Negative-type photosensitive resin composition, patterning process, method for forming cured coating, interlayer insulating film, surface protecting film, and electronic component

Abstract

The object of this invention is to provide a photosensitive resin composition that can undergo a polyimide ring-closing reaction at low temperatures, exhibits excellent stability, and is capable of forming fine patterns using a polyimide precursor. This photosensitive resin composition, after curing, provides resistance to chemicals. Furthermore, a patterning method using this photosensitive resin composition is provided, as well as an interlayer insulating film characterized by a cured film comprising the photosensitive resin composition and a semiconductor device. A negative photosensitive resin composition comprises: (A) a polymeric compound having a polyimide precursor structure, (C) a photopolymerization initiator, (D) an organic compound represented by the following general formula (1), and (E) a solvent.

Description

[Technical Field]

[0001] This invention relates to a negative photosensitive resin composition, a pattern forming method using the negative photosensitive resin composition that can be developed with an organic solvent, a method for forming a hardened film, an interlayer insulating film, a surface protective film, and electronic components. [Previous Technology]

[0002] With the miniaturization and high performance of various electronic devices such as personal computers, digital cameras, and mobile phones, the requirements for further miniaturization, thinning, and high density of semiconductor devices are also rapidly increasing. Therefore, there is a need to develop photosensitive insulating materials that can cope with the increase in substrate area as productivity improves, and that are fine and have a high aspect ratio on the substrate in high-density mounting technologies such as wafer-scale packaging (CSP) or three-dimensional stack-up.

[0003] In high-density mounting technology such as three-dimensional stacking, polyimide film has been effectively used as a protective film and interlayer insulating film for photosensitive insulating materials that can form patterns on the substrate. Its insulation, mechanical strength and adhesion to the substrate have been continuously studied and developed.

[0004] Polyimide and the like that forming the polyimide film have low solubility in solvents. Therefore, they are used in the state of precursors before the cyclization reaction of polyimide. After coating and laminating on a substrate, the polyimide precursor is heated to cyclize and form a hardened film, which is then used for protective films, interlayer insulating films, etc.

[0005] To date, materials have been proposed as precursors for polyimides capable of forming patterns, for example, materials in which photosensitive groups are introduced into the carboxyl groups of polyamide via ester bonds (Patent Document 1, Patent Document 2). However, in these proposals, after forming the patterned film, in order to obtain the target polyimide film, amide treatment must be performed at a high temperature exceeding 300°C. In order to withstand this high temperature, there are problems such as limitations on the substrate, oxidation of copper in the wiring, or potential thermal damage to electronic components.

[0006] Patent Document 3 discloses a polyimide precursor composition comprising a polyimide precursor, a thermal alkali generating agent that generates alkali by heating, and a solvent. The aforementioned polyimide precursor is polyamide, and the aforementioned thermal alkali generating agent is a neutral compound that is thermally decomposed by heating at a temperature below 200°C to generate a secondary amine. Since the secondary amine generated by thermal decomposition promotes the cyclocloning reaction of the polyimide, it shows that processing at temperatures below 200°C is possible.

[0007] However, for hardened films using the composition described in Patent Document 3, the corrosion resistance and chemical resistance required for protective coatings, interlayer insulating films, etc., are sometimes poor. In addition, there are problems with storage stability, such as gelation caused by the cyclization reaction of the polyimide precursor resin during the storage of the composition.

[0008] On the other hand, Patent Documents 4 and 5 disclose compositions containing a polyimide precursor and an imidazole-based catalyst that promotes the amide ring-closing reaction of the amide. However, they do not disclose photosensitive resin compositions capable of forming patterns on a substrate as required in high-density mounting technology, nor do they disclose low-temperature amide formation. Furthermore, the imidazole-based amide catalysts described in Patent Documents 4 and 5, except for N-tert-butoxycarbonyl imidazole (N-Boc-imidazole), have storage stability issues due to gelation during the storage of the composition. In addition, if the amount of imidazole-based amide catalysts added is as described in Patent Documents 4 and 5, heat-induced pattern deformation (heat flow) occurs during the curing reaction after pattern formation, making it undesirable to have fine and high aspect ratio patterns or a decrease in the glass transition temperature (Tg.) of the resulting cured film, thus making them unsuitable for use in protective films, interlayer insulating films, etc.

[0009] On the other hand, Patent Document 6 discloses a method that uses an active esterifying agent as a compound capable of amide imidization at a lower temperature, unlike a hot alkali generating agent that generates alkali by heating. However, the carbonate and ester compounds of bis(pentafluorophenyl) carbonate, bis(4-nitrophenyl) carbonate, di(N-succinimidyl) carbonate, and 4-nitrophenyl trifluoroacetate shown in Patent Document 6 have higher decomposition temperatures, which is expected to more effectively promote the amide ring-closing reaction in the heating step of providing the hardened coating.

[0010] In addition, the active esterifying agents pentafluorophenol and 1-hydroxy-7-azabenzotriazole shown in Patent Document 6 contain hydroxyl groups, which causes a problem of deterioration in the storage stability of photosensitive resin compositions containing polyimide precursor resins.

[0011] On the other hand, Patent Document 7 discloses the addition of amide as a compound capable of promoting amide imidization reaction. However, since the amide compound shown in Patent Document 7 contains hydroxyl and amino groups, it is undeniable that it degrades the storage stability of photosensitive resin compositions containing polyamide precursor resins.

[0012] Thus, there is an urgent need to develop a photosensitive resin composition that uses a polyimide precursor and possesses all of the following characteristics without lacking any one of them: the ability to form fine patterns; the ability to obtain a hardened film by low-temperature heating; the hardened protective coating and interlayer insulating film possessing heat resistance in various steps; resistance to various chemicals used; and good storage stability of the composition. [Prior Art Documents] [Patent Documents]

[0013] Patent Document 1: Japanese Patent Application Publication No. 49-115541; Patent Document 2: Japanese Patent Application Publication No. 55-45746; Patent Document 3: Japanese Patent Application Publication No. 2007-056196; Patent Document 4: Japanese Patent No. 7436606; Patent Document 5: Japanese Patent Application Publication No. 2022-159241; Patent Document 6: Japanese Patent Application Publication No. 2024-19341; Patent Document 7: Japanese Patent No. 7252020 [Summary of the Invention]

[0014] [Problem to be Solved by the Invention] The present invention has been made in view of the above-mentioned circumstances. The object of the present invention is to provide a photosensitive resin composition using a polyimide precursor that can undergo a cyclo-closing reaction of propylene oxide at low temperatures, exhibits excellent stability, and is capable of forming fine patterns. Furthermore, a pattern forming method using this photosensitive resin composition, an interlayer insulating film composed of a cured film formed by curing the photosensitive resin composition, a surface protective film, and electronic components are provided. [Means for Solving the Problem]

[0015] That is, in order to solve the above-mentioned problems, the present invention provides a negative photosensitive resin composition, characterized in that it contains: (A) a polymeric compound having a polyimide precursor structure, (C) a photopolymerization initiator, (D) an organic compound represented by the following general formula (1), and (E) a solvent; [Chemical 1] In the formula, T represents any structure in the following general formulas (2) to (4), and W represents an alkyl or aryl group that can also be substituted by an alkoxy group having 4 to 15 carbon atoms. [Chemical 2] In the formula, V represents a divalent organic group, and * represents a bond. [Chemical 3] In the formula, Q represents a halogen atom or a nitro group, and RC represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms. n represents an integer from 3 to 5 when Q is a halogen atom, and 1 when Q is a nitro group. * represents a bond. In formula [Chemistry 4], Ar represents a substituted or unsubstituted aromatic ring structure, or a heterocyclic structure with heteroatoms, and * represents a bond.

[0016] When the organic compound shown in the above general formula (1) is added to the negative photosensitive resin composition containing the polyimide precursor structure, the temperature of the curing reaction of the curing film, i.e. the pyrimide ring-closing reaction, is lower than 200°C.

[0017] In addition, the organic compound represented by the above general formula (1) can inhibit the aggregation and gelation of the polymer compound containing the polyimide precursor structure with the organic compound by the presence of the -(C=O)-OW group, and can inhibit the deterioration of the storage stability of the photosensitive resin composition.

[0018] At this time, component (A) is preferably a polymeric compound having the polyimide precursor structure shown in the following general formula (5). [Chemical 5] In the formula, X is a tetravalent organic group, Y is a divalent organic group, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R1 and R2 is a group shown in the following general formula (6). [Chemical 6] In the formula, M1, M2 and M3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer from 2 to 10. * indicates a bond.

[0019] From the viewpoint of the strength of the obtained hardened film, it is preferable to be a polymeric compound containing structural units of such polyimide precursors.

[0020] Furthermore, it is preferable to include (B) a polymeric compound having two or more vinyl unsaturated groups.

[0021] By using a crosslinking agent containing two or more photopolymerizable unsaturated bonds in one molecule, it is possible to promote the photopolymerization-based crosslinking of component (A) in the exposed portion and improve the contrast between the exposed portion and the unexposed portion.

[0022] In addition, at this time, it is preferable that W in the general formula (1) of the above (D) component is a third butyl group.

[0023] When W is a third butyl group, it represents a compound in which the oxygen atom of structure T of the organic compound shown in the above general formula (1) is protected by a third butoxycarbonyl group (Boc group). The third butoxycarbonyl group (Boc group) is deprotected in the heating step of the hardening reaction in the range of 100°C to 150°C, which can generate an organic compound that can promote the amide ring-closing reaction, and therefore can be amided at temperatures below 200°C.

[0024] In addition, at this time, W in the general formula (1) of the above (D) component is preferably benzyl.

[0025] When W is benzyl, it represents a compound in which the oxygen atom of structure T of the organic compound shown in the above general formula (1) is protected by a benzyloxycarbonyl protecting group (Z group). The benzyloxycarbonyl protecting group (Z group) is deprotected in the heating step of the hardening reaction in the range of 120°C to 190°C, which can generate an organic compound that can promote the amide ring-closing reaction, and therefore can be amided at temperatures below 200°C.

[0026] Preferably, the above general formula (2) is a negative photosensitive resin composition with the structure shown in the following general formula (2-1). [Chemical 7] In the formula, Ra and Rb represent hydrogen atoms, straight-chain, branched or cyclic alkyl groups having 1 to 15 carbon atoms, or aryl groups having 6 to 15 carbon atoms. Ra and Rb may also be bonded to each other and form a ring together with the carbon atoms they are bonded to. * indicates a bond.

[0027] If the above general formula (2) is the structure shown in the above general formula (2-1), the hydroxyl group of the N-hydroxy-polyimide compound that promotes the polyimide reaction is protected by the third butoxycarbonyl (Boc group) and benzyloxycarbonyl protecting group (Z group) described above, which can make the photosensitive resin composition containing polyimide precursor resin have good storage stability.

[0028] Preferably, the above general formula (3) is a negative photosensitive resin composition with the structure shown in the following general formula (3-1) or (3-2). [Chemical 8] In the formula, * represents a bond. [Chemical 9] In the formula, * represents a bond.

[0029] When the aforementioned general formula (3) is the structure shown in the above general formula (3-1) or (3-2), the hydroxyl groups of 4-nitrophenol and pentafluorophenol, which are active esterifying agents for promoting the amide reaction, are protected by the third butoxycarbonyl (Boc group) and benzyloxycarbonyl protecting group (Z group) described above, so that the photosensitive resin composition containing polyamide precursor resin has good storage stability.

[0030] If the organic compound containing the aforementioned general formula (3) is the structure shown in the above general formula (3-1) or (3-2), then from the perspective of the ease of obtaining the raw materials, the safety of the compound, and the low toxicity, further preferred examples can be listed.

[0031] Preferably, the above general formula (4) is a negative photosensitive resin composition with the structure shown in the following general formula (4-1). [Chemical 10] In the formula, Rd represents a straight-chain, branched, or cyclic alkyl group having 1 to 15 carbon atoms or halogen atoms, or an aryl group having 6 to 15 carbon atoms, and k represents an integer from 0 to 4. * represents a bond.

[0032] If the above general formula (4) is the structure shown in the above general formula (4-1), then the hydroxyl group of 1-hydroxy-benzotriazole, which is an active esterifying agent that promotes the amide reaction, is protected with the third butoxycarbonyl (Boc group) and benzyloxycarbonyl protecting group (Z group) described above, which enables the photosensitive resin composition containing polyamide precursor resin to have good storage stability.

[0033] In addition, it is preferable to contain 1 to 10 parts by mass of the above-mentioned component (D) relative to 100 parts by mass of component (A) above.

[0034] When the organic compound in component (D) is 10 parts by mass or less, the added organic compound does not act as a plasticizer, and the formed pattern does not deform due to heat; that is, no heat flow occurs, and the pattern formation is not impaired. Furthermore, after curing, the glass transition point (Tg.) of the obtained cured film does not decrease. The high requirement for the glass transition point (Tg.) of the obtained cured film is due to the requirement for heat resistance during the manufacturing process of electronic components formed using interlayer insulating films and surface protective films that utilize the obtained cured film.

[0035] In addition, in this invention, the (F) thermal crosslinking agent is preferably one or more crosslinking agents selected from formaldehyde or formaldehyde-alcohol modified amine condensates, phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups per molecule, compounds in which the hydrogen atoms of the hydroxyl groups of polyphenols are replaced with glycidyl groups, compounds in which the hydrogen atoms of the hydroxyl groups of polyphenols or polyols are replaced with substituents shown in the following formula (F-1), and compounds containing two or more nitrogen atoms of glycidyl groups shown in the following formula (F-2). [Chemical 11] In the formula, the dashed line represents an atomic bond, Rf is a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and c is 1 or 2.

[0036] (F) is a component that, after the pattern of the negative photosensitive resin composition of the present invention is formed, causes a cross-linking reaction during post-curing, thereby further improving the strength of the cured material.

[0037] As the above-mentioned negative photosensitive resin composition, it is preferable to further contain (G) antioxidant.

[0038] By using an antioxidant containing component (G), excessive cross-linking between components (A) or between components (A) and (B) during patterning can be suppressed, thereby improving contrast. In addition, by providing rust prevention for metal materials, metal oxidation caused by external moisture, photoacid generators, thermal acid generators, etc., as well as the associated reduction in adhesion and peeling, can be suppressed.

[0039] As the above-mentioned negative photosensitive resin composition, it is preferable to further contain (H) silane compound.

[0040] The negative photosensitive resin composition of the present invention preferably includes a metal adhesion modifier for improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion modifiers include silane compounds.

[0041] As the above-mentioned negative photosensitive resin composition, it is preferable to further contain (I) a polymerization inhibitor.

[0042] By including (I) a polymerization inhibitor, a thermal polymerization inhibitor can be added to improve the viscosity and photosensitivity stability of the composition solution during storage.

[0043] In addition, the present invention provides a pattern forming method, which includes: (1) coating the above-described photosensitive resin composition onto a substrate to form a photosensitive material film; (2) then exposing the photosensitive material film to high-energy rays or electron beams with a wavelength of 190 to 500 nm through a light shield after heat treatment; and (3) developing the film using a developer solution with an organic solvent after irradiation.

[0044] Such a pattern forming method for negative photosensitive resin compositions, particularly in a negative photosensitive resin composition containing a polymeric polyimide precursor structure having a polymeric unsaturated bond group as described above, can be hardened without causing shape changes in the obtained pattern by using an organic compound containing component (D) of the present invention, thus demonstrating a pattern forming method capable of forming fine patterns.

[0045] Then, the present invention can provide a method for forming a hardened film, characterized in that it includes the step of heating and hardening a patterned film obtained by the above-described pattern forming method at a temperature of 100 to 300°C.

[0046] By performing such a pattern forming method, the hardening reaction after pattern formation, namely the amide ring-closing reaction, can be carried out at low temperature.

[0047] In addition, the present invention provides an interlayer insulating film, which is a hardened film formed by hardening the negative photosensitive resin composition described above.

[0048] The hardened film formed by curing the photosensitive resin composition of the present invention is beneficial as an interlayer insulating film.

[0049] In addition, the present invention provides a surface protective film, which is a hardened film formed by hardening the negative photosensitive resin composition described above.

[0050] The hardened film formed by curing the photosensitive resin composition of the present invention is beneficial as an interlayer insulating film and a surface protective film.

[0051] In addition, the present invention provides an electronic component having the interlayer insulating film described above.

[0052] In addition, the present invention provides an electronic component having the aforementioned surface protective film.

