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

Abstract

To provide: a photosensitive resin composition that allows an imide ring-closing reaction at low temperature, that has excellent stability of the composition, that uses a polyimide precursor enabling fine patterning, and that can impart resistance against chemicals after curing; a patterning process using the photosensitive resin composition; an interlayer insulating film comprising a cured coating formed by curing the photosensitive resin composition; and a semiconductor device.SOLUTION: A negative-type photosensitive resin composition includes: (A) a polymer compound including a polyimide precursor structure; (C) a photopolymerization initiator; (D) an organic compound represented by the general formula (1) in the figure; and (E) a solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a negative photosensitive resin composition, a pattern formation method using the negative photosensitive resin composition that is developable with an organic solvent, a cured film formation method, an interlayer insulating film, a surface protective film, and an electronic component. [Background technology]

[0002] As various electronic devices such as personal computers, digital cameras, and mobile phones become smaller and more powerful, there is a rapidly increasing demand for smaller, thinner, and higher-density semiconductor elements. Therefore, there is a need for the development of photosensitive insulating materials that can accommodate the increase in substrate area required for improved productivity and that can be fabricated with fine, high-aspect ratio patterns on substrates for high-density packaging technologies such as chip-size packages (CSPs) and three-dimensional stacking.

[0003] In high-density packaging technologies such as three-dimensional stacking, photosensitive insulating materials that can be patterned on substrates have long been used as protective coatings and interlayer insulating films. Their insulating properties, mechanical strength, and adhesion to substrates have continued to attract attention, and they are still being actively developed.

[0004] Polyimides and other materials used to form polyimide films have low solubility in solvents, so they are used in the precursor state before the imide ring-closure reaction. After coating or laminating them on a substrate, they are heated to cyclize the polyimide precursor and form a cured film, which can be used as a protective coating or interlayer insulating film.

[0005] Previously, materials that are precursors of patternable polyimides have been proposed, such as those in which a photosensitive group is introduced into the carboxyl group of a polyamic acid via an ester bond (Patent Documents 1 and 2). However, these proposals require an imidization treatment at a high temperature exceeding 300°C after forming a patterned coating to obtain the desired polyimide coating, which has problems such as limitations on the base substrate to withstand such high temperatures, oxidation of copper in wiring, and the risk of thermal damage to electronic components.

[0006] Patent Document 3 discloses a polyimide precursor composition containing a polyimide precursor, a thermal base generator that generates a base upon heating, and a solvent, wherein the polyimide precursor is a polyamic acid, and the thermal base generator is a neutral compound that undergoes thermal decomposition to generate a secondary amine when heated at a temperature of 200°C or less. It is disclosed that the secondary amine generated by thermal decomposition promotes an imide ring-closing reaction, making it possible to treat the polyimide precursor composition at 200°C or less.

[0007] However, a cured film using the composition described in Patent Document 3 may be inferior in corrosion resistance and chemical resistance, which are properties required for protective coatings, interlayer insulating films, etc. Furthermore, the composition has a storage stability problem in that a cyclization reaction of the polyimide precursor resin progresses during storage, causing gelation and the like.

[0008] Meanwhile, Patent Documents 4 and 5 disclose compositions containing imidazoles as imidization catalysts that promote the imide ring-closure reaction with a polyimide precursor. However, they do not disclose photosensitive resin compositions capable of forming patterns on substrates, as required for high-density packaging technology, nor do they disclose low-temperature imidization. Furthermore, the imidazoles used as imidization catalysts in Patent Documents 4 and 5, with the exception of N-tert-butoxycarbonylimidazole (N-Boc-imidazole), have storage stability issues, resulting in gelation of the composition during storage. Furthermore, the imidazoles used as imidization catalysts in Patent Documents 4 and 5, when added in amounts that cause thermal deformation of the pattern (thermal flow) during the curing reaction after pattern formation, precluding the creation of fine patterns with high aspect ratios. Furthermore, the glass transition temperature (Tg) of the resulting cured film is lowered, making them unsuitable for use in protective coatings, interlayer insulating films, and the like.

[0009] On the other hand, Patent Document 6 discloses the use of an activated esterifying agent, which is a compound that can promote imidization at a lower temperature, unlike a thermal base generator that generates a base by heat. However, the carbonate compounds and ester compounds of the activated esterifying agents disclosed in Patent Document 6, such as bis(pentafluorophenyl)carbonate, bis(4-nitrophenyl)carbonate, di(N-succinimidyl)carbonate, and 4-nitrophenyl trifluoroacetate, have relatively high decomposition temperatures, and it is desirable to more effectively promote the imide ring-closure reaction in the heating step that produces a cured coating.

[0010] Furthermore, the active esterifying agents disclosed in Patent Document 6, pentafluorophenol and 1-hydroxy-7-azabenzotriazole, contain a hydroxy group, and therefore pose the problem of deteriorating the storage stability of a photosensitive resin composition containing a polyimide precursor resin.

[0011] Furthermore, Patent Document 7 discloses the addition of an imide compound as a compound capable of accelerating the imidization reaction. However, the imide compound disclosed in Patent Document 7 contains a hydroxyl group and an amino group, and therefore, it cannot be denied that it poses a problem of deteriorating the storage stability of a photosensitive resin composition containing a polyimide precursor resin.

[0012] Thus, it is desired to quickly develop a photosensitive resin composition using a polyimide precursor that has all of the following characteristics: it is possible to form a fine pattern; it is possible to obtain a cured film by heating at a low temperature; the cured protective coating or interlayer insulating film has heat resistance in various processes and resistance to the various chemicals used; and the composition has good storage stability. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] Japanese Unexamined Patent Publication No. 115541 / 1983 [Patent Document 2] Japanese Patent Application Publication No. 55-45746 [Patent Document 3] Japanese Patent Application Laid-Open No. 2007-056196 [Patent Document 4] Patent No. 7436606 [Patent Document 5] Patent Publication No. 2022-159241 [Patent Document 6] Patent Publication No. 2024-19341 [Patent Document 7] Patent No. 7252020 Summary of the Invention [Problem to be solved by the invention]

[0014] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive resin composition using a polyimide precursor that can undergo an imide ring-closure reaction at low temperatures, has excellent composition stability, and is capable of forming fine patterns, and that can impart resistance to chemicals after curing. It is also an object of the present invention to provide a pattern formation method using the photosensitive resin composition, and an interlayer insulating film, a surface protective film, and an electronic component that are made of a cured coating formed by curing the photosensitive resin composition. [Means for solving the problem]

[0015] That is, in order to solve the above problems, the present invention provides: A negative photosensitive resin composition, (A) a polymer compound having a polyimide precursor structure, (C) a photopolymerization initiator; (D) an organic compound represented by the following general formula (1): (E) a solvent; The present invention provides a negative photosensitive resin composition comprising: [ka] (In the formula, T represents any one of the structures of the following general formulae (2) to (4), and W represents an alkyl group or an aryl group which may be substituted with an alkoxy group having 4 to 15 carbon atoms.) [ka] (In the formula, V represents a divalent organic group, and * represents a bond.) [ka] (wherein Q represents a halogen atom or a nitro group, and R C 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 of 3 to 5 when Q is a halogen atom, and represents 1 when Q is a nitro group. * represents a bond. [ka] (In the formula, Ar represents a substituted or unsubstituted aromatic ring structure or a heterocyclic ring structure having a heteroatom, and * represents a bond.)

[0016] Addition of the organic compound represented by the general formula (1) to a negative-type photosensitive resin composition containing a polyimide precursor structure makes it possible to reduce the temperature of the curing reaction to obtain a cured film, i.e., the imide ring-closure reaction, to 200°C or less.

[0017] Furthermore, the organic compound represented by the general formula (1) has a protecting group for the -(C=O)-OW group, which can prevent aggregation of the organic compound with a polymer compound containing a polyimide precursor structure, i.e., gelation, and thus can prevent deterioration of the storage stability of the photosensitive resin composition.

[0018] In this case, the component (A) is preferably a polymer compound having a polyimide precursor structure represented by the following general formula (5). [ka] (wherein X is a tetravalent organic group, Y is a divalent organic group, and R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and R 1 and R 2 At least one of the above is a group represented by the following general formula (6): [ka] (In the formula, M 1 , M 2 and M 3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10. * represents a bond.

[0019] A polymer compound containing such a structural unit of a polyimide precursor is preferred from the viewpoint of the film strength of the resulting cured film.

[0020] Furthermore, it is preferable to contain (B) a polymerizable compound having two or more ethylenically unsaturated groups.

[0021] Inclusion of a crosslinking agent having two or more photopolymerizable unsaturated bonds in one molecule in this manner can promote crosslinking by photopolymerization of component (A) in the exposed areas, thereby improving the contrast between the exposed and unexposed areas.

[0022] In this case, it is preferable that W in the general formula (1) of the component (D) is a tert-butyl group.

[0023] When W is a tert-butyl group, it represents a compound in which the oxygen atom of the structure T of the organic compound represented by the general formula (1) above is protected with a tert-butoxycarbonyl group (Boc group). The tert-butoxycarbonyl group (Boc group) is deprotected at a temperature between 100 and 150°C during the heating step of the curing reaction, producing an organic compound that can promote the imide ring-closure reaction, making imidization possible at temperatures below 200°C.

