370g of a 10% aqueous hydrochloric acid solution was added dropwise under ice cooling to stop the reaction. 800g of 4-methyl-2-pentanone was added to the reaction solution, and the organic layer was separated and extracted, and then washed 6 times with 600g of water. The solvent of the obtained organic layer was distilled off to obtain 180g of a tetracarboxylic acid diester compound (X-1).

[0583] [Synthesis Example 19] Synthesis of polyimide precursor (A-18)

[0584] In a 1 L flask equipped with a stirrer and a thermometer, 44.0 g (77.1 mmol) of (X-1) and 176 g of N-methyl-2-pyrrolidone were added and dissolved by stirring at room temperature. Then, 18.8 g (158.1 mmol) of thionyl chloride was added dropwise under ice cooling so as to keep the temperature of the reaction solution at 10°C or lower. After the addition, the mixture was stirred for 2 hours under ice cooling. Then, 4.6 g (19.3 mmol) of (DC-1) was added, and then, under ice cooling, a solution in which 2.7 g (9.6 mmol) of (DA-2), 30.0 g (81.9 mmol) of (6FAP), 1.0 g (9.6 mmol) of (PAP), and 15.3 g (192.8 mmol) of pyridine were dissolved in 135 g of N-methyl-2-pyrrolidone was added dropwise so as to keep the temperature of the reaction solution at 10°C or lower. After the addition was completed, the temperature was returned to room temperature, and the reaction solution was added dropwise to 3 L of water under stirring. The precipitate was filtered and washed with water appropriately, and then dried under reduced pressure at 40° C. for 48 hours to obtain a polyimide precursor (A-18). The molecular weight of the polymer was measured by GPC, and the weight average molecular weight was 35,000 in terms of polystyrene.

[0585] [Synthesis Example 2] to [Synthesis Example 10], [Synthesis Example 12] to [Synthesis Example 16], [Comparative Synthesis Examples 1 and 2] Synthesis of polyimide resins or polyamide-imide resins (A-2) to (A-10), (A-12) to (A-16), (A-19), (A-20)

[0586] The diamine compound, the monoamine compound, the tetracarboxylic dianhydride, and the dicarboxylic acid dichloride were used in the same weight as shown in Table 1 below. In the case of polyimide resin, the same formulation as in Synthesis Example 1 was used. In the case of polyamide-imide resin, the same formulation as in Synthesis Example 11 was used to obtain resins (A-2) to (A-10), (A-12) to (A-16), (A-19), and (A-20). The molecular weight of each polymer was measured by GPC, and the weight average molecular weight calculated in terms of polystyrene is shown in Table 1 below.

[0587] In addition, (A-19) and (A-20) obtained in Comparative Synthesis Examples 1 and 2 do not contain the structural units represented by the above-mentioned general formulae (1) and (2) which are essential in the present invention.

[0588] [Table 1]

[0589]

[0590]

[0591] II. Preparation of Photosensitive Resin Composition

[0592] The polymers synthesized in the above-mentioned Synthesis Examples 1 to 19 and Comparative Synthesis Examples 1 and 2 were used as base resins, and a resin composition with a resin conversion of 20% by mass was prepared with the composition and blending amount described in Tables 2 and 3. Thereafter, after stirring, mixing, and dissolving, precision filtration was performed using a 0.5 μm filter made of Teflon (registered trademark) to obtain a photosensitive resin composition. In the table, PGMEA of the solvent represents propylene glycol monomethyl ether acetate, and GBL represents γ-butyrolactone.

[0593] [Table 2]

[0594]

[0595]

[0596] Photosensitive resin compositions 1 to 20 shown in Table 2 are positive photosensitive resin compositions of the present invention. Comparative photosensitive resin compositions 1 and 2 are positive photosensitive resin compositions of the present invention, except that the polymer of the present invention is replaced with the polymer synthesized in Comparative Synthesis Examples 1 and 2 as the base resin.