[0053] Such electronic components exhibit excellent reliability due to the protective coating (interlayer insulating film or surface protective film) that provides heat resistance, chemical resistance, and insulation. [Effects of the Invention]

[0054] As described above, according to the present invention, a negative photosensitive resin composition can be provided, which contains a polymeric compound with a polyimide precursor structure. Regardless of the molecular structure of the polyimide precursor, a cyclo-closing reaction of the polyimide can be performed at low temperature, and it exhibits high storage stability. Furthermore, since curing can be performed without causing shape changes in the resulting pattern, fine patterns can be formed. In addition, the cured film obtained after pattern formation exhibits excellent chemical resistance and a high glass transition temperature (Tg.).

Implementation Method

[0055] As mentioned above, there is a need to develop a photosensitive resin composition using a polyimide precursor that can undergo a cyclo-closing reaction of polyimide at low temperatures, has excellent stability, and can form fine patterns. This photosensitive resin composition can be given resistance to chemicals after curing.

[0056] The inventors conducted in-depth research in order to achieve the above-mentioned objective and found that the composition of adding an organic compound of the following general formula (1) to a photosensitive resin composition containing a polymeric compound containing a polyimide precursor structure can be achieved without impairing the formation of fine patterns and can carry out a curing reaction after pattern formation, i.e., a polyimide ring-closing reaction, at temperatures below 200°C.

[0057] Furthermore, it was found that the obtained hardened film exhibits excellent chemical resistance and a high glass transition point (Tg.). Additionally, it was further discovered that the photosensitive resin composition also exhibits good storage stability, thus completing the present invention.

[0058] That is, the present invention provides a negative photosensitive resin composition, characterized by comprising: (A) a polymeric compound having a polyimide precursor structure, (C) a photopolymerization initiator, (D) an organic compound represented by the following general formula (1), and (E) a solvent; [Chemical 12]In the formula, T represents any structure in the following general formulas (2) to (4), and W represents an alkyl or aryl group that can also be substituted by an alkoxy group having 4 to 15 carbon atoms. [Chemical 13]In the formula, V represents a divalent organic group, and * represents a bond. [Chemical 14]In the formula, Q represents a halogen atom or a nitro group, and RC represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms. n represents an integer from 3 to 5 when Q is a halogen atom, and 1 when Q is a nitro group. * represents a bond. In formula [Chem. 15], Ar represents a substituted or unsubstituted aromatic ring structure or a heterocyclic structure with heteroatoms, and * represents a bond.

[0059] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0060] [(A) Composition] From the viewpoint of the strength of the obtained hardened film, the polymeric compound containing the structural unit of the polyimide precursor of the present invention is preferably the polymeric compound shown in the following formula (5). [Chemical 16] In the formula, X is a tetravalent organic group, Y is a divalent organic group, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R1 and R2 is a group shown in the following general formula (6). [Chemical 17] In the formula, M1, M2 and M3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer from 2 to 10. * indicates a bond.

[0061] X in the above general formula (5) is a tetravalent organogroup, but there is no limitation as long as it is a tetravalent organogroup. Preferably, it is a tetravalent organogroup of alicyclic aliphatic group or aromatic group with 4 to 40 carbon atoms. More preferably, it is a tetravalent organogroup shown in the following formula (7). In addition, the structure of X can be one type or a combination of two or more types. [Chemical 18] In the formula, Re1 and Re2 are each independently methyl or phenyl, b1 and b2 are integers from 1 to 20, and the dashed lines represent atomic bonds.

[0062] Y in the above general formula (5) is a divalent organogroup. There is no limitation as long as it is a divalent organogroup. It is more preferably a divalent organogroup with 6 to 40 carbon atoms, more preferably a divalent cyclic organogroup containing 1 to 4 substituent aromatic or aliphatic rings, or a divalent aliphatic group without a cyclic structure, or a siloxane. As a further preferred Y, the structure shown in the following formula (8) or (9) can be given. In addition, the structure of Y can be one type or a combination of two or more types. [Chemical 19] In the formula, b3 is an integer from 1 to 20, s1 is an integer from 1 to 40, s2 and s3 are each independently an integer from 0 to 40, and the dashed line represents an atomic bond.

[0063] [Chemical 20] In the formula, b4 is an integer from 1 to 4, Re4 is a fluorine atom, methyl, ethyl, propyl, n-butyl, methoxy, ethoxy, propoxy, butoxy, or trifluoromethyl. When b4 is 2 or more, Re4 can be the same or different. b5 is an integer from 1 to 40. The dashed line represents an atomic bond.

[0064] R1 and R2 in the above general formula (5) are each independently a hydrogen atom or a monovalent organic group. The monovalent organic group can be a straight-chain, branched, or cyclic alkyl group with 1 to 6 carbon atoms, or an organic group shown in the above general formula (6). Moreover, at least one of R1 and R2 is an organic group shown in the above general formula (6).

[0065] M1 in the above general formula (6) is not limited as long as it is a hydrogen atom or a monovalent organic group with 1 to 3 carbon atoms. From the viewpoint of the photosensitivity of negative photosensitive resin composition, it is preferred to be a hydrogen atom or a methyl group.

[0066] M2 and M3 in the above general formula (6) are not limited as long as they are each independently hydrogen atoms or monovalent organic groups with 1 to 3 carbon atoms. From the viewpoint of the photosensitivity of negative photosensitive resin composition, hydrogen atoms are preferred.

[0067] In the above general formula (6), m is an integer from 2 to 10. From the viewpoint of photosensitivity, it is preferably an integer from 2 to 4. More preferably, m is 2.

[0068] In addition, the polymeric compounds of the present invention may contain, in addition to the structural units shown in the above general formula (5), any one or more of the structural units shown in the following general formulas (10) to (12). [Chemical 21] In the formula, X1 is a tetravalent organic group that is the same as or different from X above, and Y1 is a divalent organic group that is the same as or different from Y above. [Chemical 22] In the formula, X2 is a divalent organic group, and Y2 is a divalent organic group that is the same as or different from Y above. [Chemical 23] In the formula, Y3 is a divalent organic group that is the same as or different from Y above, and X3 is a tetravalent organic group.

[0069] X1 in the above general formula (10) is a tetravalent organogroup, which may be the same as or different from X above, as long as it is a tetravalent organogroup, there is no limitation. Preferably, it is a tetravalent alicyclic aliphatic group with 4 to 40 carbons or a tetravalent aromatic group with 6 to 40 carbons, and may also contain a siloxane skeleton. More preferably, it is a tetravalent organogroup shown in the above formula (7). In addition, the structure of X1 can be one type or a combination of two or more types.

[0070] Y1 in the above general formula (10) is a divalent organogroup, which may be the same as or different from the above Y. There is no limitation as long as it is a divalent organogroup. It is preferably a divalent organogroup with 6 to 40 carbon atoms, more preferably a divalent cyclic organogroup containing 1 to 4 aromatic or aliphatic rings with substituents, or a divalent aliphatic group without a cyclic structure, or a siloxane. As a further preferred Y1, the structure shown in the above formula (8) or (9) can be given. In addition, the structure of Y1 can be one type or a combination of two or more types.

[0071] If the resin composition contains a polymer compound comprising the structural unit shown in the above general formula (10), the mechanical strength, adhesion to the substrate, and heat resistance of the hardened film obtained by forming the pattern can be improved, which is ideal. In addition, the structural unit (10) does not need to undergo a ring-closing reaction in the post-curing process, which can relatively reduce the curing reaction temperature, which is also ideal.

[0072] X2 in the above general formula (11) is a divalent organogroup, and there is no limitation as long as it is a divalent organogroup. Preferably, it is a divalent organogroup with an aliphatic chain 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. More preferably, it is a divalent organogroup shown in the following formula (13). In addition, the structure of X2 can be one type or a combination of two or more types. [Chemical 24] In the formula, Ra3 is independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, b4 is an integer from 1 to 30, and the dashed line represents an atomic bond.

[0073] Y2 in the above general formula (11) is a divalent organogroup, which may be the same as or different from the above Y, as long as it is a divalent organogroup, there is no limitation. Preferably, it is a divalent organogroup with 6 to 40 carbon atoms, a divalent cyclic organogroup containing 1 to 4 aromatic or aliphatic rings with substituents, or a divalent aliphatic group without a cyclic structure, or a siloxane. More preferably, it can be a structure shown in the above formula (8) or (9). In addition, the structure of Y2 can be one type or a combination of two or more types.

[0074] Y3 in the above general formula (12) is a divalent organic group, which may be the same as or different from the above Y, as long as it is a divalent organic group, there is no limitation. Preferably, it is a divalent organic group with an aliphatic chain structure of 4 to 40 carbons, a divalent alicyclic aliphatic group of 4 to 40 carbons, or a divalent aromatic group of 6 to 40 carbons. More preferably, it is a divalent organic group shown in the above formula (13). In addition, the structure of Y3 can be one type or a combination of two or more types.

[0075] X3 in the above general formula (12) is a tetravalent organogroup. There is no limitation as long as it is a tetravalent organogroup. It is more preferably a tetravalent organogroup with 6 to 40 carbon atoms, more preferably a tetravalent cyclic organogroup containing 1 to 4 aromatic or aliphatic rings with substituents, or a tetravalent aliphatic group without a cyclic structure, or a siloxane. As a further preferred X3, the structure shown in the following formula (14) can be given. In addition, the structure of X3 can be one type or a combination of two or more types. [Chemical 25] In the formula, b12, b13 and b14 are integers from 1 to 10; b15 is an integer from 1 to 20, and the dashed line represents an atomic bond.

[0076] If the resin composition contains a polymer having the structural unit shown in the aforementioned general formula (12), the mechanical strength, adhesion to the substrate, and heat resistance of the hardened film obtained by patterning can be improved, which is ideal. In addition, in the case of the structure shown in general formula (12), there is no need to perform a ring-closing reaction in the post-curing process, which can relatively reduce the curing reaction temperature, which is also ideal.

[0077] The suitable molecular weight of the polymer of the present invention is preferably 5,000 to 100,000, more preferably 7,000 to 50,000. If the molecular weight is 5,000 or higher, it is easy to form a composition containing the polymer of the present invention on a substrate to the desired film thickness. If the molecular weight is 100,000 or lower, the viscosity of the aforementioned photosensitive composition will not increase significantly, and a film can also be easily formed. Furthermore, in the present invention, the weight-average molecular weight is a polystyrene equivalent value obtained by gel permeation chromatography (GPC) using DMF as the dissolution solution at a temperature of 40°C.

[0078] [Method for manufacturing polymeric compounds] The polymeric compounds contained in the negative photosensitive resin composition of the present invention preferably contain structural units represented by the following general formula (5). [Chemical 26] In the formula, X is a tetravalent organic group, Y is a divalent organic group, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R1 and R2 is a group represented by the following general formula (6). [Chemical 27] In the formula, M1, M2 and M3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer from 2 to 10. * indicates a bond.

[0079] A polymer containing the structural unit shown in the above general formula (5) can be obtained by reacting a tetracarboxylic acid diester compound shown in the following general formula (15) with a diamine shown in the following general formula (16). [Chemical 28] In the formula, X, R1 and R2 are the same as above. [Chemical 29] In the formula, Y is the same as above.

[0080] In the above general formula (15), at least one of R1 and R2 is an organic group represented by the above general formula (6). By reacting the tetracarboxylic dianhydride represented by the following general formula (17) with a compound with a terminal hydroxyl group represented by the following general formula (18) under the presence of an alkaline catalyst such as pyridine, the organic group represented by the above general formula (6) can be introduced. The tetracarboxylic dianhydride represented by the following general formula (17) is the basis of X in the above general formula (5) (for example, the tetravalent organic group represented by the above formula (7)). The compound with a terminal hydroxyl group represented by the following general formula (18) can be introduced into the organic group represented by the above general formula (6). [Chemical 30] In the formula, X represents a tetravalent organic group, which has the same meaning as X in the above general formula (5). [Chemical 31] In the formula, M1, M2, M3 and m are synonymous with M1, M2, M3 and m in the above general formula (6).

[0081] As a preferred example of the tetracarboxylic acid dianhydride shown in the above general formula (17), examples include aromatic acid dianhydrides, alicyclic acid dianhydrides, aliphatic acid dianhydrides, and acid dianhydrides containing a siloxane skeleton.

[0082] Aromatic acid dianhydrides, such as: benzopyroxene 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'-triphenyltetracarboxylic acid dianhydride, 3,3',4,4'-oxophthalic acid dianhydride, 2,3,3',4'-oxophthalic acid dianhydride, 2,3,2',3'-oxophthalic acid dianhydride, diphenyl tannin-3,3',4,4'-tetracarboxylic acid dianhydride, diphenyl ketone-3,3' 4,4'-Tetracarboxylic acid 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)phenyl dianhydride, p-phenylbis(trimethoxy)benzoic acid dianhydride, bis(1,3-disidel-1,3-dihydroisophenyl) (Furfural-5-carboxylic acid) 1,4-phenylene, 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)pyridine dianhydride, 9,9-bis(4-(3,4-dicarboxyphenoxy)phenyl)pyridine 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-di-di-) Carboxybenzo(phenyl)hexafluoropropane dianhydride, 1,6-difluorobenzopyroxane dianhydride, 1-trifluoromethylbenzopyroxane dianhydride, 1,6-di(trifluoromethyl)benzopyroxane 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 whose aromatic rings are substituted with alkyl, alkoxy, halogen atoms, etc., but not limited to these.

[0083] Alicyclic acid dianhydrides, such as: 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,4,5-cyclopentanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cycloheptanetetracarboxylic acid dianhydride, 2,3,4-cycloheptan ... ,5-Tetrahydrofuran tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic dianhydride, tricyclo[ [6,3,0,02,6]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]heptane-tetracarboxylic 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'-oxodicyclohexanetetracarboxylic dianhydride, 5-(2,5-disideloxytetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and "Rikacid" (registered trademark) BT-100 (the above are trade names, manufactured by Shin Nippon Rikka Co., Ltd.) and their derivatives, or acid dianhydride compounds substituted with alicyclic organic alkyl, alkoxy, halogen atoms, etc., but not limited to these.

[0084] Examples of aliphatic acid dianhydrides include, for example, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-pentanetetracarboxylic acid dianhydride, and their derivatives, but are not limited to these.

[0085] Examples of acid dianhydrides containing a siloxane skeleton include, for example, 1,3-bis(3,4-dicarboxyphenyl)-1133-tetramethyldisiloxane dianhydride, 3,3'-(1,1,3,3-tetramethyl-1,3-disiloxanediyl)bis-3,1-propanediyl)bis(dihydro-2,5-furandione), and their derivatives, but are not limited to these.

[0086] These aromatic acid dianhydrides, alicyclic acid dianhydrides, aliphatic acid dianhydrides, and acid dianhydrides containing a siloxane skeleton can be used alone or in combination of two or more.

[0087] M1 in the above general formula (18) is not limited as long as it is a hydrogen atom or a monovalent organic group with 1 to 3 carbon atoms. From the viewpoint of the photosensitivity of negative photosensitive resin composition, it is preferred to be a hydrogen atom or a methyl group.

[0088] M2 and M3 in the above general formula (18) are not limited as long as they are each independently hydrogen atoms or monovalent organic groups with 1 to 3 carbon atoms. From the viewpoint of the photosensitivity of negative photosensitive resin composition, hydrogen atoms are preferred.

[0089] In the above general formula (18), m is an integer from 2 to 10. From the viewpoint of photosensitivity, it is preferably an integer from 2 to 4. More preferably, m is 2.

[0090] Among the compounds with hydroxyl groups at the end shown in the above general formula (18), preferred compounds include, for example, 2-propenyloxyethanol, 1-propenyloxy-3-propanol, 2-methylpropenyloxyethanol, 1-methylpropenyloxy-3-propanol, etc.

[0091] In addition, R1 and R2 in the above general formula (5) can be straight-chain, branched, or cyclic alkyl groups having 1 to 6 carbon atoms. A method for introducing straight-chain, branched, or cyclic alkyl groups having 1 to 6 carbon atoms into the above general formula (5) (i.e., R1 and R2 become straight-chain, branched, or cyclic alkyl groups having 1 to 6 carbon atoms) can be exemplified by simultaneously introducing a straight-chain, branched, or cyclic alcohol having 1 to 6 carbon atoms into the reaction of a compound with a terminal hydroxyl group as shown in the above general formula (18) with a tetracarboxylic acid dianhydride in the presence of an alkaline catalyst such as pyridine.

[0092] Among the preferred alcohols that can be used at this time are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentanol, 1-hexanol, 2-hexanol, 3-hexanol, cyclopentanol, cyclohexanol, etc.