[0024] Furthermore, in this case, it is preferable that W in the general formula (1) of the component (D) is a benzyl group.

[0025] When W is a benzyl group, it represents a compound in which the oxygen atom of the structure T of the organic compound represented by the general formula (1) is protected with a benzyloxycarbonyl protecting group (Z group). The benzyloxycarbonyl protecting group (Z group) is deprotected at a temperature between 120°C and 190°C during the heating step of the curing reaction, producing an organic compound that can promote the imide ring-closure reaction, making imidization possible at temperatures below 200°C.

[0026] The negative photosensitive resin composition is preferably one in which the general formula (2) has a structure represented by the following general formula (2-1). [ka] (In the formula, R a and R brepresents 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; R a and R b may be bonded to each other to form a ring together with the carbon atoms to which they are attached. * indicates a bond.)

[0027] When the general formula (2) has the structure represented by the general formula (2-1) above, the hydroxyl group of the N-hydroxy-imide compound that promotes the imidization reaction is protected with the above-described tert-butoxycarbonyl group (Boc group) or benzyloxycarbonyl protecting group (Z group), thereby improving the storage stability of the photosensitive resin composition containing the polyimide precursor resin.

[0028] A negative photosensitive resin composition in which the general formula (3) has a structure represented by the following general formula (3-1) or (3-2) is preferred. [ka] (In the formula, * represents a bond.) [ka] (In the formula, * represents a bond.)

[0029] When the general formula (3) has a structure represented by the general formula (3-1) or (3-2), the hydroxy group of 4-nitrophenol or pentafluorophenol, which is an active esterifying agent that promotes the imidization reaction, is protected with the above-described tert-butoxycarbonyl group (Boc group) or benzyloxycarbonyl protecting group (Z group), and the storage stability of the photosensitive resin composition containing the polyimide precursor resin can be improved.

[0030] If the general formula (3) is an organic compound containing a structure represented by the general formula (3-1) or (3-2), it can be cited as a more preferred example in terms of ease of availability of raw materials, safety of the compound, low toxicity, etc.

[0031] A negative photosensitive resin composition in which the general formula (4) has a structure represented by the following general formula (4-1) is preferred. [ka] (In the formula, R d represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms which may have a halogen atom, or an aryl group having 6 to 15 carbon atoms, and k represents an integer of 0 to 4. * represents a bond.

[0032] When the general formula (4) has a structure represented by the following general formula (4-1), the hydroxy group of 1-hydroxy-benzotriazole, which is an active esterifying agent that promotes the imidization reaction, is protected with the above-described tert-butoxycarbonyl group (Boc group) or benzyloxycarbonyl protecting group (Z group), thereby improving the storage stability of a photosensitive resin composition containing a polyimide precursor resin.

[0033] It is also preferable that the component (D) is contained in an amount of 1 to 10 parts by mass per 100 parts by mass of the component (A).

[0034] When the amount of the organic compound of 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 undergo thermal deformation, i.e., thermal flow, and pattern formation is not impaired. Furthermore, after curing, the glass transition temperature (Tg.) of the resulting cured film does not decrease. The resulting cured film is required to have a high glass transition temperature (Tg.) because it is required to have heat resistance in the process of manufacturing electronic components formed using the resulting cured film as an interlayer insulating film or a surface protective film.

[0035] Furthermore, the present invention preferably includes, as the thermal crosslinking agent (F), one or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or a formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, a compound in which the hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group, a compound in which the hydrogen atom of a hydroxyl group of a polyhydric phenol or a hydroxyl group of a polyhydric alcohol is substituted with a substituent represented by the following formula (F-1), and a compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (F-2). [ka] (In the formula, the dotted line represents a bond, Rf represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and c represents 1 or 2.)

[0036] The component (F) is a component that undergoes a crosslinking reaction during post-curing after pattern formation of the negative photosensitive resin composition of the present invention, thereby further increasing the strength of the cured product.

[0037] The negative photosensitive resin composition preferably further contains (G) an antioxidant.

[0038] The inclusion of the antioxidant component (G) suppresses unnecessary cross-linking between components (A) or between components (A) and (B) during patterning, improving contrast. Its rust-preventing effect on metal materials also prevents metal oxidation caused by external moisture, photoacid generators, and thermal acid generators, as well as the resulting loss of adhesion and peeling.

[0039] The negative photosensitive resin composition preferably further contains a silane compound (H).

[0040] The negative-type photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, etc., and examples of the metal adhesion improver include silane compounds.

[0041] The negative photosensitive resin composition preferably further contains (I) a polymerization inhibitor.

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

[0043] The present invention also provides a pattern forming method comprising: (1) applying the photosensitive resin composition described above onto a substrate to form a photosensitive film; (2) a step of exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask after the heat treatment; (3) developing the exposed film using an organic solvent developer; It is possible to provide a pattern forming method comprising the steps of:

[0044] The pattern formation method for such a negative-type photosensitive composition is a pattern formation method that enables the formation of a fine pattern, since the negative-type photosensitive resin composition uses, as the base resin (A), a polymeric compound containing a polyimide precursor structure, which is a polymer having the above-described polymerizable unsaturated bond group, and contains the organic compound as component (D) of the present invention, and the resulting pattern can be cured without causing any change in shape.

[0045] The present invention can provide a method for forming a cured coating, which comprises the step of subsequently heating the patterned coating obtained by the above-mentioned pattern formation method at a temperature of 100 to 300°C and post-curing it.

[0046] By carrying out such a pattern formation method, the curing reaction after pattern formation, that is, the imide ring-closing reaction, can be carried out at a low temperature.

[0047] The present invention also provides an interlayer insulating film, which is a cured film obtained by curing the above-described negative photosensitive resin composition.

[0048] The cured film obtained by curing the photosensitive resin composition of the present invention is useful as an interlayer insulating film.

[0049] The present invention also provides a surface protection film which is a cured coating formed by curing the above-described negative photosensitive resin composition.

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

[0051] The present invention also provides an electronic component having the above-described interlayer insulating film.

[0052] The present invention also provides an electronic component having the above-described surface protection film.

[0053] Such electronic components have excellent reliability because they have a protective coating (interlayer insulating film or surface protective film) that is heat-resistant, chemical-resistant, and insulating. [Effects of the Invention]

[0054] As described above, the present invention provides a negative-type photosensitive resin composition containing a polymer compound having a polyimide precursor structure that can undergo an imide ring-closing reaction at low temperatures regardless of the molecular structure of the polyimide precursor and has high storage stability. Furthermore, since the composition can be cured without causing any change in the shape of the resulting pattern, it is possible to form a fine pattern. Furthermore, the cured film obtained by curing after pattern formation exhibits excellent chemical resistance and a high glass transition temperature (Tg). DETAILED DESCRIPTION OF THE INVENTION

[0055] As described above, there has been a need for the development of a photosensitive resin composition that uses a polyimide precursor that can undergo an imide ring-closure reaction at low temperatures, has excellent composition stability, is capable of forming fine patterns, and can impart resistance to chemicals after curing.

[0056] As a result of extensive research to achieve the above object, the present inventors have found that a photosensitive resin composition using a polymer compound containing a polyimide precursor structure, to which an organic compound represented by the following general formula (1) is added, can achieve fine pattern formation without impairing the formation of a fine pattern, and that the curing reaction after pattern formation, i.e., the imide ring-closing reaction, can be carried out at 200°C or less.

[0057] The inventors also found that the obtained cured film has excellent chemical resistance and a high glass transition temperature (Tg.), and further found that the storage stability of the photosensitive resin composition is also good, leading to the completion of the present invention.

[0058] That is, the present invention provides a negative photosensitive resin composition, (A) a polymer compound having a polyimide precursor structure, (C) a photopolymerization initiator; (D) an organic compound represented by the following general formula (1): (E) a solvent; The negative photosensitive resin composition is characterized by comprising: [ka] (In the formula, T represents any one of the structures of the following general formulae (2) to (4), and W represents an alkyl group or an aryl group which may be substituted with an alkoxy group having 4 to 15 carbon atoms.) [ka] (In the formula, V represents a divalent organic group, and * represents a bond.) [ka] (wherein Q represents a halogen atom or a nitro group, and R C 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 of 3 to 5 when Q is a halogen atom, and represents 1 when Q is a nitro group. * represents a bond. [ka] (In the formula, Ar represents a substituted or unsubstituted aromatic ring structure or a heterocyclic ring structure having a heteroatom, and * represents a bond.)

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

[0060] [Component (A)] The polymer compound containing the structural unit of the polyimide precursor according to the present invention is preferably a polymer compound represented by the following formula (5), from the viewpoint of the film strength of the resulting cured film. [ka] (wherein X is a tetravalent organic group, Y is a divalent organic group, and R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and R 1 and R 2 At least one of the above is a group represented by the following general formula (6): [ka] (In the formula, M 1 , M 2 and M 3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10. * represents a bond.

[0061] X in the above general formula (5) is a tetravalent organic group, but is not limited thereto as long as it is a tetravalent organic group. It is preferably a tetravalent organic group of an alicyclic aliphatic group or aromatic group having 4 to 40 carbon atoms. It is more preferably a tetravalent organic group represented by the following formula (7). The structure of X may be one type or a combination of two or more types. [ka] (In the formula, R e1 , R e2 are each independently a methyl group or a phenyl group, b1 and b2 are integers of 1 to 20, and the dotted lines represent bonds.