[0597] [Table 3]

[0598]

[0599] Photosensitive resin compositions 21 to 38 shown in Table 3 are negative photosensitive resin compositions of the present invention. Comparative photosensitive resin compositions 3 and 4 are negative photosensitive resin compositions of the present invention, except that the polymer of the present invention is replaced with the polymer synthesized in Comparative Synthesis Examples 1 and 2 as the base resin.

[0600] In addition, in Tables 2 and 3, the detailed descriptions of the diazoquinone compound photosensitizer (PAC-1), photoacid generator (PAG-1), crosslinking agents (CL-1) to (CL-3), thermal acid generator (E-1), protective amine compound (F-1), antioxidant (G-1), silane compound (H-1), surfactant (I-1), dissolution inhibitor (J-1), and basic compound (K-1) are as follows. In addition, parts by weight and parts by mass have the same meaning.

[0601] Photosensitive agent (PAC-1)

[0602] [Chemistry 84]

[0603]

[0604] In the formula, Q represents a 1,2-diazonaphthoquinonesulfonyl group represented by the following formula (57) or a hydrogen atom, and 90% of Q is substituted by a 1,2-diazonaphthoquinonesulfonyl group represented by the following formula (57).

[0605] [Chemistry 85]

[0606]

[0607] Photoacid generator (PAG-1)

[0608] [Chemistry 86]

[0609]

[0610] Crosslinking agent (CL-1)

[0611] [Chemistry 87]

[0612]

[0613] Crosslinking agent (CL-2)

[0614] Epoxy resin: EP4000L crosslinking agent (CL-3) manufactured by ADEKA Co., Ltd.

[0615] [Chemistry 88]

[0616]

[0617] Thermal Acid Generator (E-1)

[0618] [Chemistry 89]

[0619]

[0620] Protected amine compound (F-1)

[0621] [Chemistry 90]

[0622]

[0623] Antioxidant (G-1)

[0624] Hindered phenol antioxidant: Sumilizer GA-80 silane compound (H-1) manufactured by Sumitomo Chemical Co., Ltd.

[0625] Aminosilane coupling agent: KBM-573 surfactant (I-1) manufactured by Shin-Etsu Chemical Co., Ltd.

[0626] Fluorine-based surfactant: PF-6320 dissolution inhibitor (J-1) manufactured by OMNOVA

[0627] [Chemistry 91]

[0628]

[0629] Basic compound (K-1)

[0630] [Chemistry 92]

[0631]

[0632] III. Pattern Formation

[0633] 5 mL of the above-mentioned photosensitive resin compositions 1 to 38 and comparative photosensitive resin compositions 1 to 4 were dispensed onto a silicon substrate and then the substrate was rotated, i.e., the coating was performed by spin coating so that the film thickness after the post-curing heating after pattern formation was 5 μm. That is, the reduction in film thickness after the post-curing step was studied in advance, and the rotation speed during coating was adjusted so that the film thickness after post-curing was 5 μm.

[0634] Then, pre-bake at 100°C for 2 minutes on a hot plate. Then, i-ray exposure and pattern formation are performed using an i-ray stepper NSR-2205i11 manufactured by Nikon. When forming the pattern, masks for positive and negative patterns are used in combination with the photosensitive resin composition used. The mask has a pattern of 20μm holes arranged in a 1:1 ratio vertically and horizontally, and can form a hole pattern with a scale of 10μm from 50μm to 20μm, a scale of 5μm from 20μm to 10μm, and a scale of 1μm from 10μm to 1μm.

[0635] Then, the heating step was carried out under the conditions shown in Table 5 below.

[0636] In the development step, an alkali aqueous solution was used as a developer, and a 2.38% tetramethylammonium hydroxide aqueous solution was used as a developer. After immersion development with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution was performed three times for 1 minute, rinsed with ultrapure water.