[0093] Regarding the reaction between the tetracarboxylic dianhydride shown in the aforementioned general formula (17) and the compound with a hydroxyl terminal shown in the aforementioned general formula (18), in the presence of an alkaline catalyst such as pyridine, in a reaction solvent, at a reaction temperature of 20°C to 50°C for 4 to 10 hours, the tetracarboxylic dianhydride shown in the aforementioned general formula (17) and the compound with a hydroxyl terminal shown in the aforementioned general formula (18) are stirred, dissolved and mixed to carry out a half-esterification reaction of the dianhydride, thereby obtaining a solution in which the desired tetracarboxylic acid diester compound shown in the aforementioned general formula (15) is dissolved in the reaction solvent.

[0094] The obtained tetracarboxylic acid diester compound can be separated, or the obtained solution can be directly used for the reaction with diamine in the next step described below.

[0095] Preferably, the solvent used for the above reaction is a solvent that can well dissolve the above tetracarboxylic acid diester and the polymer having the structural unit of polyimide precursor obtained by the subsequent polycondensation reaction of the above tetracarboxylic acid diester with diamine. Examples of solvents include: N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, etc. Alternatively, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons can also be used. Specifically, examples include 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-dichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, and xylene. These can be used individually or in mixtures of two or more, depending on the need.

[0096] Ideal examples of the diamine represented by the above general formula (16) include, for example, (2-methyl-4-amino)phenyl-4-aminobenzoate, (3-methyl-4-amino)phenyl-4-aminobenzoate, (2-ethyl-4-amino)phenyl-4-aminobenzoate, (3-ethyl-4-amino)phenyl-4-aminobenzoate, (2-propyl-4-amino)phenyl-4-aminobenzoate, (3-propyl-4-amino)phenyl-4-aminobenzoate, (2-isopropyl-4-amino)phenyl-4-aminobenzoate, (3-isopropyl-4-amino)phenyl-4-aminobenzoate, (2-butyl-4-amino)phenyl-4-aminobenzoate, (3-butyl-4-amino)phenyl-4-aminobenzoate, (3-butyl-4-amino)phenyl-4-aminobenzoate, (2-methyl ... (-amino)phenyl-4-aminobenzoate, (2-isobutyl-4-amino)phenyl-4-aminobenzoate, (3-isobutyl-4-amino)phenyl-4-aminobenzoate, (2-pentyl-4-amino)phenyl-4-aminobenzoate, (3-pentyl-4-amino)phenyl-4-aminobenzoate, (2-hexyl-4-amino)phenyl-4-aminobenzoate, (3-hexyl-4-amino)phenyl-4-aminobenzoate, (2-methoxy-4-amino)phenyl-4-aminobenzoate, (3-methoxy-4-amino)phenyl-4-aminobenzoate, (2-ethoxy-4-amino)phenyl-4-aminobenzoate, (3-ethoxy-4-amino)phenyl-4-aminobenzoate Benzyl benzoate, (2-propoxy-4-amino)phenyl-4-aminobenzoate, (3-propoxy-4-amino)phenyl-4-aminobenzoate, (2-butoxy-4-amino)phenyl-4-aminobenzoate, (3-butoxy-4-amino)phenyl-4-aminobenzoate, (2-pentoxy-4-amino)phenyl-4-aminobenzoate, (3-pentoxy-4-amino)phenyl-4-aminobenzoate, (2-phenyl-4-amino)phenyl-4-aminobenzoate, (3-phenyl-4-amino)phenyl-4-aminobenzoate, (2-methylphenyl-4-amino)phenyl-4-aminobenzoate, (3-methylphenyl-4-amino)phenyl-4-aminobenzoate (2-Ethylphenyl-4-amino)phenyl-4-aminobenzoate, (3-Ethylphenyl-4-amino)phenyl-4-aminobenzoate, (2-propylphenyl-4-amino)phenyl-4-aminobenzoate, (3-propylphenyl-4-amino)phenyl-4-aminobenzoate, (2-Butylphenyl-4-amino)phenyl-4-aminobenzoate, (3-Butylphenyl-4-amino)phenyl-4-aminobenzoate, (2-Fluorophenyl-4-amino)phenyl-4-aminobenzoate, (3-Fluorophenyl-4-amino)phenyl-4-aminobenzoate, (2-Chlorophenyl-4-amino)phenyl-4-aminobenzoate, (3-Chlorophenyl-4-amino)phenyl-4-aminobenzoate(2-Bromophenyl-4-amino)phenyl-4-aminobenzoate, (3-Bromophenyl-4-amino)phenyl-4-aminobenzoate, (2-methoxyphenyl-4-amino)phenyl-4-aminobenzoate, (3-methoxyphenyl-4-amino)phenyl-4-aminobenzoate, (2-ethoxyphenyl-4-amino)phenyl-4-aminobenzoate, (3-ethoxyphenyl-4-amino)phenyl-4-aminobenzoate, (2-ethoxyphenyl-4-amino)phenyl-4-aminobenzoate, (2-aminophenyl-4-amino)phenyl-4-aminobenzoate, (3-aminophenyl-4-amino)phenyl-4-aminobenzoate, (2-nitrophenyl-4-amino)phenyl-4-amino Benzoate esters, (3-nitrophenyl-4-amino)phenyl-4-aminobenzoate esters, (2-cyanophenyl-4-amino)phenyl-4-aminobenzoate esters, (3-cyanophenyl-4-amino)phenyl-4-aminobenzoate esters, (2-phenylethyl-4-amino)phenyl-4-aminobenzoate esters, (3-phenylethyl-4-amino)phenyl-4-aminobenzoate esters, (2-anilino-4-amino)phenyl-4-aminobenzoate esters, (3-anilino-4-amino)phenyl-4-aminobenzoate esters, (2-(4,4'-biphenyl)-4-amino)phenyl-4-aminobenzoate esters, (3-(4,4'-biphenyl)-4-amino)phenyl-4-aminobenzoate esters, (2-naphthyl-4-amino) ) Phenylacetyl-4-aminobenzoate, (3-naphthyl-4-amino)phenyl-4-aminobenzoate, (2-methylphenoxy-4-amino)phenyl-4-aminobenzoate, (3-methylphenoxy-4-amino)phenyl-4-aminobenzoate, (2-ethylphenoxy-4-amino)phenyl-4-aminobenzoate, (3-ethylphenoxy-4-amino)phenyl-4-aminobenzoate, (2-propylphenoxy-4-amino)phenyl-4-aminobenzoate, (3-propylphenoxy-4-amino)phenyl-4-aminobenzoate, (2-methoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (3-methoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (2 (3-ethoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (2-benzyl-4-amino)phenyl-4-aminobenzoate, (3-benzyl-4-amino)phenyl-4-aminobenzoate, (2-methylbenzyl-4-amino)phenyl-4-aminobenzoate, (3-methylbenzyl-4-amino)phenyl-4-aminobenzoate, (2-ethylbenzyl-4-amino)phenyl-4-aminobenzoate, (3-ethylbenzyl-4-amino)phenyl-4-aminobenzoate, (2-propylbenzyl-4-amino)phenyl-4-aminobenzoate, (3-propylbenzyl-4-amino)phenyl-4-aminobenzoate(2-Methoxybenzyl-4-amino)phenyl-4-aminobenzoate, (3-Methoxybenzyl-4-amino)phenyl-4-aminobenzoate, (2-Ethoxybenzyl-4-amino)phenyl-4-aminobenzoate, (3-Ethoxybenzyl-4-amino)phenyl-4-aminobenzoate, (2-Aminobenzyl-4-amino)phenyl-4-aminobenzoate, (3-Aminobenzyl-4-amino)phenyl-4-aminobenzoate, (2-Nitrobenzyl-4-amino)phenyl-4-aminobenzoate, (3-Nitrobenzyl-4-amino)phenyl-4-aminobenzoate Benzoate esters, (2-cyanobenzyl-4-amino)phenyl-4-aminobenzoate, (3-cyanobenzyl-4-amino)phenyl-4-aminobenzoate, (2-benzyloxy-4-amino)phenyl-4-aminobenzoate, (3-benzyloxy-4-amino)phenyl-4-aminobenzoate, (2-methylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-methylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (2-ethylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-ethylbenzyloxy-4-amino)phenyl-4- Aminobenzoate, (2-propylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-propylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (2-methoxybenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-methoxybenzyloxy-4-amino)phenyl-4-aminobenzoate, (2-ethoxybenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-ethoxybenzyloxy-4-amino)phenyl-4-aminobenzoate, 4-(4-aminophenoxy)-3-methylaniline, 4-(4-aminophenoxy)-2 4-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)-2-isobutylaniline.

[0097] 4-(4-aminophenoxy)-3-pentylaniline, 4-(4-aminophenoxy)-2-pentylaniline, 4-(4-aminophenoxy)-3-hexylaniline, 4-(4-aminophenoxy)-2-hexylaniline, 4-(4-aminophenoxy)-3-(trifluoromethyl)aniline, 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 Amines, 4-(4-aminophenoxy)-3-butoxyaniline, 4-(4-aminophenoxy)-2-butoxyaniline, 4-(4-aminophenoxy)-3-phenylaniline, 4-(4-aminophenoxy)-2-phenylaniline, 4-(4-aminophenoxy)-3-methylphenylaniline, 4-(4-aminophenoxy)-2-methylphenylaniline, 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 Amines, 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-(phenylethyl)phenylaniline, 4-(4-aminophenoxy) 2-(phenylethyl)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)-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, 4-((4-aminophenyl)thio)-3-methoxyphenylaniline, 4-((4-aminophenyl)thio)-3-propoxy ...-3-propoxyaniline, 4-((4-aminophenyl)-3-propoxyaniline)-3-propoxyaniline, 4-((4-aminophenyl)-3-propoxyaniline)-3-propoxy (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)-2-butylaniline, 4-((4-aminophenyl)methyl)-2-butylaniline, 4-((4-aminophenyl)methyl)-2-butylaniline, 4-((4-aminophenyl)methyl)-2-ethyl ... 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)-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)methyl ketone, (4 (4-amino-2-ethylphenyl)(4-aminophenyl) methyl ketone, (4-amino-2-propylphenyl)(4-aminophenyl) methyl ketone, (4-amino-2-isopropylphenyl)(4-aminophenyl) methyl ketone, (4-amino-2-butylphenyl)(4-aminophenyl) methyl ketone, (4-amino-2-(trifluoromethyl)phenyl)(4-aminophenyl) methyl ketone, 4-amino-2-methoxyphenyl)(4-aminophenyl) methyl ketone, 4-amino-2-ethoxyphenyl)(4-aminophenyl) methyl ketone, (4-amino-2-(phenyl)phenyl)(4-aminophenyl) methyl ketone, (4-amino-2-(methoxyphenyl)phenyl)(4-aminophenyl) methyl ketone, but not limited to these.

[0098] Here, a polymeric compound containing a polyimide precursor having the structural unit shown in the above general formula (5) can be obtained, for example, by reacting a tetracarboxylic acid diester compound shown in the above general formula (15) with a diamine shown in the above general formula (16) in the presence of a condensing agent. That is, the tetracarboxylic acid diester compound represented by the above general formula (15) is used in the reaction in a state dissolved in the above reaction solvent. In the reaction solution, a known dehydrating condensing 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 and mixed. After the tetracarboxylic acid diester compound represented by the above general formula (15) is made into a polyanhydride, a substance obtained by dissolving or dispersing the diamine represented by the above general formula (16) in another solvent is added dropwise to it to cause polycondensation. Thus, a polymeric compound having a polyimide precursor containing the structural unit represented by the above general formula (2) can be obtained.

[0099] In addition, as another method for reacting the tetracarboxylic acid diester compound of the above general formula (15) with the diamine compound of the above general formula (16) to obtain a polymeric compound having a polyimide precursor containing the structural unit of the above general formula (5), the following method can be listed: the tetracarboxylic acid diester compound of the above general formula (15) is converted into chlorothiazide using a chlorinating agent such as thionyl chloride or dichlorooxalic acid, and then reacted with the diamine of the above general formula (16) to carry out the synthesis.

[0100] In the reaction of converting the above-mentioned tetracarboxylic acid diester to acetic acid using a chlorinating agent, a basic compound can be used. Examples of such basic compounds include pyridine, 4-dimethylaminopyridine, and triethylamine.

[0101] Then, the acetic acid of the obtained tetracarboxylic acid diester is reacted with the diamine shown in the above general formula (16) under the presence of an alkaline catalyst, thereby obtaining a polymeric compound having the target polyimide precursor containing the structural unit shown in the above general formula (5). At this time, examples of alkaline catalysts include pyridine, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[4.3.0]non-5-ene.

[0102] In the method for preparing a polymer having a polyimide precursor, the solvent used in the chloropolymerization process is preferably a solvent that sufficiently dissolves the tetracarboxylate diester and its chloropolymer, and more sufficiently dissolves the polymer obtained by the polycondensation reaction of the tetracarboxylate diester and its chloropolymer with a diamine. The same solvent as described above can be used. Specifically, examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphatrimethylenetriamine, and γ-butyrolactone. In addition to polar solvents, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons can also be used. Examples of such organic solvents include 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-dichloroethane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, and xylene. These organic solvents can be used alone or in combination of two or more.

[0103] In addition, as described above, the polymer compound containing the polyimide precursor used in the negative photosensitive resin composition of the present invention may contain, in addition to the structural unit shown in the general formula (5) above, the structural unit shown in the general formula (10) below. [Chemical 32] In the formula, X1 and Y1 are the same as described above.

[0104] A polymer containing the structural unit shown in the aforementioned general formula (10) can be obtained by reacting a tetracarboxylic dianhydride shown in the following general formula (19) with a diamine shown in the following general formula (20). First, acetic acid is synthesized by reacting the tetracarboxylic dianhydride shown in the following general formula (19) with the diamine shown in the following general formula (20), followed by chemical acetilimation and acetilimation by heating and dehydration, thereby obtaining a polymer containing the structural unit (10).

[0105] The aforementioned structural unit (10) can be manufactured by dissolving a diamine in a high-boiling-point and highly polar solvent such as γ-butyrolactone or N-methyl-2-pyrrolidone, adding an acid anhydride, and reacting at 0°C to 80°C, preferably 10°C to 50°C, to produce acetic acid. In chemical acetilimation, for example, by adding acetic anhydride and pyridine, a acetilimation reaction is carried out. In acetilimation by heating and dehydration, a non-polar solvent such as xylene is added, and the mixture is heated to 100°C to 200°C, preferably 130°C to 180°C, while removing water from the reaction system, the acetilimation reaction is carried out. [Chemical 33] In the formula, X1 is the same as above. [Chemical 34] In the formula, Y1 is the same as above.

[0106] As for the tetracarboxylic dianhydride represented by the aforementioned general formula (19), the examples shown in the tetracarboxylic dianhydride represented by the aforementioned general formula (17) can be cited as ideal examples.

[0107] As a diamine represented by the aforementioned general formula (20), examples of diamines represented by the aforementioned general formula (16) can be cited as ideal examples.

[0108] In addition, as described above, the polymer compound containing a polyimide precursor used in the negative photosensitive resin composition of the present invention may contain, in addition to the structural unit shown in the general formula (5) above, the structural unit shown in the general formula (11) below. [Chemical 35] In the formula, X2 and Y2 are the same as described above.

[0109] A polymer containing the structural unit shown in the above general formula (11) can be obtained by performing the same reaction steps as those for the above structural unit (5). That is, it can be obtained by reacting a dicarboxylic acid compound shown in the following general formula (21) in the presence of a dehydrating condensing agent, converting it to chloroacetate using a chlorinating agent, and then reacting it with the diamine shown in the above general formula (22). [Chemical 36] In the formula, X2 is the same as above. [Chemical 37] In the formula, Y2 is the same as above.

[0110] Examples of dicarboxylic acid compounds represented by the above 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, octafluoroadipic acid, Pimelic acid, 2,2,6,6-tetramethyl pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azeladic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid Diacid, eicosanedioic acid, hexadecanedioic acid, docosanedioic acid, triicosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, heptacosanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontandioic acid, triacontandioic acid, triacontanedioic acid, diglycolic acid, etc.