[0062] Y in the above general formula (5) is a divalent organic group, and is not limited as long as it is a divalent organic group, but is preferably a divalent organic group having 6 to 40 carbon atoms, and more preferably a divalent cyclic organic group containing 1 to 4 substituted aromatic or aliphatic rings, or a divalent aliphatic group without a cyclic structure, or a siloxane group. More preferred examples of Y include structures represented by the following formulas (8) and (9). Furthermore, the structure of Y may be one type or a combination of two or more types. [ka] (In the formula, b3 represents an integer of 1 to 20, s1 represents an integer of 1 to 40, s2 and s3 each independently represents an integer of 0 to 40, and the dotted lines represent bonds.)

[0063] [ka] (wherein b4 is an integer of 1 to 4, and R e4 is a fluorine atom, a methyl group, an ethyl group, a propyl group, an n-butyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a trifluoromethyl group, and when b4 is 2 or more, R e4 may be the same or different, b5 is an integer of 1 to 40, and the dotted line represents a bond.

[0064] R in the above general formula (5) 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and the monovalent organic group can be a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group represented by the above general formula (6), and R 1 and R 2 At least one of the above is an organic group represented by the general formula (6).

[0065] M in the above general formula (6) 1is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but is preferably a hydrogen atom or a methyl group from the viewpoint of the photosensitive properties of the negative photosensitive resin composition.

[0066] M in the above general formula (6) 2 and M 3 are not limited as long as they are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but are preferably hydrogen atoms from the viewpoint of the photosensitive properties of the negative photosensitive resin composition.

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

[0068] Furthermore, the polymer compound of the present invention can further contain, in addition to the structural unit represented by the above general formula (5), one or more structural units represented by the following general formulae (10) to (12). [ka] (In the formula, X1 is a tetravalent organic group that may be the same as or different from X, and Y1 is a divalent organic group that may be the same as or different from Y.) [ka] (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.) [ka] (In the formula, Y3 is a divalent organic group that is the same as or different from Y, and X3 is a tetravalent organic group.)

[0069] X1 in the general formula (10) above is a tetravalent organic group, but may be the same as or different from the above X, and is not limited as long as it is a tetravalent organic group. Preferably, it is a tetravalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a tetravalent aromatic group having 6 to 40 carbon atoms, and may contain a siloxane skeleton. More preferably, it is a tetravalent organic group represented by the above formula (7). Furthermore, the structure of X1 may be one type or a combination of two or more types.

[0070] Y1 in the general formula (10) above is a divalent organic group, which may be the same as or different from Y. There are no particular limitations on the divalent organic group, but it is preferably a divalent organic group having 6 to 40 carbon atoms, and more preferably a divalent cyclic organic group containing 1 to 4 substituted aromatic or aliphatic rings, or a divalent aliphatic group without a cyclic structure, or a siloxane group. More preferred examples of Y1 include the structures represented by the formulas (8) and (9). The structure of Y1 may be one type or a combination of two or more types.

[0071] Resin compositions containing polymeric compounds containing structural units represented by the general formula (10) are preferred because they can improve the mechanical strength, adhesion to the substrate, and heat resistance of the cured coating obtained by pattern formation. Furthermore, structural unit (10) is preferred because it eliminates the need for a ring-closing reaction during post-curing, allowing for a relatively lower curing reaction temperature.

[0072] X2 in the above general formula (11) is a divalent organic group, and is not limited as long as it is a divalent organic group. Preferably, it is a divalent organic group having an aliphatic chain length structure of 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 organic group represented by the following formula (13). Furthermore, the structure of X2 may be one type or a combination of two or more types. [ka] (In the formula, R a3are each independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, b4 is an integer of 1 to 30, and the dotted line represents a bond.

[0073] Y2 in the general formula (11) above is a divalent organic group, but it may be the same as or different from the above Y, and is not limited as long as it is a divalent organic group. It is preferably a divalent organic group having 6 to 40 carbon atoms, and is a divalent cyclic organic group containing 1 to 4 substituted aromatic or aliphatic rings, or a divalent aliphatic group or siloxane group without a cyclic structure. More preferred examples include structures represented by the above formulas (8) or (9). The structure of Y2 may be one type or a combination of two or more types.

[0074] Y3 in the general formula (12) above is a divalent organic group, which may be the same as or different from Y above, and is not limited as long as it is a divalent organic group. Preferably, it is a divalent organic group having an aliphatic chain length structure with 4 to 40 carbon atoms, a divalent alicyclic aliphatic group with 4 to 40 carbon atoms, or a divalent aromatic group with 6 to 40 carbon atoms. More preferably, it is a divalent organic group represented by the formula (13) above. Furthermore, the structure of Y3 may be one type or a combination of two or more types.

[0075] X3 in the general formula (12) above is a tetravalent organic group, and is not limited as long as it is a tetravalent organic group, but is preferably a tetravalent organic group having 6 to 40 carbon atoms, and more preferably a tetravalent cyclic organic group containing 1 to 4 substituted aromatic or aliphatic rings, or a tetravalent aliphatic group without a cyclic structure, or a siloxane group. More preferred X3 includes a structure represented by the following formula (14). Furthermore, the structure of X3 may be one type or a combination of two or more types. [ka] (In the formula, b 12 , b 13 , and b 14 is an integer between 1 and 10, and b 15 is an integer from 1 to 20, and the dotted lines represent bonds.

[0076] Resin compositions containing a polymer containing a structural unit represented by the general formula (12) are preferred because they can improve the mechanical strength, adhesion to the substrate, and heat resistance of the cured film obtained by pattern formation. Furthermore, when the structure represented by the general formula (12) is contained, it is preferable because a ring-closing reaction is not required during post-curing, and the curing reaction temperature can be relatively lowered.

[0077] The polymer of the present invention preferably has a molecular weight of 5,000 to 100,000, more preferably 7,000 to 50,000. When the molecular weight is 5,000 or more, it becomes easy to form a film of a desired thickness on a substrate from a photosensitive resin composition containing the polymer of the present invention. When the molecular weight is 100,000 or less, the viscosity of the photosensitive resin composition does not become significantly high, and film formation is easy. In the present invention, the weight-average molecular weight is measured by GPC using DMF as an eluent at 40°C, and is a value calculated as polystyrene by gel permeation chromatography (GPC).

[0078] [Method of manufacturing polymer compounds] The polymer compound contained in the negative photosensitive resin composition of the present invention preferably contains a structural unit represented by the following general formula (5). [ka] (wherein X is a tetravalent organic group, Y is a divalent organic group, and R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and R 1 and R 2 At least one of the above is a group represented by the following general formula (6): [ka] In the formula, M1, M2, and M3 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m represents an integer of 2 to 10. * represents a bond.

[0079] The polymer containing the structural unit represented by the general formula (5) can be obtained by reacting a tetracarboxylic acid diester compound represented by the following general formula (15) with a diamine represented by the following general formula (16). [ka] (In the formula, X, R 1 and R 2 is the same as above.) [ka] (wherein Y is the same as above).

[0080] In the above general formula (15), R 1 and R 2 At least one of the above is an organic group represented by the general formula (6), and the organic group represented by the general formula (6) can be introduced by reacting a tetracarboxylic dianhydride represented by the following general formula (17) with a compound having a terminal hydroxyl group represented by the following general formula (18) in the presence of a basic catalyst such as pyridine. Here, the tetracarboxylic dianhydride represented by the following general formula (17) is the origin of X in the above general formula (5) (for example, the tetravalent organic group represented by the above formula (7)), and the compound having a terminal hydroxyl group represented by the following general formula (18) is capable of introducing the organic group represented by the general formula (6). [ka] (wherein X represents a tetravalent organic group and has the same meaning as X in general formula (5) above). [ka] (In the formula, M 1 , M 2 , M 3 and m is M in the above general formula (6). 1 , M 2 , M 3 , and m.)

[0081] Suitable examples of the tetracarboxylic acid dianhydride represented by the above general formula (17) include aromatic acid dianhydrides, alicyclic acid dianhydrides, aliphatic acid dianhydrides, and siloxane skeleton-containing acid dianhydrides.

[0082] Examples of aromatic acid dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-terphenyltetracarboxylic dianhydride, 3,3',4,4'-oxyphthalic dianhydride, 2,3,3',4'-oxyphthalic dianhydride, 2,3,2',3'-oxyphthalic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, benzophenone, benzophenone, benzophenone-3,3',4,4'- ... Diazepam-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1,4-(3,4-dicarboxyphenoxy)benzene dianhydride, p-phenylenebis( Trimellitic acid monoester anhydride), bis(1,3-dioxo-1,3-dihydroisobenzfuran-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)fluorene dianhydride, 9,9-bis(4-(3,4-dicarboxyphenoxy)phenyl)fluorene dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride Anhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzoyloxy)phenyl)hexafluoropropane dianhydride, 1,6-difluoropyromellitic dianhydride, 1-trifluoromethylpyromellitic dianhydride, 1,6-ditrifluoromethylpyromellitic dianhydride, 2,2'-bis(trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,Examples of the dianhydride include, but are not limited to, 2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, and acid dianhydride compounds in which the aromatic ring of these dianhydrides is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

[0083] Examples of the alicyclic acid dianhydride include 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, and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride. , 1,2,3,4-cycloheptanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic 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]heptanetetracarboxylic dianhydride, bicyclo[2,2,1]heptane-5-carboxymethyl 2,3,6-tricarboxylic dianhydride, 7-oxabicyclo[2,2,1]heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecahydroanthracene-1,2,8,9-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride, 3,3',4,4'-oxydicyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,Examples of suitable dianhydrides include, but are not limited to, 2-dicarboxylic acid anhydrides, "Rikacid" (registered trademark) BT-100 (all trade names, manufactured by New Japan Chemical Co., Ltd.), and derivatives thereof, as well as acid dianhydrides in which the alicyclic ring of these dianhydrides is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

[0084] Examples of the aliphatic acid dianhydride include, but are not limited to, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and derivatives thereof.