[0637] Then, the obtained pattern on the substrate was post-cured in an oven at 200° C. for 2 hours while purging with nitrogen.

[0638] Then, each substrate was cut in such a way that the shape of the obtained hole pattern could be observed, and the hole pattern shape was observed using a scanning electron microscope (SEM). The diameter of the minimum opening hole when the film thickness after post-curing was 5 μm was obtained, and the shape of the pattern was evaluated. These results and the sensitivity that can form the minimum pattern are combined and shown in Tables 4 and 5.

[0639] In addition, the pattern shape of the holes was evaluated based on the following criteria, and the evaluation results are shown in Tables 4 and 5.

[0640] Good: The hole is observed to be rectangular or tapered (the upper part of the hole is larger than the bottom part)

[0641] Bad: Reverse taper (a shape where the size of the upper part of the hole is smaller than the size of the bottom), overhang shape (a shape where the upper part of the hole has an overhang), significant film loss, or residue is observed at the bottom of the hole

[0642] IV. Elongation at break, breaking strength

[0643] The photosensitive resin compositions 1 to 38 and comparative photosensitive resin compositions 1 to 4 were spin-coated on an aluminum substrate to a film thickness of 10 μm after curing, and then pre-baked on a hot plate at 100° C. for 3 minutes to obtain a photosensitive resin film.

[0644] Afterwards, an oven was used to cure the film at 200°C while purging with nitrogen for 2 hours to obtain a photosensitive resin cured film. Then, the wafer with the cured film was cut into strips of 10 mm wide and 60 mm long, and immersed in 20% by mass hydrochloric acid to peel the cured film from the substrate. The obtained cured film was subjected to the determination of elongation at break and fracture strength using a universal testing machine (AUTOGRAPH) AGX-1KN manufactured by Shimadzu Corporation. The measurement was performed 10 times for each sample, and the average values ​​are shown in Tables 4 and 5.

[0645] First, Table 4 shows the results of patterning using positive photosensitive resin compositions (photosensitive resin compositions 1 to 20, comparative photosensitive resin compositions 1 and 2) and the elongation at break and the strength at break of the cured films.

[0646] [Table 4]

[0647]

[0648]

[0649] As shown in Table 4, the positive photosensitive resin composition of the present invention exhibits a good pattern shape in alkaline aqueous solution development, and the minimum hole size is less than 5 μm relative to the finished film thickness of 5 μm, so an aspect ratio of 1 or more can be achieved.

[0650] Furthermore, the positive photosensitive composition of the present invention can obtain a cured film having good mechanical properties even when cured at a low temperature of 200° C. or lower.

[0651] On the other hand, when comparing Examples 1 to 2 of the compositions not containing the crosslinking agent of the component (C) with Comparative Example 1, the compositions using the comparative photosensitive resin composition 1 have the same pattern shape and minimum pore size as the composition of the present invention, but in terms of mechanical properties, the elongation at break and the breaking strength are inferior to those of the cured film obtained from the composition of the present invention. Similarly, when comparing Examples 3 to 20 of the compositions containing the crosslinking agent of the component (C) with Comparative Example 2, the compositions using the comparative photosensitive resin composition 2 have the same pattern shape and minimum pore size as the composition of the present invention, but in terms of mechanical properties, the elongation at break and the breaking strength are inferior to those of the cured film obtained from the composition of the present invention.

[0652] Then, Table 5 shows the results of patterning using the negative photosensitive resin composition (photosensitive resin compositions 21 to 38, comparative photosensitive resin compositions 3 and 4) and the elongation at break and the breaking strength of the cured film.

[0653] [Table 5]

[0654]

[0655]

[0656] As shown in Table 5, the negative photosensitive resin composition of the present invention exhibits a good pattern shape in alkaline aqueous solution development, and the minimum hole size exhibits a smaller value than the finished film thickness of 5 μm, so an aspect ratio of 1 or more can be achieved.