[0111] Furthermore, as dicarboxylic acid compounds having an aromatic ring, examples 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'-diphenyl ketone dicarboxylic acid, 3,4'-diphenyl ketone dicarboxylic acid, 3,3'-diphenyl ketone dicarboxylic acid, 4,4'-hexafluoroisopropylidene dibenzoic acid, 4,4'-dicarboxylated diphenylamide, 1 4-Phenylenediethane, 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)sulfonate, 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-naphthalenedicarboxylic acid, etc., but not limited to these. Furthermore, they can be used alone or in combination.

[0112] As a diamine represented by the aforementioned general formula (22), examples of diamines represented by the aforementioned general formula (16) can be cited as ideal examples.

[0113] In addition, as described above, the polymer compound containing a polyimide precursor used in the negative photosensitive resin composition of the present invention may contain, in addition to the structural unit shown in the general formula (5) above, the structural unit shown in the general formula (12) below. [Chemical 38] In the formula, X3 and Y3 are the same as described above.

[0114] For a polymer containing the structural unit shown in the above general formula (12), the dicarboxylic acid compound shown in the following general formula (23) is reacted in the presence of a dehydrating condensing agent, and then converted to acetic acid using a chlorinating agent. This is followed by reaction with the dihydroxydiamine compound shown in the following general formula (24) to synthesize hydroxyacetic acid (polyazolium precursor). After a heating and dehydration step, an acetic acid ring is formed, thereby obtaining a polymer containing the structural unit shown in the above general formula (12). [Chemical 39] In the formula, Y3 is the same as above. [Chemical 40] In the formula, X3 is the same as above.

[0115] As a dicarboxylic acid compound represented by the above general formula (23), the example shown in the dicarboxylic acid compound represented by the above general formula (21) can be cited as an ideal example.

[0116] Dihydroxydiamine compounds represented by the above general formula (24) include, for example: 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 Examples of '-(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)cyclohexane, 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane, 4,4'-(1,4-phenylbis(oxy))bis(2-aminophenol), 9,9-bis(3-amino-4-hydroxyphenyl)cyclohexane, etc., but not limited to these. Furthermore, they can be used alone or in combination.

[0117] (Molecular weight of polymer and introduction of capping agent) The preferred molecular weight of the above-mentioned polymer compound is 5,000 to 100,000, more preferably 7,000 to 50,000. If the molecular weight is 5,000 or higher, it is easy to form a film of the negative photosensitive resin composition of the present invention using the above-mentioned polymer on the substrate to the desired film thickness. If the molecular weight is 100,000 or lower, the viscosity of the aforementioned negative photosensitive resin composition becomes moderate, and film formation is not a problem.

[0118] For the above-mentioned polymer, in order to control the molecular weight in the polycondensation reaction and suppress the change in molecular weight of the obtained polymer over time, i.e., gelation, an end-capping agent can be used to cap both ends. Examples of end-capping agents that react with dianhydrides include monoamines and monohydric alcohols. Examples of end-capping agents that react with diamines include acid anhydrides, monocarboxylic acids, monochlorodimethylamine compounds, monoreactive ester compounds, dicarbonates, and vinyl ethers. In addition, by reacting the end-capping agent, various organic groups can be introduced as end groups.

[0119] Monoamines that can be used as end-capping agents for anhydride groups, such as 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, 2, 4-Dioxy-6-amino-sym-triazine (2,4-dioxy-6-amino-sym-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 The following are examples of naphthalene-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 to these. They can be used alone or in combination.

[0120] On the other hand, monohydric alcohols that can be used as end-capping agents for 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-hexadecanol, 1-heptadecanol, 2-hepta ... 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, isononol, 3,7-dimethyl... 3-Octanol, 2,4-dimethyl-1-heptanol, 2-heptadecylol, 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, monohydroxymethylcyclopentane, monohydroxymethyldicyclopentane, monohydroxymethyltricyclodecane, norbenzyl alcohol, pinoresinol, etc., but not limited to these. Furthermore, one of them may be used alone, or two or more may be used in combination.

[0121] Examples of acid anhydrides, monocarboxylic acids, monochloro compounds, and monoactive ester compounds used as end-capping agents for amino groups include phthalic anhydride, maleic anhydride, nalidix anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, 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, and 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 others, as well as monochlorocarboxylic acids whose carboxyl groups are acetylated, and terephthalic acid, phthalic acid, and malonic acid, etc. Monochloro compounds obtained by acetylchlorination of only the single carboxyl group of dicarboxylic acids such as acids, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norcamphen-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 monochloro compounds with N-hydroxybenzotriazole and N-hydroxy-5-norcamphen-2,3-dimethylimidene.

[0122] Examples of dicarbonate compounds used as end-capping agents for the amino group include dibutyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.

[0123] Examples of vinyl ether compounds used as end-capping agents for the amino group include butyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, tributyl vinyl ether, benzyl vinyl ether, etc.

[0124] Other compounds used as end-capping agents for the amino end group include benzoyl chloride, methyl chloroformate, 2,2,2-trichloroethyl chloroformate, tributyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, benzyl chloroformate, allyl chloroformate, ethyl chloroformate, isopropyl chloroformate, butyl isocyanate, 1-naphthyl isocyanate, octadecyl isocyanate, phenyl isocyanate, methanesulfonyl chloride, p-toluenesulfonyl chloride, etc.

[0125] Relative to the total amount of tetracarboxylic acid dianhydride and dicarboxylic acid components, the proportion of the capping agent at the anhydride end is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, and even more preferably 5 to 20 mol%. Relative to the diamine component, the proportion of the capping agent at the amino end is preferably in the range of 0.1 to 100 mol%, particularly preferably 5 to 90 mol%. Alternatively, multiple different end groups can be introduced by reacting multiple capping agents.

[0126] [(D) Component] Next, the organic compound represented by the following general formula (1) of the (D) component of the present invention will be described. [Chemical 41] In the formula, T represents any structure in the following general formulas (2) to (4), and W represents an alkyl or aryl group that can also be substituted by an alkoxy group having 4 to 15 carbon atoms. [Chemical 42] In the formula, V represents a divalent organic group, and * represents a bond. [Chemical 43] In the formula, Q represents a halogen atom or a nitro group, and RC represents a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms. n represents an integer from 3 to 5 when Q is a halogen atom, and 1 when Q is a nitro group. * represents a bond. [Chemical 44] In the formula, Ar represents a substituted or unsubstituted aromatic ring structure, or a heterocyclic structure having heteroatoms, and * represents a bond.

[0127] In particular, the above general formula (2) is preferably the structure shown in the following general formula (2-1). [Chemical 45] In the formula, Ra and Rb represent hydrogen atoms, straight-chain, branched or cyclic alkyl groups having 1 to 15 carbon atoms, or aryl groups having 6 to 15 carbon atoms. Ra and Rb can also be bonded to each other and form a ring together with the carbon atoms they are bonded to. * indicates a bond.

[0128] The above general formula (2) in the above general formula (1) as component (D) is an ideal example of an organic compound or structure represented by the above general formula (2) or (2-1), and the structures of the following general formulas (2-2) and (2-3) can be cited. [Chemical 46] In the formula, * represents a bond. [Chemical 47] In the formula, * represents a bond.

[0129] Then, an organic compound in which T in the above general formula (1) of component (D) comprises the structure shown in the following general formula (3) will be described. [Chemical 48] In the formula, Q represents a halogen atom or a nitro group, RC represents a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms. n represents an integer from 3 to 5 when Q is a halogen atom, and 1 when Q is a nitro group. * represents a bond.

[0130] (D) The T in the above general formula (1) of the component can be listed as a preferred structure of the above general formula (3) as the following general formula (3-4). [Chemical 49] In the formula, * represents a bond.

[0131] Furthermore, the above general formula (3) is preferably the structure shown in formula (3-1) or (3-2) below. [Chemical 50] In the formula, * represents a bond. [Chemical 51] In the formula, * represents a bond.

[0132] (D) In ​​the above general formula (1) of the component, T shown in the above general formula (3) is an organic compound shown in the following general formula (3-1) or (3-2). From the perspective of the ease of obtaining the raw materials, the safety of the compound, and the low toxicity, it can be listed as a further preferred example.

[0133] If the aforementioned general formula (3) is the structure shown in the above general formula (3-1) or (3-2), then the hydroxyl groups of 4-nitrophenol and pentafluorophenol, which are active esterifying agents that promote amide esterification reaction, are protected by the third butoxycarbonyl (Boc group) and benzyloxycarbonyl protecting group (Z group) described above, which can make the photosensitive resin composition containing polyamide precursor resin have good storage stability.

[0134] Then, an organic compound in which T in the above general formula (1) of component (D) contains the structure shown in the following general formula (4) will be described. [Chemical 52] In the formula, Ar represents a substituted or unsubstituted aromatic ring structure or a heterocyclic structure having heteroatoms, and * represents a bond.

[0135] (D) The T in the above general formula (1) of the component can be listed as a preferred structure of the above general formula (4) as the following general formula (4-2). [Chemical 53] In the formula, * represents a bond.

[0136] Furthermore, in the above general formula (1) of component (D), T shown in the above general formula (4) is preferably the structure shown in the following general formula (4-1). [Chemical 54] In the formula, Rd represents a straight-chain, branched, or cyclic alkyl group having 1 to 15 carbon atoms or halogen atoms, or an aryl group having 6 to 15 carbon atoms, and k represents an integer from 0 to 4. * represents a bond.

[0137] T in the above general formula (1) as component (D), the specific structure shown in the above general formula (4-1) can be specifically exemplified by the structure shown in the following general formula (4-3). [Chemical 55] In the formula, * represents a bond.

[0138] (D) The T in the above general formula (1) of the component is an organic compound with the structure shown in the above general formula (4-3). From the perspective of the ease of obtaining the raw materials and the preservation stability of the negative photosensitive resin composition of the present invention containing the organic compound is not easily deteriorated, it is even more preferable.

[0139] Next, W in the above general formula (1) of component (D) will be explained. W in the above general formula (1) of component (D) is preferably a third butyl group. When W is a third butyl group, it indicates a compound in which the organic group shown in general formula (1) is protected with a third butoxycarbonyl group (N-Boc group). The third butoxycarbonyl group (N-Boc group) is deprotected in the heating step of the curing reaction in the range of 100°C to 150°C to generate a hydroxyl compound that can promote the cyclocloning reaction of amide, i.e., an active esterifying agent, and thus amide imidization can be carried out at temperatures below 200°C.

[0140] Furthermore, in this case, W in the general formula (1) of component (D) is preferably benzyl. When W is benzyl, it indicates a compound in which the organic compound shown in the above general formula (1) is protected with a benzyloxycarbonyl protecting group (Z group). The benzyloxycarbonyl protecting group (Z group) is deprotected in the heating step of the curing reaction in the range of 120°C to 190°C, which can generate an active esterifying agent that can promote the cyclocloning reaction of amide, and thus amide oxidation can be carried out at temperatures below 200°C.

[0141] More ideal organic compounds represented by the above formula (1) can be exemplified by the following compounds. [Chemistry 56][Chemistry 57]

[0142] The above-mentioned organic compound is preferably used as component (D) of the negative photosensitive resin composition of the present invention, from the perspective that the organic compound or the raw material of the organic compound can be easily obtained.

[0143] The organic compound represented by the above general formula (1) can be obtained, for example, by the method shown in the following reaction formula, but is not limited thereto. [Chemistry 58]

[0144] In this formula, T and W are the same as above. A is a halogen atom or a base as shown in the following formula (27). [Chem. 59] Here, the dashed line represents an atomic bond. W is the same as above.

[0145] More specifically, when T of the above general formula (1) of the organic compound that is component (D) is the above general formula (2) or (2-1), it can be obtained by the method shown in the following reaction formula. [Chemical 60] In the formula, V, W and A are the same as above. [Chemical 61] In the formula, W, A, Ra and Rb are the same as above.

[0146] Furthermore, more specifically, when T of the above general formula (1) of the organic compound that is component (D) is the above general formula (3), (3-1) or (3-2), it can be obtained by the method shown in the following reaction formula. [Chemical 62] In the formula, Q, W and A are the same as above. [Chemical 63] In the formula, Q, W and A are the same as above. [Chemical 64] In the formula, W and A are the same as above.

[0147] Furthermore, more specifically, when T of the above general formula (1) of the organic compound that is component (D) is the above general formula (4), (4-1) or (4-2), it can be obtained by the method shown in the following reaction formula. [Chemical 65] In the formula, Ar, W, and A are the same as above. [Chemical 66] In the formula, W and A are the same as above.

[0148] The organic compound of general formula (1) that is the component (D) of the negative photosensitive resin composition of the present invention can be obtained by reacting the hydroxyl compound of general formula (1) having a structure of T in the above reaction formula with a halocarbonate (in the above reaction formula, A in formula (26) represents a halogen atom) or by reacting the hydroxyl compound of general formula (1) having a structure of T in the above reaction formula with a dicarbonate (in the above reaction formula, A represents a compound of formula (27)).

[0149] When the organic compound of the above general formula (1) which is the component (D) of the negative photosensitive resin composition of the present invention is an organic compound of the third butyl group, it can be obtained by reacting the above general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4) and (25-4-1) of the above general formula (1) with di-tert-butyl dicarbonate (in the above reaction formula, A of formula (26) represents the compound of formula (27) and W represents the third butyl group).

[0150] When W is an organic compound of the above general formula (1) that is the component (D) of the negative photosensitive resin composition of the present invention, the organic compound of the above general formula (1) having a structure of T can be reacted with the benzyloxycarbonyl halide (the above reaction formula) by the above general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4) and (25-4-1) of the above general formula (1) with the benzyloxycarbonyl halide (the above reaction formula). In the above reaction formula (26), A represents a halogen atom and W represents a benzyl compound, or the above general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4) and (25-4-1) of the above general formula (1) with the structure of T are reacted with dibenzyl carbonate (in the above reaction formula, A of formula (26) represents formula (27) and W represents a benzyl compound).

[0151] The reaction of the organic compound of the above general formula (1) which is the component (D) of the negative photosensitive resin composition of the present invention is carried out by using the above general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4) and (25-4-1) of the hydroxy compound having the T structure in the above reaction formula with a halocarbonate. In the case of solvent-free solvent or solvents such as dichloromethane, acetonitrile, diethyl ether, tetrahydrofuran, N,N-dimethylformamide, toluene, hexane, etc., the above hydroxy compound, benzyl chlorocarbonate, 4-methoxybenzyl chlorocarbonate, etc., the corresponding halocarbonate, triethylamine, pyridine, 2,6-dimethylpyridine, N,N-dimethylaniline and other bases are added sequentially or simultaneously, and the reaction is carried out by cooling or heating as needed.

[0152] The reaction of the organic compound of the above general formula (1) which is the component (D) of the negative photosensitive resin composition of the present invention is carried out by using the above general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4) and (25-4-1) of the hydroxyl compound having the T structure in the above reaction formula with dicarbonate. The reaction can be carried out by adding the above hydroxyl compound, dicarbonate, triethylamine, pyridine, 2,6-dimethylpyridine, N,N-dimethylaniline and other bases in sequence or simultaneously in solvents such as dichloromethane, acetonitrile, diethyl ether, tetrahydrofuran, N,N-dimethylformamide, toluene, hexane and the like. Cooling or heating is performed as needed.

[0153] The amount of halocarbonate and diester shown in the above reaction formula (26) varies depending on the conditions. For example, it is preferably 1.0 to 5.0 mol relative to 1 mol of the above hydroxyl compound, and particularly preferably 1.0 to 2.0 mol. The amount of base varies depending on the conditions. For example, it is preferably 0 to 5.0 mol relative to 1 mol of the above hydroxyl compound, and particularly preferably 0 to 2.0 mol. The reaction time, from the point of view of yield, is expected to be about 0.5 to 24 hours, typically monitored by gas chromatography (GC) or silicone thin-layer chromatography (TLC) to complete the reaction. The above general formula (1) organic compound of component (D) of the negative photosensitive resin composition of the present invention, which is intended to be obtained from the reaction mixture by conventional aqueous treatment, can be purified by conventional methods such as distillation, chromatography, and recrystallization as needed. Alternatively, sometimes post-treatment of the aqueous system can be omitted, and the salts produced in the reaction can be filtered and separated, or the reaction solution can be directly supplied to the purification process.

[0154] On the other hand, it is preferable to contain 1 to 10 parts by mass of the organic compound of component (D) relative to 100 parts by mass of the aforementioned component (A). If the organic compound of component (D) is 10 parts by mass or less, the added organic compound of component (D) will not act as a plasticizer, will not cause thermal deformation or thermal flow of the formed pattern, and will not impair the pattern formation. In addition, the glass transition point (Tg.) of the obtained cured film will not decrease after curing. The reason for requiring a high glass transition point (Tg.) of the obtained cured film is the requirement for heat resistance in the steps of manufacturing electronic components using interlayer insulating films and surface protective films that employ the obtained cured film.