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

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

[0087] M in the above general formula (18) 1 is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but is preferably a hydrogen atom or a methyl group from the viewpoint of the photosensitive properties of the negative photosensitive resin composition.

[0088] M in the above general formula (18) 2 and M 3 are not limited as long as they are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but are preferably hydrogen atoms from the viewpoint of the photosensitive properties of the negative photosensitive resin composition.

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

[0090] Among the compounds having a hydroxyl group at the terminal represented by the above general formula (18), suitable compounds include, for example, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-methacryloyloxyethyl alcohol, and 1-methacryloyloxy-3-propyl alcohol.

[0091] In addition, R in the above general formula (5) 1 and R 2 may be a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. A linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms is introduced into the above general formula (5) (i.e., R 1 and R 2 is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms), a method in which a compound having a terminal hydroxyl group, represented by the above general formula (18), and a tetracarboxylic dianhydride are reacted in the presence of a basic catalyst such as pyridine, and a linear, branched, or cyclic alcohol having 1 to 6 carbon atoms is simultaneously added.

[0092] Suitable alcohols that can be used in this case include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, cyclopentanol, and cyclohexanol.

[0093] The reaction of the tetracarboxylic dianhydride represented by the general formula (17) with the compound having a terminal hydroxyl group represented by the general formula (18) can be carried out by stirring, dissolving, and mixing the tetracarboxylic dianhydride represented by the general formula (17) and the compound having a terminal hydroxyl group represented by the general formula (18) in a reaction solvent in the presence of a basic catalyst such as pyridine at a reaction temperature of 20 to 50°C for 4 to 10 hours, thereby causing a half-esterification reaction of the acid dianhydride to proceed, and the desired tetracarboxylic diester compound represented by the general formula (15) can be obtained as a solution dissolved in the reaction solvent.

[0094] The resulting tetracarboxylic acid diester compound may be isolated, or the resulting solution may be used as is in the reaction with a diamine in the next step described below.

[0095] The reaction solvent is preferably one that can dissolve the tetracarboxylic acid diester compound and the polymer having structural units of a polyimide precursor obtained by the subsequent polycondensation reaction of the tetracarboxylic acid diester compound with a diamine. Examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and γ-butyrolactone. Ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons can also be used. Specific 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-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, and xylene. These solvents may be used alone or in combination as needed.

[0096] Suitable examples of the diamine represented by the general formula (16) include (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, and (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, (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 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, (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-aminobenzoate, (3-nitrophenyl-4-amino)phenyl-4-aminobenzoate, ( 2-cyanophenyl-4-amino)phenyl-4-aminobenzoate, (3-cyanophenyl-4-amino)phenyl-4-aminobenzoate, (2-phenylethyl-4-amino)phenyl-4-aminobenzoate, (3-phenylethyl-4-amino)phenyl-4-aminobenzoate, (2-phenylamino-4-amino)phenyl-4-aminobenzoate, (3-phenylamino-4-amino)phenyl-4-aminobenzoate, (2-(4,4'-biphenyl)-4-amino)phenyl-4-aminobenzoate,(3-(4,4'-biphenyl)-4-amino)phenyl-4-aminobenzoate, (2-naphthyl-4-amino)phenyl-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 (2-ethoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (3-ethoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (2-benzyl-4-amino)phenyl-4-aminobenzoate, (3-benzyl-4-amino)phenyl-4-aminobenzoate, (2-methoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (3-methoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (2-ethoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (3-ethoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (2-benzyl-4-amino)phenyl-4-aminobenzoate, (3-benzyl-4-amino)phenyl (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,(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-ethyl (2-propylbenzyloxy-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 benzyloxybenzoate, (2-ethoxybenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-ethoxybenzyloxy-4-amino)phenyl-4-aminobenzoate, 4-(4-aminophenoxy)-3-methylbenzenamine, 4-(4-aminophenoxy)-2-methylbenzenamine, 4-(4-aminophenoxy)-3-ethylbenzenamine, 4-(4-aminophenoxy)-2-ethylbenzenamine, 4-(4-aminophenoxy)-3-propyl Benzenamine, 4-(4-aminophenoxy)-2-propylbenzenamine, 4-(4-aminophenoxy)-3-isopropylbenzenamine, 4-(4-aminophenoxy)-2-isopropylbenzenamine, 4-(4-aminophenoxy)-3-butylbenzenamine, 4-(4-aminophenoxy)-2-butylbenzenamine, 4-(4-aminophenoxy)-3-isobutylbenzenamine, 4-(4-aminophenoxy)-2-isobutylbenzenamine,