[0657] Furthermore, the negative photosensitive composition of the present invention can obtain a cured film having good mechanical properties even when cured at a low temperature of 200° C. or lower.

[0658] On the other hand, the cured films using comparative photosensitive resin composition 3 and comparative photosensitive resin composition 4 had the same pattern shape and minimum hole size as the composition of the present invention, but were inferior in terms of mechanical properties in terms of elongation at break and strength at break.

[0659] This specification includes the following inventions.

[0660] [1] A polymer characterized by comprising a structural unit represented by the following general formula (1) and / or (2) and a structural unit represented by the following general formula (3) and / or (4).

[0661] [Chemistry 93]

[0662]

[0663] In the formula, X1 is a tetravalent organic group, R1 to R4 are monovalent organic groups having 1 to 15 carbon atoms which may be different or the same and may also contain heteroatoms, or hydrogen atoms, and at least one of them is a monovalent organic group having 1 to 15 carbon atoms which may also contain heteroatoms, and L is a divalent organic group or a divalent atom excluding a -OC(=O)- bond or a -C(=O)-O- bond.

[0664] [Chemistry 94]

[0665]

[0666] In the formula, X2 is a divalent organic group, and R1 to R4 and L are the same as described above.

[0667] [Chemistry 95]

[0668]

[0669] In the formula, X3 is a tetravalent organic group which is the same as or different from the aforementioned X1, s is 0 or 1, Z is a divalent bonding group, and when s=0, the two aromatic rings in the formula are directly bonded without a bonding group in between.

[0670] [Chemistry 96]

[0671]

[0672] In the formula, X4 is a divalent organic group which is the same as or different from the above X2, and s and Z are the same as described above.

[0673] [2]: A polymer as described in [1] above, wherein in the general formulae (1) and (2), either of R1 and R2 is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom, and the other is a hydrogen atom, and R3 and R4 are hydrogen atoms.

[0674] [3]: The polymer according to [1] or [2], wherein in the general formula (1) and (2), one of R1 and R2 is an aromatic group having 6 to 12 carbon atoms, and the other is a hydrogen atom.

[0675] [4]: A polymer as described in any one of [1] to [3] above, wherein the L in the general formula (1) and (2) is at least one selected from any one of an oxygen atom, a sulfur atom, a carbonyl group, a linear alkylene group having 1 to 15 carbon atoms, and a branched alkylene group having 3 to 15 carbon atoms.

[0676] [5]: A polymer as described in any one of [1] to [4] above, wherein the Z in the general formulae (3) and (4) is at least one bonding group selected from any one of the groups represented by the following formulae (5), (6), (7) and (8).

[0677] [Chemistry 97]

[0678]

[0679] In the formula, dotted lines represent atomic bonds.

[0680] [6]: A positive photosensitive resin composition comprising:

[0681] (A) the polymer according to any one of [1] to [5] above,

[0682] (B) is a photosensitizer that generates acid due to light and increases the dissolution rate in an alkaline aqueous solution, and has a diazoquinone structure, and

[0683] (D) Solvent.

[0684] [7]: The positive photosensitive resin composition as described in the above [6] further contains the following component (C).

[0685] (C) one or more crosslinking agents selected from the group consisting of amino condensates modified with formaldehyde or formaldehyde-alcohol, phenolic compounds having an average of more than two hydroxymethyl or alkoxyhydroxymethyl groups in one molecule, compounds in which the hydrogen atoms of the hydroxyl groups of polyphenols are substituted with glycidyl groups, compounds in which the hydrogen atoms of the hydroxyl groups of polyphenols or polyols are substituted with substituents represented by the following formula (C-1), and compounds containing two or more nitrogen atoms having glycidyl groups represented by the following formula (C-2).

[0686] [Chemistry 98]

[0687]

[0688] In the formula, dotted lines represent atomic bonds, Rc is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.