[0155] The negative photosensitive resin composition of the present invention is composed of: a negative photosensitive resin composition comprising: (A) a polymeric compound having a polyimide precursor structure, (C) a photopolymerization initiator, (D) an organic compound represented by general formula (1), and (E) a solvent.

[0156] (A) The polymeric compound having a polyimide precursor structure and (D) the organic compound represented by general formula (1) have been described above. Then, the photopolymerization initiator (C) will be explained.

[0157] [(C) Component] As the photopolymerization initiator of (C), any compound previously used as a photopolymerization initiator for UV curing can be selected. For example: benzophenone, methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fumonisin and other benzophenone derivatives; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexylphenyl ketone and other acetophenone derivatives; thioxanthone, 2-methylthioxanthrone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives; phenylethylene glycol, phenylethylene glycol dimethyl ketal, phenylethylene glycol-β-methoxyethyl acetal and other phenylethylene glycol derivatives; benzoin, benzoin methyl ether and other benzoin derivatives; 1-phenyl-1,2-butane Oximes such as diketone-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime; N-aryl glycine acids such as N-phenylglycine; peroxides such as benzoyl peroxide; and aromatic biimidazoles are preferred, but not limited to these. Furthermore, they can be used alone or in combination of two or more. Of the photopolymerization initiators mentioned above (C), oximes are preferred, especially from the viewpoint of photosensitivity.

[0158] The amount of photopolymerization initiator (C) is 0.1 to 20 parts by mass relative to 100 parts by mass of the polymer of the present invention having polyimide precursor structural units as the base resin (A), and preferably 2 to 15 parts by mass from the viewpoint of photosensitivity characteristics. By incorporating 0.1 parts or more of the photopolymerization initiator (C) relative to 100 parts by mass of the base resin (A), the photosensitivity of the photosensitive resin composition is excellent; on the other hand, by incorporating 20 parts or less, the thick film curing properties of the photosensitive resin composition are excellent.

[0159] [(E) Composition] Next, the solvent for (E) of the negative photosensitive resin composition of the present invention will be described. The solvent may be selected without limitation, as long as it can dissolve the base resin of (A), the photopolymerization initiator of (C), and the organic compound of general formula (1) of (D). Examples of solvents for (E) 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; and 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, tributyl acetate, tributyl propionate, propylene glycol monotertyl ether acetate, and γ-butyrolactone. One or more of these solvents may be used. In particular, ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, or mixtures thereof are preferred solvents.

[0160] The amount of the solvent is preferably 50 to 2,000 parts by mass relative to the total amount of the base resin (A) and the photopolymerization initiator (C) in 100 parts by mass, and particularly preferably 100 to 1,000 parts by mass.

[0161] [(B) Composition] Furthermore, the negative photosensitive resin composition of the present invention is preferably a polymeric compound containing (B) having two or more vinyl unsaturated groups.

[0162] By using a crosslinking agent containing two or more photopolymerizable unsaturated bonds in one molecule, the photopolymerization-based crosslinking of component (A) in the exposed portion can be promoted, thereby improving the contrast between the exposed portion and the unexposed portion.

[0163] As (B) a polymerizable compound having two or more vinyl unsaturated groups, it is preferably a (meth)acrylic acid compound, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate (the number of each ethylene glycol unit is 2 to 20), polyethylene glycol dimethacrylate (the number of each ethylene glycol unit is 2 to 20), poly(1,2-propanediol) diacrylate, poly(1,2-propanediol) dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolpropane tetraacrylate. Tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, glyceryl diacrylate, glyceryl dimethacrylate, methylene diacrylamide, N-hydroxymethylacrylamide, ethylene glycol diglycidyl ether-methacrylic acid adduct, glyceryl diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-methacrylic acid adduct, N,N'-bis(2-methacryloxyethyl)urea, etc., but not limited to these.

[0164] Compared to 100 parts by mass of the polymer compound having the structural unit of the polyimide precursor of the present invention, (B) the polymeric compound having two or more vinyl unsaturated groups is preferably blended in the range of 1 to 100 parts by mass, more preferably in the range of 3 to 50 parts by mass. If it deviates from the range of 1 to 100 parts by mass, the target effect may not be obtained, or it may have an adverse effect on the developability. Furthermore, as a comonomer, one compound may be used, or multiple compounds may be used in combination.

[0165] [(F) Component] The negative photosensitive resin composition of the present invention may further include (F) one or more crosslinking agents selected from formaldehyde or formaldehyde-alcohol modified amine condensates, phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups per molecule, compounds in which the hydrogen atoms of the hydroxyl groups of polyphenols are replaced with glycidyl groups, compounds in which the hydrogen atoms of the hydroxyl groups of polyphenols or polyols are replaced with substituents shown in the following formula (F-1), and compounds containing two or more nitrogen atoms of glycidyl groups shown in the following formula (F-2) as thermal crosslinking agent (F) component. [Chemical 67] In the formula, the dashed line represents an atomic bond, Rf is a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and c is 1 or 2.

[0166] Examples of the above-mentioned amino condensates modified with formaldehyde or formaldehyde-alcohol include melamine condensates modified with formaldehyde or formaldehyde-alcohol, or urea condensates modified with formaldehyde or formaldehyde-alcohol.

[0167] To prepare melamine condensates modified with formaldehyde or formaldehyde-alcohol, for example, the melamine monomer is first hydroxymethylated and modified with formalin according to known methods, or further alkoxylated and modified with an alcohol to obtain the modified melamine shown in the following general formula (23). Furthermore, the alcohol is preferably a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms.

[0168] [Chemical 68] In the formula, R5 can be the same or different, and can be hydroxymethyl, alkoxymethyl containing alkoxy groups of 1 to 4 carbon atoms, or a hydrogen atom, but at least one of them is hydroxymethyl or the above-mentioned alkoxymethyl. Examples of the above-mentioned R5 include alkoxymethyl such as hydroxymethyl, methoxymethyl, ethoxymethyl, and hydrogen atoms.

[0169] Specifically, the modified melamine represented by the above general formula (23) can be listed as trimethoxymethyl monohydroxymethyl melamine, dimethoxymethyl monohydroxymethyl melamine, trihydroxymethyl melamine, hexahydroxymethyl melamine, hexamethoxymethyl melamine, etc. Then, according to conventional methods, the modified melamine represented by the above general formula (23) or its polymer (e.g., dimer, trimer, or other oligomers) is subjected to addition condensation polymerization with formaldehyde until the desired molecular weight is achieved, thereby obtaining a melamine condensate modified with formaldehyde or formaldehyde-alcohol.

[0170] Furthermore, the preparation of the above-mentioned urea condensate modified with formaldehyde or formaldehyde-alcohol can be achieved, for example, by modifying the urea condensate of the desired molecular weight with formaldehyde through hydroxymethylation, or by further modifying it with an alcohol through alkoxylation, according to known methods. Specific examples of the above-mentioned urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensates, ethoxymethylated urea condensates, propoxymethylated urea condensates, etc. Also, one or more of these modified melamine condensates and modified urea condensates can be used in combination.

[0171] Then, examples of phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups per molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and compounds shown in formulas (F-3) to (F-8) below. [Chemical 69]

[0172] Furthermore, one or more of the above-mentioned crosslinking agents may be used.

[0173] On the other hand, compounds obtained by replacing the hydrogen atom of the hydroxyl group of a polyol with an epoxypropyl group are, for example, 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. Ideal examples of compounds in which the hydrogen atom of the hydroxyl group of a polyphenol is replaced with an epoxypropyl group are compounds shown in formulas (F-9) to (F-15) below. [Chemical 70] In these formulas, d is 2 ≤ d ≤ 3.

[0174] In addition, preferred examples of compounds other than those in formulas (F-9) to (F-15) mentioned above include Epiclon 850-S, Epiclon HP-4032, Epiclon HP-7200, Epiclon HP-820, Epiclon HP-4700, Epiclon EXA-4710, Epiclon HP-4770, Epiclon EXA-859 CRP, Epiclon EXA-4880, Epiclon EXA-4850, Epiclon EXA-4816, Epiclon EXA-4822 (the above are trade names, manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.), RIKARESIN BPO-20E, and RIKARESIN. BEO-60E (the above are product names, manufactured by Shin Nippon Rikka Co., Ltd.), EP-4003S, EP-4000S, EP-4000S, EP-4000L (the above are product names, manufactured by ADEKA Co., Ltd.), jER828EL, YX7105 (the above are product names, manufactured by Mitsubishi Chemical Co., Ltd.), etc.

[0175] One or two of these compounds that replace the hydroxyl group of a polyphenol with an epoxy propoxy group (compounds that replace the hydrogen atom of the hydroxyl group of a polyphenol with an epoxy propoxy group) can be used as crosslinking agents.

[0176] As a compound in which the hydrogen atom of the hydroxyl group of a polyphenol is replaced by a substituent as shown in the following formula (F-1), examples can be given of compounds containing two or more of such substituents as shown in the following formula (F-16). [Chemical 71] In the formula, the dashed line represents a bond. [Chemical 72] In the formula, e is 1 ≤ e ≤ 3.

[0177] In addition, ideal examples of compounds other than those in formulas (F-9) to (F-16) mentioned above include: 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanebutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenediacarboxylic acid-bis[(3-ethyl-3-oxetanebutyl)methyl] ester, and the ARON OXETANE series manufactured by Toa Synthetic Co., Ltd.

[0178] On the other hand, as a compound containing two or more nitrogen atoms having an epoxypropyl group as shown in the following formula (F-2), the compound shown in the following formula (F-17) can be cited. [Chemical 73] In the formula, the dashed line represents an atomic bond, Rf is a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and c is 1 or 2. [Chemical 74] In the formula, L represents a straight-chain, branched, or cyclic alkyl group having 2 to 12 carbon atoms, or a divalent aromatic group. Also, L here applies only in the above formula.

[0179] As a compound represented by the above formula (F-17), for example, compounds represented by the following formulas (F-18) to (F-21) can be exemplified. [Chemical 75]

[0180] On the other hand, as a compound containing two or more nitrogen atoms having an epoxypropyl group as shown in the above formula (F-2), the compounds shown in the following formulas (F-22) and (F-23) are preferred. [Chemical 76]

[0181] These compounds containing two or more nitrogen atoms with glycidyl groups as shown in the above formula (F-2) can use one or two as crosslinking agents.

[0182] The epoxy group has a large ring strain and high reactivity, while the oxetane group is highly basic and readily bonds with acids. It has been reported that by combining an oxetane group with the epoxy group, the reactivity of cationic polymerization is significantly improved.

[0183] Component (F) is a component that, after the pattern of the negative photosensitive resin composition of the present invention is formed, induces a cross-linking reaction during post-curing, thereby further improving the strength of the cured product. From the viewpoint of photocurability and heat resistance, the weight-average molecular weight of such component (F) is preferably 150 to 10,000, and particularly preferably 200 to 3,000.

[0184] In the negative photosensitive resin composition of the present invention, the amount of component (F) is preferably 0.5 to 100 parts by mass relative to 100 parts by mass of component (A), and particularly preferably 1 to 80 parts by mass.

[0185] [(G) Component] The negative photosensitive resin composition of the present invention preferably further contains an antioxidant (G). By using an antioxidant containing component (G), excessive cross-linking between components (A) or between components (A) and (B) during patterning can be suppressed, thereby improving contrast. Furthermore, by providing rust prevention for metallic materials, metal oxidation caused by external moisture, photoacid generators, thermal acid generators, etc., as well as associated reduction in adhesion and peeling, can be suppressed.

[0186] If specific examples of (G) antioxidants that may be used herein are given, hindered phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferably listed. However, they are not limited to these. In addition, these (G) antioxidants may be used alone or in combination of two or more.

[0187] Among the specific examples of the antioxidants described above (G), hindered phenolic antioxidants may be further illustrated by pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan, Irganox 1010), thiodiethyl bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan, Irganox 1035), octadecyl[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan, Irganox 1076), octyl 1-3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamate (manufactured by BASF Japan, Irganox 1135), and 4,6-bis(octylthiomethyl-o-cresol) (BASF Japan, Irganox). 1520L), Sumilizer GA80 (manufactured by Sumitomo Chemical Co., Ltd., trade name), ADK STAB AO-20 (manufactured by ADEKA Co., Ltd., trade name), ADK STAB AO-30 (manufactured by ADEKA Co., Ltd., trade name), ADK STAB AO-40 (manufactured by ADEKA Co., Ltd., trade name), ADK STAB AO-50 (manufactured by ADEKA Co., Ltd., trade name), ADK STAB AO-60 (manufactured by ADEKA Co., Ltd., trade name), ADK STAB AO-80 (manufactured by ADEKA Co., Ltd., trade name), ADK STAB AO-330 (manufactured by ADEKA Co., Ltd., trade name), and hindered phenolic antioxidants as described in International Publication No. 2017 / 188153, etc.

[0188] Among the specific examples of the antioxidants described above (G), phosphorus-based antioxidants may be further exemplified as triphenyl phosphite, tri(methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tri(2-ethylhexyl) phosphite, tri(nonylphenyl) phosphite, tri(octylphenyl) phosphite, tri[decyl poly(oxyethyl) phosphite, tri(cyclohexylphenyl) phosphite, tricyclohexyl phosphite, tri(decyl) thiophosphite, triisodecyl thiophosphite, etc. Phosphine bis(2-ethylhexyl) ester, phenyl diisodecyl phosphite, tetradecyl poly(oxyethyl)-bis(ethylphenyl) ester, phenyl dicyclohexyl phosphite, phenyl diisooctyl phosphite, phenyl di(tridecyl) ester, diphenyl cyclohexyl phosphite, diphenyl isooctyl phosphite, diphenyl-2-ethylhexyl phosphite, diphenyl isodecyl phosphite, diphenyl cyclohexylphenyl phosphite, diphenyl thiophosphite (tridecyl) ester, etc.

[0189] Among the specific examples of antioxidants (G) above, sulfur-based antioxidants can be further exemplified by ADK STAB AO-412S (manufactured by ADEKA Corporation, trade name), AO-503S (manufactured by ADEKA Corporation, trade name), Sumilizer TP-D (manufactured by Sumitomo Chemical Corporation, trade name), etc.

[0190] Sulfur-based and phosphorus-based antioxidants can be expected to decompose peroxides.

[0191] Furthermore, the content of the antioxidant (G) relative to 100 parts by mass of the polymer of component (A) is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass. By having a content of 0.1 parts by mass or more, the adhesion to metal materials can be improved, and peeling can be suppressed. In addition, by having a content of 10 parts by mass or less, the developability of the composition and the toughness of the hardened film will not deteriorate.

[0192] [(H) Components] The negative photosensitive resin composition of the present invention preferably further contains (H) silane compounds. The negative photosensitive resin composition of the present invention preferably contains a metal adhesion modifier for improving adhesion to metal materials used in electrodes, wiring, etc., and examples of metal adhesion modifiers include silane compounds.

[0193] Examples of silane compounds include the compounds described in paragraph 0167 of International Publication No. 2015-199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication No. 2011-080992, the compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and the compounds described in paragraph 0055 of International Publication No. 2014-097594. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358, it is also preferable to use two or more different silane coupling agents.

[0194] The (H)silane compound that can be used herein is not particularly limited, but it is preferably an alkoxysilane. In addition, preferred examples are shown below. γ-Glycidoxypropyltriethoxysilane, γ-Glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate-propyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, Triethoxysilylpropylethylaminocarbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutyryl)propylamine, silanes containing amide groups as described in Japanese Patent No. 6414060, silane compounds containing thiourea groups as described in International Publication No. 2016 / 140024 and Japanese Patent No. 5987984, and silane compounds containing thiol groups as described in Japanese Patent Application Publication No. 2017-044964, etc. However, these are not limited to. Furthermore, these (H)silane compounds can be used alone or in combination of two or more.

[0195] Furthermore, the silane coupling agent is preferably a compound represented by formulas (H-1) to (H-7) below. [Chemical 77]

[0196] The content of the (H)silane compound in the metal adhesion modifier is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts by weight, and even more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the polymer having a polyimide precursor structural unit used in the negative photosensitive resin composition of the present invention. By setting it to the aforementioned lower limit or above, the adhesion between the cured film and the metal film after the curing step becomes good; by setting it to the aforementioned upper limit or below, the heat resistance and mechanical properties of the cured film after the curing step become good. The (H)silane compound in the metal adhesion modifier may be only one type or may be two or more types. When using two or more types, it is preferable that their total content is within the above range.