[0097] 4-(4-aminophenoxy)-3-pentylbenzenamine, 4-(4-aminophenoxy)-2-pentylbenzenamine, 4-(4-aminophenoxy)-3-hexylbenzenamine, 4-(4-aminophenoxy)-2-hexylbenzenamine, 4-(4-aminophenoxy)-3-(trifluoromethyl)benzenamine, 4-(4-aminophenoxy)-2-(trifluoromethyl)benzenamine, 4-(4-aminophenoxy)-3-methoxybenzenamine, 4-(4-aminophenoxy)-2-methoxybenzenamine, 4-( 4-Aminophenoxy)-3-ethoxybenzenamine, 4-(4-aminophenoxy)-2-ethoxybenzenamine, 4-(4-aminophenoxy)-3-propoxybenzenamine, 4-(4-aminophenoxy)-2-propoxybenzenamine, 4-(4-aminophenoxy)-3-butoxybenzenamine, 4-(4-aminophenoxy)-2-butoxybenzenamine, 4-(4-aminophenoxy)-3-phenylbenzenamine, 4-(4-aminophenoxy)-2-phenylbenzenamine, 4-(4-aminophenoxy)-3-methyl phenylbenzenamine, 4-(4-aminophenoxy)-2-methylphenylbenzenamine, 4-(4-aminophenoxy)-3-ethylphenylbenzenamine, 4-(4-aminophenoxy)-2-ethylphenylbenzenamine, 4-(4-aminophenoxy)-3-propylphenylbenzenamine, 4-(4-aminophenoxy)-2-propylphenylbenzenamine, 4-(4-aminophenoxy)-3-butylphenylbenzenamine, 4-(4-aminophenoxy)-2-butyl ... phenoxy)-3-fluorophenylbenzenamine, 4-(4-aminophenoxy)-2-fluorophenylbenzenamine, 4-(4-aminophenoxy)-3-chlorophenylbenzenamine, 4-(4-aminophenoxy)-2-chlorophenylbenzenamine, 4-(4-aminophenoxy)-3-bromophenylbenzenamine, 4-(4-aminophenoxy)-2-bromophenylbenzenamine, 4-(4-aminophenoxy)-3-methoxyphenylbenzenamine, 4-(4-aminophenoxy)-2-methoxyphenylbenzenamine,4-(4-aminophenoxy)-3-ethoxyphenylbenzenamine, 4-(4-aminophenoxy)-2-ethoxyphenylbenzenamine, 4-(4-aminophenoxy)-3-(phenylethyl)phenylbenzenamine, 4-(4-aminophenoxy)-2-(phenylethyl)phenylbenzenamine, 4-(4-aminophenoxy)-3-naphthylphenylbenzenamine, 4-(4-aminophenoxy)-2-naphthylphenylbenzenamine, 4-(4-aminophenoxy)-3-benzylphenylbenzenamine, 4-(4-aminophenoxy)- 4-((4-aminophenyl)thio)-2-methylbenzenamine, 4-((4-aminophenyl)thio)-3-ethylbenzenamine, 4-((4-aminophenyl)thio)-2-ethylbenzenamine, 4-((4-aminophenyl)thio)-3-propylbenzenamine, 4-((4-aminophenyl)thio)-2-propylbenzenamine, 4-((4-aminophenyl)thio)-3-isopropylbenzenamine, 4-(( 4-aminophenyl)thio)-2-isopropylbenzenamine, 4-((4-aminophenyl)thio)-3-butylbenzenamine, 4-((4-aminophenyl)thio)-2-butylbenzenamine, 4-((4-aminophenyl)thio)-3-isobutylbenzenamine, 4-((4-aminophenyl)thio)-2-isobutylbenzenamine, 4-((4-aminophenyl)thio)-3-(trifluoromethyl)benzenamine, 4-((4-aminophenyl)thio)-2-(trifluoromethyl)benzenamine, 4-((4-aminophenyl) 4-((4-aminophenyl)thio)-3-methoxybenzenamine, 4-((4-aminophenyl)thio)-2-methoxybenzenamine, 4-((4-aminophenyl)thio)-3-ethoxybenzenamine, 4-((4-aminophenyl)thio)-2-ethoxybenzenamine, 4-((4-aminophenyl)thio)-3-propoxybenzenamine, 4-((4-aminophenyl)thio)-2-propoxybenzenamine, 4-((4-aminophenyl)thio)-3-isopropoxybenzenamine, 4-((4-aminophenyl)thio)-2-isopropoxybenzenamine,4-((4-aminophenyl)thio)-3-butoxybenzenamine, 4-((4-aminophenyl)thio)-2-butoxybenzenamine, 4-((4-aminophenyl)thio)-3-phenylbenzenamine, 4-((4-aminophenyl)thio)-2-phenylbenzenamine, 4-((4-aminophenyl)thio)-3-naphthylbenzenamine, 4-((4-aminophenyl)thio)-2-naphthylbenzenamine, 4-((4-aminophenyl)thio)-3-methoxyphenylbenzenamine, 4-((4-aminophenyl)thio (e)-2-Methoxyphenylbenzenamine, 4-((4-aminophenyl)methyl)-3-methylbenzenamine, 4-((4-aminophenyl)methyl)-2-methylbenzenamine, 4-((4-aminophenyl)methyl)-3-ethylbenzenamine, 4-((4-aminophenyl)methyl)-2-ethylbenzenamine, 4-((4-aminophenyl)methyl)-3-propylbenzenamine, 4-((4-aminophenyl)methyl)-2-propylbenzenamine, 4-((4-aminophenyl)methyl)-3-isopropylbenzenamine benzophenoneamine, 4-((4-aminophenyl)methyl)-2-isopropylbenzophenoneamine, 4-((4-aminophenyl)methyl)-3-butylbenzophenoneamine, 4-((4-aminophenyl)methyl)-2-butylbenzophenoneamine, 4-((4-aminophenyl)methyl)-3-isobutylbenzophenoneamine, 4-((4-aminophenyl)methyl)-2-isobutylbenzophenoneamine, 4-((4-aminophenyl)methyl)-3-(trifluoromethyl)benzophenoneamine, 4-((4-aminophenyl)methyl)-2-(trifluoromethyl)benzophenone )benzenamine, 4-((4-aminophenyl)methyl)-3-methoxybenzenamine, 4-((4-aminophenyl)methyl)-2-methoxybenzenamine, 4-((4-aminophenyl)methyl)-3-ethoxybenzenamine, 4-((4-aminophenyl)methyl)-2-ethoxybenzenamine, 4-((4-aminophenyl)methyl)-3-propoxybenzenamine, 4-((4-aminophenyl)methyl)-2-propoxybenzenamine, 4-((4-aminophenyl)methyl)-3-isopropoxybenzenamine,4-((4-aminophenyl)methyl)-2-isopropoxybenzenamine, 4-((4-aminophenyl)methyl)-3-butoxybenzenamine, 4-((4-aminophenyl)methyl)-2-butoxybenzenamine, 4-((4-aminophenyl)methyl)-3-phenylbenzenamine, 4-((4-aminophenyl)methyl)-2-phenylbenzenamine, 4-((4-aminophenyl)methyl)-3-naphthylbenzenamine, 4-((4-aminophenyl)methyl)-2-naphthylbenzenamine, 4-((4-aminophenyl)methyl)-3-methoxyphenylbenzenamine, 4-((4-aminophenyl)methyl)-2-methoxyphenylbenzenamine, (4-amino-2-methylphenyl)(4-aminophenyl)methanone, Examples of suitable amines include, but are not limited to, (4-amino-2-ethylphenyl)(4-aminophenyl)methanone, (4-amino-2-propylphenyl)(4-aminophenyl)methanone, (4-amino-2-isopropylphenyl)(4-aminophenyl)methanone, (4-amino-2-butylphenyl)(4-aminophenyl)methanone, (4-amino-2-(trifluoromethyl)phenyl)(4-aminophenyl)methanone, 4-amino-2-methoxyphenyl)(4-aminophenyl)methanone, 4-amino-2-ethoxyphenyl)(4-aminophenyl)methanone, (4-amino-2-(phenyl)phenyl)(4-aminophenyl)methanone, and (4-amino-2-(methoxyphenyl)phenyl)(4-aminophenyl)methanone.

[0098] Here, the polymer compound having a polyimide precursor containing a structural unit represented by the general formula (5) can be obtained, for example, by reacting a tetracarboxylic acid diester compound represented by the general formula (15) with a diamine represented by the general formula (16) in the presence of a dehydrating condensation agent. That is, the tetracarboxylic acid diester compound represented by the general formula (15) is used in the reaction in a state of being dissolved in the reaction solvent, and a known dehydration condensation agent (e.g., dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc.) is added to this reaction solution under ice cooling and mixed to convert the tetracarboxylic acid diester compound represented by the general formula (15) into a polyanhydride, and then a diamine represented by the general formula (16) dissolved or dispersed in a separate solvent is added dropwise to the polyanhydride to carry out polycondensation, thereby obtaining a polymer compound having a polyimide precursor containing a structural unit represented by the general formula (2).

[0099] Another method for obtaining a polymer compound having a polyimide precursor containing a structural unit represented by the general formula (5) by reacting a tetracarboxylic acid diester compound represented by the general formula (15) with a diamine compound represented by the general formula (16) includes converting the tetracarboxylic acid diester compound represented by the general formula (15) into an acid chloride using a chlorinating agent such as thionyl chloride or dichlorooxalic acid, and reacting the acid chloride with the diamine represented by the general formula (16).

[0100] In the reaction of converting the above-mentioned tetracarboxylic acid diester compound into an acid chloride using a chlorinating agent, a basic compound such as pyridine, 4-dimethylaminopyridine, or triethylamine may be used.

[0101] Next, the acid chloride of the resulting tetracarboxylic acid diester compound is reacted with the diamine represented by the general formula (16) in the presence of a basic catalyst to obtain a polymer compound having a polyimide precursor containing the structural unit represented by the general formula (5). Examples of the basic catalyst include pyridine, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[4.3.0]non-5-ene.

[0102] Among the methods for producing a polymer compound having a polyimide precursor used in the negative-tone photosensitive resin composition of the present invention, the method using an acid chloride is preferably one that can dissolve the above-mentioned tetracarboxylic acid diester compound, its acid chloride, and the polyimide precursor polymer obtained by polycondensation with a diamine. Solvents similar to those described above can be used. Specific examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, and γ-butyrolactone. In addition to polar solvents, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons can also be used. Examples of the organic solvent 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-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, etc. These organic solvents may be used alone or in combination of two or more.

[0103] As described above, the polymer compound having a polyimide precursor used in the negative-type photosensitive resin composition of the present invention can further contain a structural unit represented by the following general formula (10), in addition to the structural unit represented by the above general formula (5). [ka] (wherein X1 and Y1 are the same as above.)

[0104] A polymer containing the structural unit represented by the general formula (10) can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (19) with a diamine represented by the following general formula (20): First, a tetracarboxylic dianhydride represented by the following general formula (19) is reacted with a diamine represented by the following general formula (20) to synthesize an amide acid, and then imidization is carried out by chemical imidization or thermal dehydration to obtain a polymer containing the structural unit (10).

[0105] The structural unit (10) can be produced by dissolving a diamine in a solvent with a high boiling point and high polarity, such as γ-butyrolactone or N-methyl-2-pyrrolidone, adding an acid anhydride, and reacting the mixture at 0 to 80°C, preferably 10 to 50°C, to form an amide acid. In chemical imidization, for example, acetic anhydride and pyridine are added to the mixture to perform the imidization reaction. In imidization by thermal dehydration, a nonpolar solvent such as xylene is added, and the mixture is heated to 100 to 200°C, preferably 130 to 180°C, to perform the imidization reaction while removing water from the reaction system. [ka] (wherein X1 is the same as defined above). [ka] (wherein Y1 is the same as defined above.)

[0106] As the tetracarboxylic dianhydride represented by the above general formula (19), the examples given for the tetracarboxylic dianhydride represented by the above general formula (17) can be mentioned as suitable examples.

[0107] As the diamine represented by the above general formula (20), the examples of the diamine represented by the above general formula (16) can be mentioned as suitable examples.

[0108] As described above, the polymer compound having a polyimide precursor used in the negative-type photosensitive resin composition of the present invention can further contain a structural unit represented by the following general formula (11), in addition to the structural unit represented by the above general formula (5). [ka] (wherein X2 and Y2 are the same as above.)

[0109] A polymer containing the structural unit represented by the general formula (11) can be obtained by the same reaction procedure as that for the structural unit (5), i.e., by reacting a dicarboxylic acid compound represented by the following general formula (21) in the presence of a dehydration condensation agent or by converting it to an acid chloride using a chlorinating agent, and then reacting the resulting compound with a diamine represented by the general formula (22). [ka] (wherein X2 is the same as defined above). [ka] (wherein Y2 is the same as defined above.)

[0110] Examples of the dicarboxylic acid compound represented by the general formula (21) include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, and pimelic acid. , 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanediol, heneicosanediol, docosanediol, tricosanediol, tetracosanediol, pentacosanediol, hexacosanediol, heptacosanediol, octacosanediol, nonacosanediol, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, and diglycolic acid.