[0689] [8]: A negative photosensitive resin composition comprising:

[0690] (A) the polymer according to any one of [1] to [5] above,

[0691] (B') a photoacid generator,

[0692] (C) one or more crosslinking agents selected from the group consisting of amino condensates modified with formaldehyde or formaldehyde-alcohol, phenolic compounds having an average of two or more methylol groups or alkoxymethylol groups in one molecule, compounds in which hydrogen atoms of hydroxyl groups of polyphenols are substituted with glycidyl groups, compounds in which hydrogen atoms of hydroxyl groups of polyphenols or polyols are substituted with substituents represented by the following formula (C-1), and compounds containing two or more nitrogen atoms having glycidyl groups represented by the following formula (C-2), and

[0693] (D) Solvent.

[0694] [Chemistry 99]

[0695]

[0696] In the formula, dotted lines represent atomic bonds, Rc is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.

[0697] [9]: A pattern forming method, characterized by comprising the following steps:

[0698] (1) coating the positive photosensitive resin composition as described in [6] or [7] above on a substrate to form a photosensitive film, (2) heating the photosensitive film, (3) exposing the photosensitive film to high-energy radiation or electron beams with a wavelength of 190 to 500 nm through a photomask, and (4) developing the film using an alkaline aqueous developer.

[0699]

[10] : A pattern forming method, characterized by comprising the following steps:

[0700] (I) coating the negative photosensitive resin composition as described in [8] above on a substrate to form a photosensitive film, (II) heating the photosensitive film, (III) exposing the photosensitive film to high-energy radiation or electron beams having a wavelength of 190 to 500 nm through a photomask, and (IV) developing the substrate subjected to the heat treatment using an alkaline aqueous developer after the irradiation.

[0701]

[11] : A method for forming a hardened film, comprising the following steps:

[0702] The patterned film obtained by the pattern forming method described in [9] or

[10] is heated at a temperature of 100 to 300° C. and post-cured.

[0703]

[12] : An interlayer insulating film characterized by being composed of a cured film formed by curing the positive photosensitive resin composition as described in [6] or [7] above.

[0704]

[13] : An interlayer insulating film characterized by being composed of a cured film formed by curing the negative photosensitive resin composition as described in [8] above.

[0705]

[14] : A surface protection film, characterized in that it is composed of a cured film formed by curing the positive photosensitive resin composition as described in [6] or [7] above.

[0706]

[15] : A surface protection film, characterized in that it is composed of a cured film formed by curing the negative photosensitive resin composition as described in [8] above.

[0707]

[16] : An electronic component characterized by having an interlayer insulating film as described in

[12] or

[13] above or a surface protective film as described in

[14] or

[15] above.

[0708] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and those having substantially the same configuration as the technical concept described in the claims of the present invention and having the same functions and effects are all included in the technical scope of the present invention.

Claims

1. A polymer characterized by comprising a structural unit represented by the following general formula (1) and / or (2) and a structural unit represented by the following general formula (3) and / or (4); In the formula, X1 is a tetravalent organic group, R1 to R4 are monovalent organic groups having 1 to 15 carbon atoms which may be different or the same and may contain heteroatoms, or hydrogen atoms, and at least one of them is a monovalent organic group having 1 to 15 carbon atoms which may contain heteroatoms, and L is a divalent organic group or a divalent atom excluding a -OC(=O)- bond or a -C(=O)-O- bond; In the formula, X2 is a divalent organic group, R1 to R4 and L are the same as above; In the formula, X3 is a tetravalent organic group that is the same as or different from the aforementioned X1, s is 0 or 1, Z is a divalent bonding group, and when s=0, the two aromatic rings in the formula are directly bonded without a bonding group in between; In the formula, X4 is a divalent organic group which is the same as or different from the above X2, and s and Z are the same as described above.

2. The polymer according to claim 1, wherein In the general formulae (1) and (2), either R1 or R2 is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom, and the other is a hydrogen atom, and R3 and R4 are hydrogen atoms.