[0197] [(I) Composition] In this invention, it is preferable to further contain a (I) polymerization inhibitor. As the (I) polymerization inhibitor, a thermal polymerization inhibitor may be added to improve the viscosity and photosensitivity stability of the composition solution during storage. As the thermal polymerization inhibitor, any known thermal polymerization inhibitor may be used as long as it does not violate the spirit of this invention. Examples include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenthiazoline, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-ditert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxyamine ammonium salt. The amount of the polymerization inhibitor (I) added to the negative photosensitive resin composition of the present invention is preferably in the range of 0.005 to 5 parts by mass relative to 100 parts by mass of the polymer compound having the structural unit of the polyimide precursor used in the negative photosensitive resin composition of the present invention.

[0198] [Others] Furthermore, the negative photosensitive resin composition of the present invention may further include components other than (A) a polymer having a polyimide precursor structure, (C) a photopolymerization initiator, and (D) an organic compound represented by general formula (1). Other components may include, for example, (J) a sensitizer, (K) a migration inhibitor, and (L) a surfactant.

[0199] Examples of sensitizers (J) include milchone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, and 4,4'-bis(diethylamino)chalcone. Ketones, p-dimethylaminocinnamylindanone, p-dimethylaminobenzylindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzyl)acetone, 1,3-bis(4'-diethylaminobenzyl)acetone, 3,3'-carbonyl-bis( 7-Diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine 4-Aldolinylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzo[a]azole, 2-(p-dimethylaminostyryl)benzo[a]thiazole, 2-(p-dimethylaminostyryl)naphtho[(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene. They can be used alone or in combinations of, for example, 2 to 5.

[0200] In addition, relative to 100 parts by mass of the polymer of component (A), the amount of sensitizer (J) is preferably set to 0.05 parts by mass to 20 parts by mass, and more preferably set to 0.1 parts by mass to 10 parts by mass.

[0201] The negative photosensitive resin composition of the present invention preferably further includes (K) a migration inhibitor. By including the migration inhibitor, the migration of metal ions from the metal layer (metal wiring) into the curable resin composition layer can be effectively suppressed.

[0202] The migration inhibitor (K) is not particularly limited, and may include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, acetazole ring, thiazole ring, pyrazole ring, isoacetazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyrazine ring, pyridine ring, piperidine ring, piperidine ring, piperidine ring, 2H-pyran ring, and 6H-pyran ring), thioureas and compounds having hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and acehydrazine derivative compounds. Particularly preferred are triazole compounds such as 1,2,4-triazole and benzotriazole, and tetraazole compounds such as 1H-tetrazole and 5-phenyltetrazole.

[0203] As a (K) migration inhibitor, anion scavengers that capture anions such as halide ions can also be used.

[0204] As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compound described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compound described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compound described in paragraph 0166 of International Publication No. 2015 / 199219, etc., can be used.

[0205] Specific examples of migration inhibitors include the following compounds. [Chem. 78]

[0206] When the negative photosensitive resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, relative to 100 parts by mass of the polymer compound having a polyimide precursor structural unit used in the negative photosensitive resin composition of the present invention.

[0207] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, it is preferable that the total number of them is within the range described above.

[0208] The (L) surfactant is preferably a nonionic surfactant, such as fluorinated surfactants, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkyl amine oxides, fluorinated organosiloxane compounds, etc.

[0209] They can use commercially available products, such as Fluorad "FC-4430" (Sumitomo 3M Corporation), Surflon "S-141" and "S-145" (both manufactured by Asahi Glass Corporation), Unidyne "DS-401", "DS-4031" and "DS-451" (both manufactured by Daikin Industries Corporation), Megafac "F-8151" (manufactured by DIC Corporation), and "X-70-093" (manufactured by Shin-Etsu Chemical Industries Corporation). Among these, Fluorad "FC-4430" (Sumitomo 3M Corporation) and "X-70-093" (manufactured by Shin-Etsu Chemical Industries Corporation) are preferred.

[0210] Furthermore, the amount of surfactant (L) incorporated is preferably 0.01 to 0.05 parts by mass relative to 100 parts by mass of the polymer of component (A). Within this range, it has the advantage of improving the coating properties of the substrate without impairing the patterning performance or the properties of the hardened film.

[0211] [Pattern Forming Method] Next, a pattern forming method for the negative photosensitive resin composition of the present invention will be described. In the present invention, a pattern forming method is provided, characterized in that it includes: (1) a step of coating the photosensitive resin composition of any of the above-mentioned claims onto a substrate to form a photosensitive material film; (2) a step of exposing the photosensitive material film to high-energy rays or electron beams with a wavelength of 190 to 500 nm through a light shield after heat treatment; and (3) a step of developing the film using a developer solution with an organic solvent after irradiation.

[0212] The negative photosensitive resin composition of the present invention can be produced using known lithography techniques. For example, it can be spin-coated onto a silicon wafer, SiO2 substrate, SiN substrate, or substrate with patterns such as copper wires, and pre-baked at 80°C to 130°C for about 50 to 600 seconds to form a resist film with a thickness of 1 μm to 50 μm, preferably 1 μm to 30 μm, and more preferably 5 μm to 20 μm. Then, a mask for forming the target pattern is placed on the resist film, and high-energy rays with wavelengths of 190 to 500 nm, such as i-rays and g-rays, are used to irradiate and expose the film to an exposure dose of about 1 to 5000 mJ / cm², preferably about 100 to 2000 mJ / cm².

[0213] Then, development is performed. The negative photosensitive resin composition of the present invention described above is suitable for organic solvent development. Ideal organic solvents for development can be the solvents used in preparing the photosensitive resin composition of the present invention. For example, ketones such as cyclohexanone and cyclopentanone, and more preferably diols such as propylene glycol monomethyl ether. Development can be performed by conventional methods such as spraying, immersion, or soaking in a developing solution. Then, as needed, washing, rinsing, and drying are performed to obtain a resist film with the desired pattern.

[0214] Furthermore, the patterned film obtained is post-cured using an oven and a heating plate at a temperature of 100–300°C, preferably 150–300°C, and even more preferably 180–250°C. If the post-curing temperature is 100°C–300°C, the cross-linking density of the photosensitive resin composition film can be increased, residual volatile components can be removed, which is preferable from the viewpoint of adhesion to the substrate, heat resistance, strength, and electrical properties. Moreover, the post-curing time can be set to 10 minutes to 10 hours.

[0215] The hardened coating obtained in this way has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength and chemical resistance. The reliability of semiconductor devices using it as a protective coating is also excellent. In particular, it can prevent cracking during temperature cycling tests and is suitable for use as a protective coating for electrical / electronic parts, semiconductor devices and the like.

[0216] That is, the present invention provides an interlayer insulating film or surface protective film composed of a hardened film formed by curing the above-mentioned negative photosensitive resin composition.

[0217] The above-mentioned protective film is effective in applications such as insulating film for semiconductor components for redistribution purposes, insulating film for multilayer printed circuit boards, solder resist film, and cover film due to its heat resistance, chemical resistance, and insulation.

[0218] Furthermore, the present invention provides an electronic component having the aforementioned interlayer insulating film or surface protective film. Such an electronic component exhibits excellent reliability due to the presence of a protective coating (interlayer insulating film or surface protective film) possessing heat resistance, chemical resistance, and insulation properties. [Example]

[0219] Hereinafter, synthetic examples, embodiments and comparative examples are shown to specifically describe the present invention, but the present invention is not limited to the following examples.

[0220] I. Synthesis of Polymer Compounds The chemical structural formulas and names of the compounds used in the synthesis examples of the polymer compounds used in the negative photosensitive resin composition of the present invention are shown below. [Chemical 79] ODA 4,4'-diaminodiphenyl ether s-ODPA 3,3',4,4'-oxophthalic dianhydride s-BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride

[0221] [Synthetic Example 1] Synthesis of tetracarboxylic acid diester compound (X-1): 100 g (322 mmol) of 3,3',4,4'-oxophthalic dianhydride (s-ODPA), 65.2 g (644 mmol) of triethylamine, 39.3 g (322 mmol) of N,N-dimethyl-4-aminopyridine, and 400 g of γ-butyrolactone were added dropwise to a 3 L flask equipped with a stirrer and thermometer. 83.8 g (644 mmol) of hydroxyethyl methacrylate (HEMA) was added dropwise while stirring at room temperature, and the mixture was stirred for 24 hours at room temperature. Then, the reaction was terminated by adding 370 g of 10% hydrochloric acid aqueous solution dropwise under ice-cold conditions. 800 g of 4-methyl-2-pentanone was added to the reaction mixture. The organic layer was separated and washed six times with 600 g of water. The solvent of the obtained organic layer was distilled off to obtain 180 g of tetracarboxylic acid diester compound (X-1) with the following structure. [Chemistry 80]

[0222] [Synthetic Example 2] Synthesis of Tetracarboxylic Acid Diester Compound (X-2) In Synthetic Example 1, 94.8 g (322 mmol) of 3,3',4,4'-oxophthalic dianhydride (s-ODPA) was replaced with 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), otherwise 172 g of tetracarboxylic acid diester compound (X-2) with the following structure was obtained using the same formulation. [Chem. 81]

[0223] [Synthetic Example 3] Synthesis of polyimide precursor (A-1) 44.0 g (77.1 mmol) of (X-1) and 176 g of N-methyl-2-pyrrolidone were added to a 1 L flask equipped with a stirrer and thermometer and dissolved by stirring at room temperature. Then, 18.8 g (158.1 mmol) of thionyl chloride was added dropwise under ice-cold conditions to keep the reaction solution temperature below 10 °C. After the addition was complete, the mixture was stirred under ice-cold conditions for 2 hours. Then, under ice-cold conditions to keep the reaction solution temperature below 10 °C, a solution obtained by dissolving 14.4 g (71.7 mmol) of 4,4'-diaminodiphenyl ether (ODA) and 25.0 g (316.2 mmol) of pyridine in 70 g of N-methyl-2-pyrrolidone was added dropwise. After the addition was complete, the mixture was brought back to room temperature. The reaction solution was then added dropwise with 3 L of water under stirring. The precipitate was separated by filtration, washed appropriately with water, and dried under reduced pressure at 40°C for 48 hours to obtain the polyimide precursor (A-1). The molecular weight of the polymer was determined by GPC at 40°C using DMF as the dissolution solution. The weight-average molecular weight converted to polystyrene was 24,000.

[0224] [Synthesis Example 4] Synthesis of polyimide precursor (A-2) The (X-1) shown in Synthesis Example 3 was replaced with (X-2) 42.8 g (77.1 mmol), and the polyimide precursor (A-2) was obtained using the same method. The molecular weight of the polymer was determined by GPC at 40°C using DMF as the dissolution solution. The weight-average molecular weight converted to polystyrene was 23,000.

[0225] II. (D) Organic Compounds In the synthesis example of the (D) organic compounds used in the negative photosensitive resin composition of the present invention, the compounds used are as follows: (D-2) N-hydroxyphthalimide (D-3) N-hydroxy-5-norcamphene-2,3-dimethylimide (D-4) N-hydroxytetrachlorophthalimide (D-5) N,N'-dihydroxypyromellitictetramethylimide (D-6) 4-nitrophenol (D-7) pentafluorophenol (D-8) 1-hydroxybenzotriazole (D-9) 1-hydroxy-6-(trifluoromethyl)benzotriazole

[0226] [Synthetic Example 5] Synthesis of N-(tert-butoxycarbonyloxy)-5-norcamphen-2,3-dimethylimine (D-3-1) In a 300 mL flask equipped with a reflux condenser, stirrer and thermometer, 62 mg (0.51 mmol) of 4-(N,N-dimethylamino)pyridine and 6.55 g (30.0 mmol) of ditert-butyl dicarbonate were stirred at 25 °C under nitrogen. 4.48 g (25.0 mmol) of (D-3)N-hydroxy-5-norcamphen-2,3-dimethylimine in 100 mL of acetonitrile was added. The mixture was then stirred at 25 °C for 12 hours. After the reaction was complete, the reaction mixture was placed in 200 mL of cold water and the organic layer was extracted three times with 30 mL of ethyl acetate. The organic layer was further washed three times with 50 mL of cold water. After drying with magnesium sulfate, the organic layer was concentrated under reduced pressure and crystallized with petroleum ether to obtain N-(tert-butoxycarbonyloxy)-5-norcamphen-2,3-dimethylimine (D-3-1) with the following structure: (5.31 g, yield 76.0%) [Chem. 82](D-3-1)N-(tert-butoxycarbonyloxy)-5-norcamphen-2,3-dimethylimine

[0227] [Synthetic Example 6] Synthesis of N-(tert-butoxycarbonyloxy)-tetrachlorophthalimide (D-4-1) The (D-3)N-hydroxy-5-norcamphene-2,3-dimethylimide from Synthetic Example 5 was replaced with 7.52 g of (D-4)N-hydroxytetrachlorophthalimide, and the reaction was carried out in the same manner to obtain N-(tert-butoxycarbonyloxy)-tetrachlorophthalimide (D-4-1) with the following structure. (7.15 g, yield 71.5%) [Chemical 83] (D-4-1)N-(tert-butoxycarbonyloxy)-tetrachlorophthalimide

[0228] [Synthetic Example 7] Synthesis of N,N'-Di(tert-butoxycarbonyloxy)pyromellitic tetramethylimide (D-5-1) The (D-3)N-hydroxy-5-norcamphene-2,3-dimethylimide from Synthetic Example 5 was replaced with 6.18 g of (D-5)N,N'-dihydroxypyromellitic tetramethylimide, and 13.10 g (60.0 mmol) of dibutyl dicarbonate was used. The reaction was carried out in the same manner to give N,N'-di(tert-butoxycarbonyloxy)pyromellitic tetramethylimide (D-5-1) with the following structure. (9.03 g, 70.1% yield) [Chemical 84] (D-5-1)N,N'-di(tert-butoxycarbonyloxy)pyromellitic tetramethylimide

[0229] [Synthesis Example 8] Synthesis of Tertiary Butyl-4-Nitrophenyl Carbonate (D-6-1) The (D-3)N-hydroxy-5-norcamphene-2,3-dimethylimine from Synthesis Example 5 was replaced with 3.48 g of (D-6)4-nitrophenol, and the reaction was carried out in the same manner to obtain tertiary butyl-4-nitrophenyl carbonate (D-6-1) with the following structure. (5.31 g, 88.8% yield) [Chemical 85] (D-6-1) Tertiary Butyl-4-Nitrophenyl Carbonate

[0230] [Synthesis Example 9] Synthesis of Tertiary Butyl-2,3,4,5,6-Pentafluorophenyl ester (D-7-1): In Synthesis Example 5, (D-3)N-hydroxy-5-norcamphene-2,3-dimethylimine was replaced with 4.60 g of (D-7) pentafluorophenol, and the reaction was carried out in the same manner to obtain tertiary butyl-2,3,4,5,6-pentafluorophenyl ester (D-7-1) with the following structure. (5.34 g, yield 75.2%) [Chemical 86] (D-7-1) Tertiary Butyl-2,3,4,5,6-Pentafluorophenyl ester

[0231] [Synthetic Example 10] Synthesis of 1-(tert-butoxycarbonyloxy)-benzotriazole (D-8-1) In Synthetic Example 5, (D-3)N-hydroxy-5-norcamphene-2,3-dimethylimine was replaced with 3.38 g of (D-8)1-hydroxybenzotriazole, and the reaction was carried out in the same manner to give 1-(tert-butoxycarbonyloxy)-benzotriazole (D-8-1) with the following structure. (4.06 g, 69.0% yield) [Chemical 87] (D-8-1)1-(tert-butoxycarbonyloxy)-benzotriazole

[0232] [Synthetic Example 11] Synthesis of 1-(tert-butoxycarbonyloxy)-6-(trifluoromethyl)benzotriazole (D-9-1) The (D-3)N-hydroxy-5-norcamphene-2,3-dimethylimine from Synthetic Example 5 was replaced with 5.08 g of (D-9)1-hydroxy-6-(trifluoromethyl)benzotriazole, and the reaction was carried out in the same manner to give 1-(tert-butoxycarbonyloxy)-6-(trifluoromethyl)benzotriazole (D-9-1) with the following structure. (5.17 g, yield 68.2%) [Chemical 88] (D-9-1)1-(tert-butoxycarbonyloxy)-6-(trifluoromethyl)benzotriazole