[0111] Furthermore, examples of dicarboxylic acid compounds having an aromatic ring include phthalic acid, isophthalic acid, terephthalic acid, 4,4'-diphenyl ether dicarboxylic acid, 3,4'-diphenyl ether dicarboxylic acid, 3,3'-diphenyl ether dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 3,4'-biphenyl dicarboxylic acid, 3,3'-biphenyl dicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylic acid, 3,3'-benzophenone dicarboxylic acid, 4,4'-hexafluoroisopropylidene dibenzoic acid, 4,4'-dicarboxydiphenylamide, 1,4-phenylenediacetic acid, bis(2-methyl-2-propanol), ... Examples of suitable carboxylic acids include, but are not limited to, bis(4-carboxyphenyl)sulfide, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-carboxyphenyl)tetraphenyldisiloxane, bis(4-carboxyphenyl)tetramethyldisiloxane, bis(4-carboxyphenyl)sulfone, bis(4-carboxyphenyl)methane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,2-bis(p-carboxyphenyl)propane, and 2,6-naphthalenedicarboxylic acid. These may be used alone or in combination.

[0112] As the diamine represented by the above general formula (22), the examples given for the diamine represented by the above general formula (16) can be mentioned as suitable examples.

[0113] As described above, the polymer compound having a polyimide precursor used in the negative-type photosensitive resin composition of the present invention can further contain a structural unit represented by the following general formula (12), in addition to the structural unit represented by the above general formula (5). [ka] (In the formula, X3 and Y3 are the same as above.)

[0114] The polymer containing the structural unit represented by the general formula (12) can be obtained by reacting a dicarboxylic acid compound represented by the following general formula (23) in the presence of a dehydrating condensation agent or by converting it into an acid chloride using a chlorinating agent, and then reacting it with a dihydroxydiamine compound represented by the following general formula (24) to synthesize a hydroxyamide (polyoxazole precursor), which is then subjected to a thermal dehydration step to form an oxazole ring. [ka] (wherein Y3 is the same as defined above.) [ka] (wherein X3 is the same as defined above.)

[0115] As the dicarboxylic acid compound represented by the above general formula (23), the examples given for the dicarboxylic acid compound represented by the above general formula (21) can be mentioned as suitable examples.

[0116] Examples of the dihydroxydiamine compound represented by the general formula (24) include 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxybiphenyl ether, 2,2'-bis(3-amino-4-hydroxyphenyl)sulfide, 2,2'-bis(3-amino-4-hydroxyphenyl)ketone, 3,3'-diamino-4,4'-dihydroxyphenylmethane, 1,2-bis(3-amino-4-hydroxyphenyl)ethane, 2,2'-bis(3-amino-4-hydroxyphenyl)difluoromethane, 4,4'-(1,1,2,2,3 ,3-hexafluoro-1,3-propanediyl)bis(2-aminophenol), 2,2'-bis(3-amino-4-hydroxyphenyl)propane, 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxyphenyl)sulfone, 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane, 4,4'-(1,4-phenylenebis(oxy))bis(2-aminophenol), 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, etc., but are not limited thereto. These may be used alone or in combination.

[0117] (Polymer molecular weight and introduction of end-capping agent) The suitable molecular weight of the polymer compound is preferably 5,000 to 100,000, more preferably 7,000 to 50,000. When the molecular weight is 5,000 or more, it becomes easy to form a film of a desired thickness on a substrate from the negative-type photosensitive resin composition of the present invention using the polymer, and when the molecular weight is 100,000 or less, the viscosity of the negative-type photosensitive resin composition becomes appropriate, and there is no problem in film formation.

[0118] The polymer may be capped at both ends with an end-capping agent for the purposes of controlling the molecular weight in the polycondensation reaction and suppressing changes in the molecular weight of the resulting polymer over time, i.e., gelation. Examples of end-capping agents that react with acid dianhydrides include monoamines and monohydric alcohols. Examples of end-capping agents that react with diamine compounds include acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds, dicarbonates, vinyl ethers, and the like. Furthermore, by reacting with an end-capping agent, various organic groups can be introduced as end groups.

[0119] Monoamines used as a terminal blocking agent for the acid anhydride group include aniline, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6- Aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, amelide, 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 phthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-Diethynylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2 -ethynyl-8-aminonaphthalene, 3,5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7-diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-aminonaphthalene, 4,8-diethynyl-2-aminonaphthalene, 4-fluoroaniline, 3-fluoroaniline, 2-fluoroaniline, 2,4-difluoroaniline, 3,4-difluoroaniline, 2,4,Examples of the fluoroaniline include, but are not limited to, 6-trifluoroaniline, 2,3,4-trifluoroaniline, and pentafluoroaniline. These may be used alone or in combination of two or more.

[0120] On the other hand, examples of monohydric alcohols that can be used as a terminal blocking agent for the acid anhydride group 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, and 1-undecanol. nol, 2-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 2-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 2-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2-heptadecanol, 1-octadecanol, 2-octadecanol, 1-nonadecanol, 2-nonadecanol, 1-icosanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-methyl- 1-Butanol, 3-Methyl-1-butanol, 2-Methyl-2-butanol, 3-Methyl-2-butanol, 2-Propyl-1-pentanol, 2-Ethyl-1-hexanol, 4-Methyl-3-heptanol, 6-Methyl-2-heptanol, 2,4,4-Trimethyl-1-hexanol, 2,6-Dimethyl-4-heptanol, Isononyl alcohol, 3,7-Dimethyl-3-octanol, 2,4-Dimethyl-1-heptanol, 2-Heptylundecanol, Ethylene glycol monoethyl ether Examples of suitable olefin solvents include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol 1-methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, cyclopentanol, cyclohexanol, cyclopentane monomethylol, dicyclopentane monomethylol, tricyclodecane monomethylol, norborneol, and terpineol. These may be used alone or in combination of two or more.

[0121] Examples of acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds that can be used as the amino group terminal capping agents include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 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, 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 Phthalene, 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-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 Monocarboxylic acids such as 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, and 8-ethynyl-2-naphthoic acid, and monoacid chloride compounds in which the carboxy group of these acids is converted into an acid chloride, as well as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,Examples of such compounds include monoacid chloride compounds in which only the monocarboxy group of dicarboxylic acids such as 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 is converted to an acid chloride, and monoactive ester compounds obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide.

[0122] Examples of dicarbonate compounds used as a terminal amino group capping agent include di-tert-butyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.

[0123] Examples of vinyl ether compounds used as a terminal amino group capping agent include butyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, tert-butyl vinyl ether, and benzyl vinyl ether.

[0124] Other compounds that can be used as a capping agent for the amino group terminal include chloroformates such as benzoyl chloride, fluorenylmethyl chloroformate, 2,2,2-trichloroethyl chloroformate, tert-butyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, benzyl chloroformate, allyl chloroformate, ethyl chloroformate, and isopropyl chloroformate; isocyanate compounds such as butyl isocyanate, 1-naphthyl isocyanate, octadecyl isocyanate, and phenyl isocyanate; methanesulfonyl chloride; and p-toluenesulfonyl chloride.

[0125] The introduction ratio of the acid anhydride terminal-capping agent 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%, based on the total amount of the tetracarboxylic dianhydride component and the dicarboxylic acid component. The introduction ratio of the amino terminal-capping agent is preferably in the range of 0.1 to 100 mol%, particularly preferably 5 to 90 mol%, based on the diamine component. Multiple different terminal groups may be introduced by reacting multiple terminal-capping agents.

[0126] [(D) component] Next, the organic compound represented by the following general formula (1), which is the component (D) of the present invention, will be described. [ka] (In the formula, T represents any one of the structures of the following general formulae (2) to (4), and W represents an alkyl group or an aryl group which may be substituted with an alkoxy group having 4 to 15 carbon atoms.) [ka] (In the formula, V represents a divalent organic group, and * represents a bond.) [ka] (wherein Q represents a halogen atom or a nitro group, and R C 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 of 3 to 5 when Q is a halogen atom, and represents 1 when Q is a nitro group. * represents a bond. [ka] (In the formula, Ar represents a substituted or unsubstituted aromatic ring structure or a heterocyclic ring structure having a heteroatom, and * represents a bond.)

[0127] Among these, the general formula (2) is preferably a structure represented by the following general formula (2-1). [ka] (In the formula, R a and R b 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; R a and R b may be bonded to each other to form a ring together with the carbon atoms to which they are attached. * indicates a bond.)

[0128] Preferred examples of the organic compound or structure represented by general formula (2) or (2-1) in general formula (1) of component (D) include structures of the following general formulas (2-2) and (2-3). [ka] (In the formula, * represents a bond.) [ka] (In the formula, * represents a bond.)

[0129] Next, the organic compound in which T in the above general formula (1) of the component (D) contains a structure represented by the following general formula (3) will be described. [ka] (wherein Q represents a halogen atom or a nitro group, and R C 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 of 3 to 5 when Q is a halogen atom, and represents 1 when Q is a nitro group. * represents a bond.

[0130] As a preferred structure of the component (D) in which T in the general formula (1) is the general formula (3), the following general formula (3-4) can be given: [ka] (In the formula, * represents a bond.)

[0131] Furthermore, the general formula (3) above preferably has a structure represented by the following formula (3-1) or (3-2). [ka] (In the formula, * represents a bond.) [ka] (In the formula, * represents a bond.)