3. The polymer according to claim 1, wherein In the general formulae (1) and (2), either R1 or R2 is an aromatic group having 6 to 12 carbon atoms, and the other is a hydrogen atom.

4. The polymer according to claim 1, wherein The L in the general formulae (1) and (2) is at least one selected from an oxygen atom, a sulfur atom, a carbonyl group, a linear alkylene group having 1 to 15 carbon atoms, and a branched alkylene group having 3 to 15 carbon atoms.

5. The polymer according to claim 1, wherein In the general formulae (3) and (4), the Z is at least one bonding group selected from any one of the groups represented by the following formulae (5), (6), (7) and (8); In the formula, dotted lines represent atomic bonds.

6. A positive photosensitive resin composition, characterized in that contain: (A) the polymer according to claim 1, (B) is a photosensitizer that generates acid due to light and increases the dissolution rate in an alkaline aqueous solution, and has a diazoquinone structure, and (D) Solvent.

7. The positive photosensitive resin composition according to claim 6, further comprising the following component (C); (C) one or more crosslinking agents selected from the group consisting of amino condensates modified with formaldehyde or formaldehyde-alcohol, phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups in one molecule, compounds in which hydrogen atoms of hydroxyl groups of polyphenols are substituted with glycidyl groups, compounds in which hydrogen atoms of hydroxyl groups of polyphenols or polyols are substituted with substituents represented by the following formula (C-1), and compounds containing two or more nitrogen atoms having glycidyl groups represented by the following formula (C-2); In the formula, dotted lines represent atomic bonds, Rc is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.

8. A negative photosensitive resin composition, characterized in that contain: (A) the polymer according to claim 1, (B') a photoacid generator, (C) one or more crosslinking agents selected from the group consisting of amino condensates modified with formaldehyde or formaldehyde-alcohol, phenolic compounds having an average of two or more methylol groups or alkoxymethylol groups in one molecule, compounds in which hydrogen atoms of hydroxyl groups of polyphenols are substituted with glycidyl groups, compounds in which hydrogen atoms of hydroxyl groups of polyphenols or polyols are substituted with substituents represented by the following formula (C-1), and compounds containing two or more nitrogen atoms having glycidyl groups represented by the following formula (C-2), and (D) solvent; In the formula, dotted lines represent atomic bonds, Rc is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.

9. A method for forming a pattern, comprising the following steps: (1) coating the positive photosensitive resin composition according to claim 6 on a substrate to form a photosensitive material film, (2) heating the photosensitive material film, (3) exposing the photosensitive material film to high-energy radiation or electron beams with a wavelength of 190 to 500 nm through a photomask, and (4) Development is performed using an alkaline aqueous solution developer.

10. A pattern forming method, characterized by comprising the following steps: (I) coating the negative photosensitive resin composition according to claim 8 on a substrate to form a photosensitive material film, (II) heating the photosensitive material film, (III) exposing the photosensitive material film to high-energy radiation or electron beams with a wavelength of 190 to 500 nm through a photomask, and (IV) After the irradiation, the substrate subjected to the heat treatment is developed using a developer of an alkaline aqueous solution.

11. A method for forming a hardened film, comprising the following steps: The patterned film obtained by the pattern forming method according to claim 9 or 10 is heated at a temperature of 100 to 300° C. and post-cured.

12. An interlayer insulating film, characterized in that: A cured film formed by curing the positive photosensitive resin composition according to claim 6.

13. An interlayer insulating film, characterized in that: A cured film formed by curing the negative photosensitive resin composition according to claim 8.

14. A surface protection film, characterized in that: A cured film formed by curing the positive photosensitive resin composition according to claim 6.

15. A surface protection film, characterized in that: A cured film formed by curing the negative photosensitive resin composition according to claim 8.

16. An electronic component characterized by comprising the interlayer insulating film according to claim 12 or 13 or the surface protective film according to claim 14 or 15.

Images