[0233] [Synthetic Example 12] Synthesis of N-(benzyloxycarbonyloxy)phthalimide (D-2-2) In a 300 mL flask equipped with a reflux condenser, stirrer and thermometer, 4.26 g (25.0 mmol) benzyl chloroformate was added dropwise to a mixed solution of 51 mg (0.51 mmol) triethylamine, 8.17 g (50.0 mmol) (D-2) N-hydroxyphthalimide and 70 g tetrahydrofuran at 0 °C, and then stirred at 50 °C for 20 hours. After the reaction was complete, the reaction solution was poured into 200 mL of cold water and the organic layer was extracted three times with 30 mL of ethyl acetate. The organic layer was further washed three times with 50 mL of cold water, dried with magnesium sulfate, concentrated under reduced pressure, and crystallized using petroleum ether to obtain N-(benzyloxycarbonyloxy)-phthalimide (D-2-2) with the following structure: (6.03 g, yield 81.2%) [Chem. 89](D-2-2)N-(benzyloxycarbonyloxy)-phthalimide

[0234] [Synthesis Example 13] Synthesis of N-(benzyloxycarbonyloxy)-5-norcamphene-2,3-dimethylimine (D-3-2) The (D-2)N-hydroxyphthalimine in Synthesis Example 12 was replaced with 4.48 g of (D-3)N-hydroxy-5-norcamphene-2,3-dimethylimine, and the reaction was carried out in the same manner to obtain N-(benzyloxycarbonyloxy)-5-norcamphene-2,3-dimethylimine (D-3-2) with the following structure. (6.18 g, yield 78.9%) [Chemical 90] (D-3-2)N-(benzyloxycarbonyloxy)-5-norcamphene-2,3-dimethylimine

[0235] [Synthetic Example 14] Synthesis of N-(benzyloxycarbonyloxy)-tetrachlorophthalimide (D-4-2) The (D-2)N-hydroxyphthalimide in Synthetic Example 12 was replaced with 7.52 g of (D-4)N-hydroxytetrachlorophthalimide, and the reaction was carried out in the same manner to give N-(benzyloxycarbonyloxy)-tetrachlorophthalimide (D-4-2) with the following structure. (6.78 g, yield 62.3%) [Chemical 91] (D-4-2)N-(benzyloxycarbonyloxy)-tetrachlorophthalimide

[0236] [Synthetic Example 15] Synthesis of N,N'-Di(benzyloxycarbonyloxy)pyromellitic tetramethylimide (D-5-2) The (D-2)N-hydroxyphthalimide from Synthetic Example 12 was replaced with 6.18 g of (D-5)N,N'-dihydroxypyromellitic tetramethylimide, and reacted with 10.23 g (60.0 mmol) of benzyl chloroformate to give N,N'-di(benzyloxycarbonyloxy)pyromellitic tetramethylimide (D-5-2) with the following structure. (7.52 g, yield 58.4%) [Chemical 92] (D-5-2)N,N'-di(benzyloxycarbonyloxy)pyromellitic tetramethylimide

[0237] [Synthesis Example 16] Synthesis of benzyl-4-nitrobenzene carbonate (D-6-2): In Synthesis Example 12, (D-2)N-hydroxyphthalimide was replaced with 3.48 g of (D-6)4-nitrophenol, and the reaction was carried out in the same manner to give benzyl-4-nitrobenzene carbonate (D-6-2) with the following structure. (5.85 g, yield 85.6%) [Chemical 93] (D-6-2)benzyl-4-nitrobenzene carbonate

[0238] [Synthesis Example 17] Synthesis of benzyl-2,3,4,5,6-pentafluorophenyl carbonate (D-7-2): In Synthesis Example 12, (D-2)N-hydroxyphthalimide was replaced with 4.60 g of (D-7)pentafluorophenol, and the reaction was carried out in the same manner to give benzyl-2,3,4,5,6-pentafluorophenyl carbonate (D-7-2) with the following structure. (4.77 g, yield 60.0%) [Chemical 94] (D-7-2)benzyl-2,3,4,5,6-pentafluorophenyl carbonate

[0239] [Synthetic Example 18] Synthesis of 1-(benzyloxycarbonyloxy)-benzotriazole (D-8-2) The (D-2)N-hydroxyphthalimide in Synthetic Example 12 was replaced with 3.38 g of (D-8)1-hydroxybenzotriazole, and the reaction was carried out in the same manner to give 1-(benzyloxycarbonyloxy)-benzotriazole (D-8-2) with the following structure. (4.13 g, yield 61.3%) [Chemical 95] (D-8-2)1-(benzyloxycarbonyloxy)-benzotriazole

[0240] [Synthetic Example 19] Synthesis of 1-(benzyloxycarbonyloxy)-6-(trifluoromethyl)benzotriazole (D-9-2) The (D-2)N-hydroxyphthalimide from Synthetic Example 12 was replaced with 5.08 g of (D-9)1-hydroxy-6-(trifluoromethyl)benzotriazole, and the reaction was carried out in the same manner to give 1-(benzyloxycarbonyloxy)-6-(trifluoromethyl)benzotriazole (D-9-2) with the following structure. (5.43 g, yield 64.4%) [Chemical 96] (D-9-2)1-(benzyloxycarbonyloxy)-6-(trifluoromethyl)benzotriazole

[0241] Furthermore, the (D-1-1)N-(tert-butoxycarbonyloxy)succinimide shown in the following structural formula uses commercially available reagents (Fujifilm and Koizumi Pure Chemicals). [Chemical 97](D-1-1)N-(tert-butoxycarbonyloxy)succinimide

[0242] In addition, the (D-2-1)N-(tert-butoxycarbonyloxy)phthalimide and (D-1-2)N-(benzyloxycarbonyloxy)succinimide shown in the following structural formulas were tested using commercially available reagents (Tokyo Kasei Corporation). [Chemical 98](D-2-1)N-(tert-butoxycarbonyloxy)phthalimide [Chemical 99](D-1-2)N-(benzyloxycarbonyloxy)succinimide

[0243] III. Imine Ring Closure Temperature In the above, 100 parts by weight of the synthesized polymer compound (A-1), 5 parts by weight of the organic compounds (D-1-1) to (D-9-2) with components (D) obtained above as shown in Tables 1 (Examples 1) to (Examples 18), and 4.0 parts by weight of the photopolymerization initiator (C-1): N-1919 manufactured by ADEKA (stock) were dissolved in γ-butyrolactone (hereinafter referred to as GBL) as a solvent. Then, the mixture was microfiltered using a 1.0 μm Teflon (registered trademark) filter to prepare a negative photosensitive resin composition. In addition, a composition of the organic compound without component (D) was prepared as a comparative example. Then, 5 mL of the obtained composition solution was dispensed onto a silicon substrate and coated by spin coating. Then, a pre-baking process of 100°C for 3 minutes was performed on a hot plate. The coating speed was adjusted to achieve a final film thickness of 0.9 μm to 1.2 μm after pre-baking. For the composition film on the coated silicon substrate, a Nikon NSR-2205i11 i-ray stepper was used for full-area exposure using i-rays at an exposure dose of 600 mJ. The resulting cured film was heated at 100°C to 250°C for 1 hour at 10°C intervals, and the absorption intensity at each temperature was measured using FT-IR with infrared spectroscopy as described below. The cured film was also heated at 300°C for 1 hour, and the absorption intensity was measured similarly. FT-IR: Nicolet iN10 MX (Thermo Fisher Scientific)

[0244] In the composition film, if the polymeric compound of the polyimide precursor undergoes a ring-closure reaction with polyimide, a new CN bond is formed, thus increasing the absorption intensity at 1379 cm⁻¹ from the CN stretching motion in the IR spectrum. On the other hand, since the C-C double bond of the benzene ring does not change after amide imidization, the absorption intensity at 1552 cm⁻¹ from the C-C stretching motion of the benzene ring does not change in the IR spectrum. Using the absorption intensity at 1552 cm⁻¹ from the C-C stretching motion of the benzene ring as an internal standard, the absorption intensity at 1379 cm⁻¹ from the CN stretching motion can be expressed as the degree of progress of the ring-closure reaction with amide imidization at each temperature, i.e., the amide imidization rate, by the following formula (30). Furthermore, the degree of progress of amide imidization at each temperature can be compared relatively. [Equation 1]

[0245] The amide ratio of the hardened film after heating at 300°C for 1 hour, calculated by the aforementioned formula (30), can be defined as the complete ring-closure reaction of the polymer compound of the polyamide precursor to the polyamide. If the amide ratio of the hardened film obtained by changing the temperature is equal to the amide ratio of the hardened film at 300°C, the aforementioned temperature can be expressed as the temperature at which the amide ring-closure reaction of the polyamide precursor of the constituent film can be completed.

[0246] In the photosensitive resin composition of the photosensitive resin composition in (Example 1) to (Example 18) of Table 1 below, the lowest temperature at which the amide ratio of the photosensitive resin composition is equal to that of the photosensitive resin composition after heating at 300°C for 1 hour is expressed as the amide ring-closing temperature of the composition film.

[0247] [Table 1]

[0248] As shown in Table 1 above, the organic compound of component (D) of the present invention can promote the amide reaction of polymeric compounds containing polyamide precursor structures and can carry out amide ring-closing reaction at low temperature, i.e. below 200°C.

[0249] IV. Preparation of the photosensitive resin composition A polymeric compound containing the polyimide precursor obtained in Synthetic Examples 3 to 4 was used as the base resin. The organic compound of component (D) of the present invention prepared above was used to prepare a resin composition of 35% by mass (resin equivalent) according to the composition and blending amount recorded in Tables 2 to 5. Then, after stirring, mixing and dissolving, the photosensitive resin composition was obtained by microfiltration using a 1.0 μm filter made of Telflon (registered trademark). In the tables, GBL represents γ-butyrolactone as the solvent.

[0250] [Table 2] Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Photosensitive resin composition 1 Photosensitive resin composition 2 Photosensitive resin composition 3 Photosensitive resin composition 4 Photosensitive resin composition 5 Photosensitive resin composition 6 Photosensitive resin composition 7 Photosensitive resin composition 8 Photosensitive resin composition 9 polymers A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight (D) Organic compounds D-1-1 5 parts by weight D-2-1 5 parts by weight D-3-1 5 parts by weight D-4-1 5 parts by weight D-5-1 5 parts by weight D-6-1 5 parts by weight D-7-1 5 parts by weight D-8-1 5 parts by weight D-9-1 5 parts by weight Photopolymerization initiator (C-1) 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight Polymerizable compound (B-1) 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight thermal crosslinking agent No additions No additions No additions No additions No additions No additions No additions No additions No additions Antioxidant (G-1) 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight Silane compounds (H-1) 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight Polymerization inhibitor (I-1) 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight Solvent GBL 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight Hole pattern shape good good good good good good good good good Minimum aperture 5μm 5μm 5μm 5μm 5μm 5μm 5μm 5μm 5μm Sensitivity 380mJ 380mJ 380mJ 380mJ 380mJ 380mJ 380mJ 380mJ 380mJ Preservation of stability excellent excellent excellent excellent excellent excellent excellent excellent excellent Drug resistance excellent excellent excellent excellent excellent excellent excellent excellent excellent

[0251] [Table 3] Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Photosensitive resin composition 10 Photosensitive resin composition 11 Photosensitive resin composition 12 Photosensitive resin composition 13 Photosensitive resin composition 14 Photosensitive resin composition 15 Photosensitive resin composition 16 Photosensitive resin composition 17 Photosensitive resin composition 18 polymers A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight (D) Organic compounds D-1-2 5 parts by weight D-2-2 5 parts by weight D-3-2 5 parts by weight D-4-2 5 parts by weight D-5-2 5 parts by weight D-6-2 5 parts by weight D-7-2 5 parts by weight D-8-2 5 parts by weight D-9-2 5 parts by weight Photopolymerization initiator (C-1) 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight Polymerizable compound (B-1) 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight thermal crosslinking agent No additions No additions No additions No additions No additions No additions No additions No additions No additions Antioxidant (G-1) 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight Silane compounds (H-1) 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight Polymerization inhibitor (I-1) 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight Solvent GBL 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight Hole pattern shape good good good good good good good good good Minimum aperture 5μm 5μm 5μm 5μm 5μm 5μm 5μm 5μm 5μm Sensitivity 400mJ 380mJ 400mJ 420mJ 400mJ 400mJ 420mJ 400mJ 400mJ Preservation of stability excellent excellent excellent excellent excellent excellent excellent excellent excellent Drug resistance excellent excellent excellent excellent excellent excellent excellent excellent excellent

[0252] [Table 4] Example 37 Example 38 Example 39 Photosensitive resin composition 21 Photosensitive resin composition 22 Photosensitive resin composition 23 polymers A-1 100 parts by weight A-1 100 parts by weight A-2 100 parts by weight (D) Organic compounds D-1-1 5 parts by weight D-2-1 5 parts by weight D-1-1 5 parts by weight Photopolymerization initiator (C-1) 4 parts by weight 4 parts by weight 4 parts by weight Polymerizable compound (B-1) 10 portions by weight 10 portions by weight 10 portions by weight thermal crosslinking agent F-1 5 parts by weight F-2 10 portions by weight No additions Antioxidant (G-1) 1 part by weight 1 part by weight 1 part by weight Silane compounds (H-1) 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight Polymerization inhibitor (I-1) 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight Solvent GBL 180 parts by weight 180 parts by weight 180 parts by weight Hole pattern shape good good good Minimum aperture 5μm 5μm 5μm Sensitivity 380mJ 380mJ 380mJ Preservation of stability excellent excellent excellent Drug resistance excellent excellent excellent

[0253] [Table 5] Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Photosensitive resin composition 24 Photosensitive resin composition 25 Photosensitive resin composition 26 Photosensitive resin composition 27 Photosensitive resin composition 28 Photosensitive resin composition 29 Photosensitive resin composition 30 Photosensitive resin composition 31 Photosensitive resin composition 32 Photosensitive resin composition 33 polymers A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight A-1 100 parts by weight (D) Organic compounds D-1 5 parts by weight D-2 5 parts by weight D-3 5 parts by weight D-4 5 parts by weight D-5 5 parts by weight D-6 5 parts by weight D-7 5 parts by weight D-8 5 parts by weight D-9 5 parts by weight No additions Photopolymerization initiator (C-1) 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight 4 parts by weight Polymerizable compound (B-1) 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight 10 portions by weight thermal crosslinking agent No additions No additions No additions No additions No additions No additions No additions No additions No additions No additions Antioxidant (G-1) 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight Silane compounds (H-1) 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight Polymerization inhibitor (I-1) 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight Solvent GBL 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight 180 parts by weight Hole pattern shape good good good good good good good good good good Minimum aperture 5μm 5μm 5μm 5μm 5μm 5μm 5μm 5μm 5μm 6μm Sensitivity 400mJ 400mJ 400mJ 400mJ 400mJ 400mJ 400mJ 400mJ 400mJ 400mJ Preservation of stability Unable to rate Difference Difference Difference Difference Unable to rate Unable to rate Difference Difference good Drug resistance excellent excellent excellent excellent excellent excellent excellent excellent excellent Difference

[0254] The photosensitive resin compositions 1-18 and 21-23 (Examples 19-39) shown in Tables 2-4 relate to the negative photosensitive resin compositions of the present invention described above. The comparative photosensitive resin compositions 24-32 (Comparative Examples 2-10) shown in Table 5 relate to negative photosensitive resin compositions containing unprotected organic compounds. These unprotected organic compounds are different from those used in the negative photosensitive resin compositions of the present invention, which typically use hydroxyl compounds as active esterifying agents protected with a third butoxycarbonyl group (N-Boc group), or different from those protected with a benzyloxycarbonyl protecting group (Z group).

[0255] Furthermore, in Table 5, the unprotected hydroxyl compounds used as active esterifying agents in the comparative photosensitive resin compositions 24-32 (Comparative Examples 2-10) are (D-2) to (D-9) used in the above-mentioned synthetic examples 5-19, and (D-1) is N-hydroxysuccinimide.

[0256] Comparative photosensitive resin composition 33 (Comparative Example 11) is a composition without the addition of the organic compounds used in the negative photosensitive resin composition of the present invention described above.

[0257] Furthermore, the details of the polymerizable compounds (B-1), photopolymerization initiators (C-1), thermal crosslinking agents (F-1), (F-2), antioxidants (G-1), silane compounds (H-1), and polymerization inhibitors (I-1) having two or more vinyl unsaturated groups in Tables 2 to 5 are as follows. Additionally, parts by weight have the same meaning as parts by mass.