[0132] In the general formula (1) of the component (D), organic compounds in which T represented by the general formula (3) is represented by the following general formula (3-1) or (3-2) are more preferred examples because of the ease of availability of raw materials, the safety of the compound, and its low toxicity.

[0133] When the general formula (3) has a structure represented by the general formula (3-1) or (3-2), the hydroxy group of 4-nitrophenol or pentafluorophenol, which is an active esterifying agent that promotes the imidization reaction, is protected with the above-described tert-butoxycarbonyl group (Boc group) or benzyloxycarbonyl protecting group (Z group), and the storage stability of the photosensitive resin composition containing the polyimide precursor resin can be improved.

[0134] Next, the organic compound in which T in the above general formula (1) of the component (D) contains a structure represented by the following general formula (4) will be described. [ka] (In the formula, Ar represents a substituted or unsubstituted aromatic ring structure or a heterocyclic ring structure having a heteroatom, and * represents a bond.)

[0135] A preferred structure of the component (D) in which T in the general formula (1) is the general formula (4) is the following general formula (4-2): [ka] (In the formula, * represents a bond.)

[0136] Furthermore, in the above general formula (1) of the component (D), T represented by the above general formula (4) preferably has a structure represented by the following general formula (4-1). [ka] (In the formula, R d represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms which may have a halogen atom, or an aryl group having 6 to 15 carbon atoms, and k represents an integer of 0 to 4. * represents a bond.

[0137] A specific example of the structure in which T in the above general formula (1) of the component (D) is represented by the above general formula (4-1) is the structure represented by the following general formula (4-3). [ka] (In the formula, * represents a bond.)

[0138] An organic compound in which T in the general formula (1) of component (D) has the structure represented by the general formula (4-3) is more preferred because the raw materials are readily available and the storage stability of the negative-tone photosensitive resin composition of the present invention containing the organic compound is less likely to deteriorate.

[0139] Next, W in the general formula (1) of component (D) will be explained. W in the general formula (1) of component (D) is preferably a tert-butyl group. When W is a tert-butyl group, it represents a compound in which the organic compound represented by general formula (1) is protected with a tert-butoxycarbonyl group (N-Boc group). The tert-butoxycarbonyl group (N-Boc group) is deprotected at a temperature between 100°C and 150°C during the heating step of the curing reaction, generating an active esterifying agent, which is a hydroxy compound that can promote imide ring-closure reaction, making imidization possible at temperatures below 200°C.

[0140] Furthermore, in this case, W in the general formula (1) of component (D) is preferably a benzyl group. When W is a benzyl group, it represents a compound in which the organic compound represented by the general formula (1) is protected with a benzyloxycarbonyl protecting group (Z group). The benzyloxycarbonyl protecting group (Z group) is deprotected at a temperature ranging from 120°C to 190°C during the heating step of the curing reaction, and an active esterifying agent, which is a hydroxy compound capable of promoting the imide ring-closure reaction, can be produced, making imidization possible at temperatures below 200°C.

[0141] Further preferred organic compounds represented by the above formula (1) include the following compounds: [ka] [ka]

[0142] The above organic compounds can be suitably used as the component (D) of the negative photosensitive resin composition of the present invention because the organic compounds are readily available or the raw materials for the organic compounds are readily available.

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

[0144] In the formula, T and W are the same as above, and A is a halogen atom or a group represented by the following formula (27). [ka] (Here, the dashed lines represent bonds. W is the same as above.)

[0145] More specifically, when T in the general formula (1) above, which is the organic compound of component (D), is the general formula (2) or (2-1) above, it can be obtained by the method shown in the following reaction scheme. [ka] (wherein V, W, and A are the same as above.) [ka] (In the formula, W, A, R a , and R b is the same as above.)

[0146] More specifically, when T in the general formula (1), which is the organic compound of component (D), is the general formula (3), (3-1), or (3-2), it can be obtained by the method shown in the following reaction scheme. [ka] (In the formula, Q, W, and A are the same as above.) [ka] (In the formula, Q, W, and A are the same as above.) [ka] (wherein W and A are the same as above.)

[0147] More specifically, when T in the general formula (1) which is the organic compound of component (D) is the general formula (4), (4-1) or (4-2), it can be obtained by the method shown in the following reaction formula: [ka] (In the formula, Ar, W, and A are the same as above.) [ka] (Wherein, W and A are the same as above.)

[0148] The organic compound of general formula (1), which is component (D) of the negative-tone photosensitive resin composition of the present invention, can be obtained by reacting a hydroxy compound having the structure T of general formula (1) of the general formulas (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4), and (25-4-1) with a halocarbonate ester (a compound in which A in formula (26) represents a halogen atom in the above reaction formula), or by reacting a hydroxy compound having the structure T of general formula (1) of the general formulas (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4), and (25-4-1) with a dicarbonate diester (a compound in which A represents the above formula (27) in the above reaction formula).

[0149] When W is an organic compound representing a tert-butyl group among the organic compounds of general formula (1) that are component (D) of the negative-type photosensitive resin composition of the present invention, the compound can be obtained by reacting a hydroxy compound having the structure T of general formula (1) in the above reaction formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4) or (25-4-1) with di-tert-butyl dicarbonate (a compound in the above reaction formula where A of formula (26) represents formula (27) and W represents a tert-butyl group).

[0150] In the organic compound of the general formula (1) which is the component (D) of the negative-type photosensitive resin composition of the present invention, when W is an organic compound representing a benzyl group, the hydroxy compound having the structure of T in the general formula (1) in the above reaction formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4) and (25-4-1) and benzyloxycarbonyl halide (in the above reaction formula, A in formula (26) is or a reaction of a hydroxy compound having the structure T of general formula (1) in the above reaction formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4) or (25-4-1) with dibenzyl carbonate (a compound in the above reaction formula (26) where A represents formula (27) and W represents a benzyl group).

[0151] The reaction to obtain the organic compound of general formula (1), which is component (D) of the negative-tone photosensitive resin composition of the present invention, using a hydroxy compound having the structure T of general formula (1) of general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4), or (25-4-1) and a halocarbonate ester may be carried out without solvent or in a solvent such as methylene chloride, acetonitrile, diethyl ether, tetrahydrofuran, N,N-dimethylformamide, toluene, or hexane, by sequentially or simultaneously adding the hydroxy compound, the corresponding halocarbonate ester such as benzyl chlorocarbonate or 4-methoxybenzyl chlorocarbonate, and a base such as triethylamine, pyridine, 2,6-lutidine, or N,N-dimethylaniline, and optionally cooling or heating.

[0152] The reaction to obtain the organic compound of general formula (1), which is component (D) of the negative-tone photosensitive resin composition of the present invention, is preferably carried out by sequentially or simultaneously adding the hydroxy compound, the carbonate diester, and a base such as triethylamine, pyridine, 2,6-lutidine, or N,N-dimethylaniline in a solvent such as methylene chloride, acetonitrile, diethyl ether, tetrahydrofuran, N,N-dimethylformamide, toluene, or hexane, and then cooling or heating as necessary, when using a hydroxy compound having the structure T of general formula (1) of general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4), or (25-4-1) and a dicarbonate diester.

[0153] The amount of the halocarbonate or carbonate diester represented by (26) in the above reaction scheme varies depending on the conditions. For example, 1.0 to 5.0 mol, particularly 1.0 to 2.0 mol, is desirable per mol of the hydroxy compound used as the raw material. The amount of base used varies depending on the conditions. For example, 0 to 5.0 mol, particularly 0 to 2.0 mol, is desirable per mol of the hydroxy compound used as the raw material. From the viewpoint of yield, it is desirable to monitor the reaction by gas chromatography (GC) or silica gel thin-layer chromatography (TLC) until the reaction is complete. The reaction time is typically about 0.5 to 24 hours. The desired organic compound of general formula (1), component (D) of the negative-tone photosensitive resin composition of the present invention, can be obtained from the reaction mixture by conventional aqueous treatment. If necessary, it can be purified by conventional methods such as distillation, chromatography, or recrystallization. Alternatively, it may be possible to omit the aqueous post-treatment and filter off the salt produced in the reaction, or to directly subject the reaction mixture to purification.

[0154] On the other hand, the organic compound of component (D) preferably contains 1 to 10 parts by mass of the component (D) per 100 parts by mass of the component (A). When the organic compound of component (D) is added in an amount of 10 parts by mass or less, the organic compound of component (D) does not act as a plasticizer, and thermal deformation of the formed pattern, i.e., thermal flow, does not occur, and pattern formation is not impaired. Furthermore, the glass transition temperature (Tg.) of the resulting cured film does not decrease after curing. The resulting cured film is required to have a high glass transition temperature (Tg.), because it is required to have heat resistance in the process of manufacturing electronic components formed using the resulting cured film as an interlayer insulating film or a surface protective film.

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

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

[0157] [(C) component] The (C) photopolymerization initiator can be any compound conventionally used as a photopolymerization initiator for UV curing. Examples include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzil, benzil dimethyl ketal, and benzyl β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; and 1-phenyl-1,2-butane. Preferred examples of the photopolymerization initiator (C) include oximes such as dione-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-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride; and aromatic biimidazoles. These may be used alone or in combination. Among the photopolymerization initiators (C), oximes are more preferred, particularly in terms of photosensitivity.