[0258] Photopolymerization initiator (C-1): ADEKA Corporation, N-1919

[0259] A polymeric compound having two or more vinyl unsaturated groups (B-1): Tetraethylene glycol dimethacrylate

[0260] Thermal crosslinking agent (F-1): [Chemical 100]

[0261] Thermal crosslinking agent (F-2): Epoxy resin: EP4000L manufactured by ADEKA (stock) Co., Ltd.

[0262] Antioxidant (G-1): Hindered phenolic antioxidant: Sumitomo Chemical Co., Ltd., Sumilizer GA-80

[0263] Silane compound (H-1): Aminosylsilane coupling agent: Shin-Etsu Chemical Industry Co., Ltd. KBM-573

[0264] Polymerization inhibitor (I-1): 2-Nitrosino-1-naphthol (Reagent: Tokyo Chemical Industry Co., Ltd.)

[0265] V. Pattern Formation: After dispensing 5 mL of the above-mentioned photosensitive resin compositions 1-18 and 21-23, and comparative photosensitive resin compositions 24-33 onto a silicon substrate, the substrate is rotated, i.e., spin-coated, to achieve a film thickness of 5 μm after post-curing heating following pattern formation. Specifically, the spin speed is adjusted to address the reduction in film thickness after the post-curing step. Then, a pre-baking process is performed at 100°C for 3 minutes on a heated plate. Next, i-ray exposure and pattern formation are performed using an i-ray stepper NSR-2205i11 manufactured by Nikon Corporation. During pattern formation, masks for positive and negative patterns are appropriately used in conjunction with the photosensitive resin compositions. The mask has a pattern of 20μm holes arranged in a 1:1 ratio, and can form hole patterns with a spacing of 10μm in the range of 50μm to 20μm, a spacing of 5μm in the range of 20μm to 10μm, and a spacing of 1μm in the range of 10μm to 1μm.

[0266] In the developing step, cyclopentanone is used as the developing solution. The organic solvent developing system is subjected to one 1-minute spray development of each organic solvent, followed by rinsing with isopropanol.

[0267] Then, the pattern on the obtained substrate was post-cured by purging with nitrogen in an oven at 200°C for 2 hours.

[0268] Then, each substrate was cut out in a manner that allowed the shape of the obtained hole pattern to be observed, and the shape of the hole pattern was observed using a scanning electron microscope (SEM). The diameter of the smallest opening hole in a 5 μm thick film after curing was determined, and the shape of the pattern was evaluated. These results, along with the sensitivity that allows the formation of the smallest pattern, are shown in Tables 2 to 5.

[0269] Furthermore, the pattern shape of the holes is evaluated according to the following criteria, and the evaluation results are shown in Tables 2 to 5. Good: The holes are observed to be rectangular or in a push-pull shape (the size of the upper part of the hole is larger than the size of the bottom part). Poor: The holes are observed to be in a push-pull shape (the size of the upper part of the hole is smaller than the size of the bottom part), an overhang shape (the shape of the upper part of the hole protrudes), a significant reduction in film, or residue is observed at the bottom of the hole.

[0270] VI. Storage Stability In the above pattern formation, 5 mL of the described photosensitive resin composition was dispensed onto a silicon substrate, the substrate was rotated, and the same coating was applied. Pre-baking was then performed on a heated plate at 100°C for 3 minutes. The film thickness after pre-baking was recorded, and the solution of the photosensitive resin composition was stored at room temperature for 3 weeks. After 3 weeks, a film was formed under the same conditions and at the same rotation speed, and the film thickness was measured. The film thickness before storage was compared with the film thickness after storage, and the storage stability was evaluated as follows. The film thickness change rate was calculated using the following formula: Film thickness change rate (%) = {(film thickness before storage - film thickness after storage) / film thickness before storage} × 100 The calculated film thickness change rate was evaluated according to the following evaluation criteria.

[0271] Excellent: Compositions whose film thickness changes by less than 10% before and after storage. Good: Compositions whose film thickness changes by 10% or more but less than 15% before and after storage. Poor: Compositions whose film thickness changes by 15% or more before and after storage. Cannot be evaluated: Compositions whose composition solution gels after 3 weeks and cannot form a film. The evaluation results are recorded in Tables 2 to 5. The smaller the film thickness change rate mentioned above, the better the storage stability of the curing composition. In addition, it is preferable that the composition solution remains stable without change.

[0272] VII. Chemical Resistance In the above pattern formation, 5 mL of the described photosensitive resin composition was dispensed onto a silicon substrate, the substrate was rotated, and the coating was repeated. The substrate was then pre-baked at 100°C on a heated plate for 3 minutes. Then, using a Nikon NSR-2205i11 i-ray stepper, i-ray exposure was performed on the entire surface without pattern formation at an exposure dose of 600 mJ. Finally, the film on the resulting substrate was post-cured using an oven at 200°C for 2 hours while being purged with nitrogen.

[0273] The obtained hardened film was immersed in the following solution under the following conditions, and the dissolution rate was calculated. Solution: A mixture of dimethyl sulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution in a ratio of 90:10 (mass ratio). Evaluation conditions: The resin layer was immersed in the above solution at 75°C for 15 minutes, and the film thickness before and after was compared to determine the change in the hardened film. The evaluation was conducted according to the following evaluation criteria, and the evaluation results are recorded in Tables 2 to 5. It can be said that the smaller the change in film thickness, the better the chemical resistance of the obtained hardened film (resin layer).

[0274] Excellent: The change in film thickness is less than 3.0 μm. Good: The change in film thickness is greater than 3.0 μm and less than 5.0 μm. Poor: The change in film thickness is greater than 5.0 μm.

[0275] As shown in Tables 2 to 5, it can be seen that negative photosensitive resin compositions containing the organic compounds of the present invention exhibit excellent resolution. Furthermore, it can be seen that storage stability and chemical resistance are also excellent.

[0276] On the other hand, it is clear that when using negative photosensitive resin compositions containing compounds other than the organic compounds of the present invention, the storage stability is poor. That is, as shown in the results of comparing the storage stability of photosensitive resin compositions 24 to 32 (Comparative Examples 2 to 10), it can be seen that, unlike the organic compounds of the present invention where the hydroxyl compound used as the active esterifying agent is protected with a third butoxycarbonyl group (N-Boc group), or unlike the organic compounds protected with a benzyloxycarbonyl protecting group (Z group), negative photosensitive resin compositions containing unprotected organic compounds have poor storage stability.

[0277] Comparative photosensitive resin composition 33 (Comparative Example 11) is a composition without the organic compounds used in the negative photosensitive resin composition of the present invention described above. The chemical resistance of the cured film of this composition is worse than that of the composition containing the nitrogen-containing compound of the present invention. This is believed to be because, as mentioned above, the amide ring-closing temperature of the composition without the nitrogen-containing organic compound of the present invention is as high as 230°C. Under the conditions of using an oven at 200°C for 2 hours in this evaluation, complete amide formation cannot be achieved, and the advantages of the polyamide, such as chemical resistance, cannot be utilized.

[0278] This specification contains the following states. [1]: A negative photosensitive resin composition, characterized by comprising: (A) a polymeric compound having a polyimide precursor structure, (C) a photopolymerization initiator, (D) an organic compound represented by the following general formula (1), and (E) a solvent; [Chemical 101] Wherein, T represents any structure in the following general formulas (2) to (4), and W represents an alkyl or aryl group that may also be substituted by an alkoxy group having 4 to 15 carbon atoms. [Chemical 102] Wherein, V represents a divalent organic group, and * represents a bond. [Chemical 103] Wherein, Q represents a halogen atom or a nitro group, and RC represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms. n represents an integer from 3 to 5 when Q is a halogen atom, and 1 when Q is a nitro group. * represents a bond. [Chem. 104] In the formula, Ar represents a substituted or unsubstituted aromatic ring structure or a heterocyclic structure having heteroatoms, and * represents a bond. [2]: A negative photosensitive resin composition as in [1], wherein the (A) component is a polymeric compound having a polyimide precursor structure as shown in the following general formula (5), [Chem. 105] In the formula, X is a tetravalent organic group, Y is a divalent organic group, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R1 and R2 is a group shown in the following general formula (6). [Chem. 106] In the formula, M1, M2 and M3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, m is an integer from 2 to 10, and * represents a bond. [3]: A negative photosensitive resin composition as in [1] or [2], wherein it includes (B) a polymeric compound having two or more vinyl unsaturated groups. [4]: A negative photosensitive resin composition of any one of [1] to [3], wherein W in the general formula (1) of component (D) is a third butyl. [5]: A negative photosensitive resin composition of any one of [1] to [3], wherein W in the general formula (1) of component (D) is a benzyl. [6]: A negative photosensitive resin composition of any one of [1] to [5], wherein the general formula (2) is the structure shown in the following general formula (2-1), [Chemical 107] wherein Ra and Rb represent hydrogen atoms, a straight-chain, branched or cyclic alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and Ra and Rb may also bond to each other and form a ring together with the carbon atoms they bond to, * indicates a bond. [7]: A negative photosensitive resin composition as described in any of [1] to [5], wherein the general formula (3) is the structure shown in formula (3-1) or (3-2) below, [Chemical 108] where * represents a bond. [Chemical 109] where * represents a bond.[8]: A negative photosensitive resin composition of any one of [1] to [5], wherein the general formula (4) is the structure shown in the following general formula (4-1), [Chemical 110] where Rd represents a straight-chain, branched or cyclic alkyl group having halogen atoms with 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, k represents an integer from 0 to 4, and * represents a bond. [9]: A negative photosensitive resin composition of any one of [1] to [8], wherein 1 to 10 parts by mass of the (D) component are contained relative to 100 parts by mass of the (A) component.

[10] : The negative photosensitive resin composition of any one of [1] to [9], wherein, as (F) thermal crosslinking agent, it comprises one or more crosslinking agents selected from formaldehyde or formaldehyde-alcohol modified amino condensates, phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups per molecule, compounds in which the hydrogen atom of the hydroxyl group of a polyphenol is replaced with an epoxypropyl group, compounds in which the hydrogen atom of the hydroxyl group of a polyphenol or a polyol is replaced with a substituent shown in the following formula (F-1), and compounds containing two or more nitrogen atoms of the epoxypropyl group shown in the following formula (F-2), wherein, [Chemical 111], the dashed line represents an atomic bond, Rf is a straight-chain, branched or cyclic alkyl group having 1 to 6 carbon atoms, and c is 1 or 2.

[11] : The negative photosensitive resin composition of any one of [1] to

[10] further comprises (G) an antioxidant.

[12] : The negative photosensitive resin composition of any one of [1] to

[11] further contains (H) silane compound.

[13] : The negative photosensitive resin composition of any one of [1] to

[12] further contains (I) polymerization inhibitor.

[14] : A pattern forming method, characterized by comprising: (1) coating the photosensitive resin composition of any one of [1] to

[13] onto a substrate to form a photosensitive film; (2) then, after heat treatment, exposing the photosensitive film to high-energy rays or electron beams with a wavelength of 190 to 500 nm through a light shield; and (3) developing the film using a developer solution with an organic solvent after irradiation.

[15] : A method for forming a hardened film, characterized by comprising heating and hardening the patterned film obtained by the pattern forming method of

[14] at a temperature of 100 to 300°C.

[16] : An interlayer insulating film, characterized in that it is a cured film formed by curing a negative photosensitive resin composition as described in any one of [1] to

[13] .

[17] : A surface protective film, characterized in that it is a cured film formed by curing a negative photosensitive resin composition as described in any one of [1] to

[13] .

[18] : An electronic component, characterized in that it has an interlayer insulating film as described in

[16] .

[19] : An electronic component, characterized in that it has a surface protective film as described in

[17] .

[0279] Furthermore, the present invention is not limited to the above-described embodiments. The above embodiments are illustrative examples, and technical solutions having a substantially the same structure and performing the same effects as those described in the claims of the present invention are all included within the technical scope of the present invention.

Claims

1. A negative photosensitive resin composition, characterized by comprising: (A) a polymeric compound having a polyimide precursor structure as shown in the following general formula (5), (C) a photopolymerization initiator, (D) an organic compound as shown in the following general formula (1), and (E) a solvent; relative to 100 parts by mass of component (A), it contains 0.1 to 20 parts by mass of component (C) and 1 to 10 parts by mass of component (D); wherein X is a tetravalent organic group, Y is a divalent organic group, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R1 and R2 is a group as shown in the following general formula (6), wherein M1, M2 and M3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, m is an integer from 2 to 10, and * denotes a bond; In the formula, T represents any structure in the following general formulas (2) to (4), W represents an alkyl or aryl group that can also be substituted by an alkoxy group with 4 to 15 carbon atoms, V represents a divalent organic group, * represents a bond, Q represents a halogen atom or a nitro group, RC represents a hydrogen atom, a straight-chain, branched or cyclic alkyl group with 1 to 15 carbon atoms, or an aryl group with 6 to 15 carbon atoms, n represents an integer of 3 to 5 when Q is a halogen atom, and 1 when Q is a nitro group, * represents a bond, Ar represents a substituted or unsubstituted aromatic ring structure, or a heterocyclic structure with heteroatoms, * represents a bond.

2. The negative photosensitive resin composition as claimed in claim 1, wherein, (B) Polymers containing two or more vinyl unsaturated groups.

3. The negative photosensitive resin composition as claimed in claim 1, wherein, In the general formula (1) of component (D), W is the third butyl group.

4. The negative photosensitive resin composition as claimed in claim 1, wherein, In the general formula (1) of component (D), W is benzyl.

5. The negative photosensitive resin composition as claimed in claim 1, wherein, The general formula (2) is the structure shown in the following general formula (2-1), where Ra and Rb represent hydrogen atoms, straight-chain, branched or cyclic alkyl groups with 1 to 15 carbon atoms, or aryl groups with 6 to 15 carbon atoms. Ra and Rb can also bond to each other and form a ring together with the carbon atoms they bond to. * indicates a bond.

6. The negative photosensitive resin composition as claimed in claim 1, wherein, The general formula (3) is the structure shown in formula (3-1) or (3-2) below, where * represents a bond, and * represents a bond.

7. The negative photosensitive resin composition as claimed in claim 1, wherein, The general formula (4) is the structure shown in the following general formula (4-1), where Rd represents a straight-chain, branched or cyclic alkyl group with 1 to 15 carbon atoms or an aryl group with 6 to 15 carbon atoms, k represents an integer from 0 to 4, and * represents a bond.

8. The negative photosensitive resin composition as claimed in claim 1, wherein, The negative photosensitive resin composition includes one or more crosslinking agents selected from formaldehyde or formaldehyde-alcohol modified amine condensates, phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups per molecule, compounds formed by replacing the hydrogen atoms of the hydroxyl groups of polyphenols with glycidyl groups, compounds formed by replacing the hydrogen atoms of the hydroxyl groups of polyphenols or polyols with substituents shown in the following formula (F-1), and compounds containing two or more nitrogen atoms of glycidyl groups shown in the following formula (F-2) as a thermal crosslinking agent (F). In the formula, the dashed line represents an atomic bond, Rf is a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and c is 1 or 2.

9. The negative photosensitive resin composition of claim 1 further contains (G) antioxidant.

10. The negative photosensitive resin composition of claim 1 further contains (H)silane compounds.

11. The negative photosensitive resin composition of claim 1 further contains (I) a polymerization inhibitor.

12. A method for forming a pattern, characterized by comprising: (1) A step of coating a photosensitive resin composition as claimed in any one of claims 1 to 11 onto a substrate to form a photosensitive film; (2) A step of exposing the photosensitive film to high-energy rays or electron beams with wavelengths of 190 to 500 nm through a light shield after heat treatment; and (3) A step of developing the film using a developer solution with an organic solvent after irradiation.

13. A method for forming a hardened film, characterized in that it includes the step of heating and hardening a patterned film obtained by the pattern forming method of claim 12 at a temperature of 100 to 300°C.

14. An interlayer insulating film, characterized in that it is a cured film formed by curing a negative photosensitive resin composition as claimed in any one of claims 1 to 11.

15. A surface protective film, characterized in that it is a cured film formed by curing a negative photosensitive resin composition as claimed in any one of claims 1 to 11.

16. An electronic component, characterized in that it has an interlayer insulating film as claimed in claim 14.

17. An electronic component, characterized in that it has a surface protective film as claimed in claim 15.

Images