[0158] The amount of the (C) photopolymerization initiator to be blended is 0.1 to 20 parts by mass relative to 100 parts by mass of the polymer having the structural unit of the polyimide precursor of the present invention, which is the (A) base resin, and from the viewpoint of photosensitivity characteristics, it is preferably 2 to 15 parts by mass. By blending 0.1 part by mass or more of the (C) photopolymerization initiator relative to 100 parts by mass of the (A) base resin, the photosensitive resin composition has excellent photosensitivity, while by blending 20 parts by mass or less, the photosensitive resin composition has excellent thick-film curing properties.

[0159] [(E) component] Next, the solvent (E) of the negative photosensitive resin composition of the present invention will be described. The organic solvent that can be selected is not limited as long as it dissolves the base resin (A), the photopolymerization initiator (C), and the organic compound (D) represented by the general formula (1). Examples of (E) solvents include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-amyl 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, tert-butyl acetate, tert-butyl propionate, propylene glycol-mono-tert-butyl ether acetate, and γ-butyrolactone, and one or more of these can be used. Particularly preferred are ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, and mixed solvents thereof.

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

[0161] [(B) Component] Furthermore, the negative photosensitive resin composition of the present invention preferably contains (B) a polymerizable compound having two or more ethylenically unsaturated groups.

[0162] Inclusion of a crosslinking agent having two or more photopolymerizable unsaturated bonds in one molecule in this manner can promote crosslinking by photopolymerization of component (A) in the exposed areas, thereby improving the contrast between the exposed and unexposed areas.

[0163] (B) As the polymerizable compound having a group containing two or more ethylenically unsaturated groups, a (meth)acrylic compound is preferable, and examples thereof include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate (each having 2 to 20 ethylene glycol units), polyethylene glycol dimethacrylate (each having 2 to 20 ethylene glycol units), poly(1,2-propylene glycol) diacrylate, poly(1,2-propylene glycol) dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolpropane tetraacrylate, tetraethylene glycol Preferred examples include glycerol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, glycerol diacrylate, glycerol dimethacrylate, methylenebisacrylamide, N-methylolacrylamide, ethylene glycol diglycidyl ether-methacrylic acid adduct, glycerol diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-methacrylic acid adduct, and N,N'-bis(2-methacryloyloxyethyl)urea, but are not limited to these.

[0164] The (B) polymerizable compound having a group containing two or more ethylenically unsaturated groups is preferably blended in an amount of 1 to 100 parts by mass, more preferably 3 to 50 parts by mass, per 100 parts by mass of the polymer compound having the structural unit of the polyimide precursor of the present invention. If the amount deviates from the range of 1 to 100 parts by mass, the intended effect may not be obtained, or the developability may be adversely affected. Note that one type of compound may be used as the copolymerizable monomer, or several types may be used in combination.

[0165] [Component (F)] The negative-type photosensitive resin composition of the present invention may further contain, as a thermal crosslinking agent component (F), one or more crosslinking agents selected from (F) amino condensates modified with formaldehyde or formaldehyde-alcohol, phenol compounds having an average of two or more methylol groups or alkoxymethylol groups per molecule, compounds in which the hydrogen atoms of hydroxyl groups of polyhydric phenols are substituted with glycidyl groups, compounds in which the hydrogen atoms of hydroxyl groups of polyhydric phenols or hydroxyl groups of polyhydric alcohols are substituted with substituents represented by the following formula (F-1), and compounds containing two or more nitrogen atoms and having glycidyl groups represented by the following formula (F-2). [ka] (In the formula, the dotted line represents a bond, Rf represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and c represents 1 or 2.)

[0166] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include a melamine condensate modified with formaldehyde or formaldehyde-alcohol, and a urea condensate modified with formaldehyde or formaldehyde-alcohol.

[0167] The melamine condensate modified with formaldehyde or formaldehyde-alcohol can be prepared, for example, by first modifying a melamine monomer by methylolation with formalin according to a known method, or by further modifying the melamine monomer by alkoxylation with an alcohol to obtain a modified melamine represented by the following general formula (23): The alcohol is preferably a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms.

[0168] [ka] (In the formula, R5 may be the same or different and is a methylol group, an alkoxymethyl group including an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, provided that at least one R5 is a methylol group or the above alkoxymethyl group.) Examples of R5 include alkoxymethyl groups such as a methylol group, a methoxymethyl group, and an ethoxymethyl group, and a hydrogen atom.

[0169] Specific examples of modified melamine represented by the general formula (23) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethylol melamine, etc. Next, the modified melamine represented by the general formula (23) or a polymer thereof (for example, an oligomer such as a dimer or trimer) is subjected to addition condensation polymerization with formaldehyde according to a conventional method until a desired molecular weight is reached, thereby obtaining a melamine condensate modified with formaldehyde or a formaldehyde-alcohol.

[0170] The above-mentioned urea condensate modified with formaldehyde or formaldehyde-alcohol can be prepared, for example, by methylolating a urea condensate having a desired molecular weight with formaldehyde to modify it, or by further alkoxylating it with an alcohol to modify it, according to a known method. Specific examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, and propoxymethylated urea condensate. The modified melamine condensates and modified urea condensates may be used alone or in combination of two or more.

[0171] Next, examples of phenol compounds having an average of two or more methylol groups or alkoxymethylol groups per molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and compounds represented by the following formulas (F-3) to (F-8). [ka]

[0172] The above crosslinking agents can be used alone or in combination of two or more.

[0173] On the other hand, examples of compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are substituted with glycidyl groups include compounds obtained by reacting the hydroxyl groups of bisphenol A, tris(4-hydroxyphenyl)methane, and 1,1,1-tris(4-hydroxyphenyl)ethane with epichlorohydrin in the presence of a base. Suitable examples of compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are substituted with glycidyl groups include the compounds represented by the following formulas (F-9) to (F-15). [ka] (wherein d is 2≦d≦3.)

[0174] Furthermore, preferred examples of compounds other than those represented by the above formulas (F-9) to (F-15) include Epicron 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron EXA-4710, Epicron HP-4770, Epicron EXA-859CRP, Epicron EXA-4880, Examples of suitable inks include Epicron EXA-4850, Epicron EXA-4816, and Epicron EXA-4822 (all trade names, manufactured by Dainippon Ink and Chemicals, Inc.), Rikaresin BPO-20E and Rikaresin BEO-60E (all trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4000S, and EP-4000L (all trade names, manufactured by Adeka Corporation), and jER828EL and YX7105 (all trade names, manufactured by Mitsubishi Chemical Corporation).

[0175] One or two of these compounds in which the hydroxyl groups of polyhydric phenols are substituted with glycidoxy groups (compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are substituted with glycidyl groups) can be used as the crosslinking agent.

[0176] Examples of compounds in which the hydrogen atoms of the hydroxyl groups of a polyhydric phenol are substituted with substituents represented by the following formula (F-1) include compounds containing two or more of the substituents and represented by the following formula (F-16). [ka] (In the formula, dotted lines represent bonds.) [ka] (wherein e is 1≦e≦3.)

[0177] Furthermore, preferred examples of compounds other than those represented by the above formulas (F-9) to (F-16) include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, and the Aronoxetane series manufactured by Toagosei Co., Ltd.

[0178] On the other hand, examples of the compound containing two or more nitrogen atoms having a glycidyl group, represented by the following formula (F-2), include those represented by the following formula (F-17). [ka] (In the formula, the dotted line represents a bond, Rf represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and c represents 1 or 2.) [ka] (In the formula, L represents a linear, branched, or cyclic alkylene group having 2 to 12 carbon atoms, or a divalent aromatic group. Note that L here applies only to the above formula.)

[0179] Examples of the compound represented by the above formula (F-17) include compounds represented by the following formulae (F-18) to (F-21). [ka]

[0180] On the other hand, as the compound containing two or more nitrogen atoms having a glycidyl group represented by the above formula (F-2), compounds represented by the following formulas (F-22) and (F-23) can be suitably used. [ka]

[0181] One or two of these compounds containing two or more nitrogen atoms having a glycidyl group, as represented by the above formula (F-2), can be used as the crosslinking agent.

[0182] The epoxy group has a large ring distortion and is highly reactive, while the oxetane group is highly basic and easily combines with acids. It has been reported that combining the epoxy group with the oxetanyl group significantly improves the reactivity of cationic polymerization.

[0183] Component (F) is a component that undergoes a crosslinking reaction during post-curing after pattern formation of the negative-type photosensitive resin composition of the present invention, thereby further increasing the strength of the cured product. From the viewpoints 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] The amount of component (F) blended in the negative photosensitive resin composition of the present invention is preferably 0.5 to 100 parts by mass, and particularly preferably 1 to 80 parts by mass, per 100 parts by mass of component (A).

[0185] [(G) component] The negative-type photosensitive resin composition of the present invention preferably further contains an antioxidant (G). The antioxidant (G) suppresses unnecessary crosslinking between components (A) or between components (A) and (B) during patterning, thereby improving contrast. Furthermore, its rust-preventing effect on metal materials can suppress metal oxidation caused by external moisture, photoacid generators, thermal acid generators, etc., as well as the resulting loss of adhesion and peeling.

[0186] Specific examples of the (G) antioxidant that can be used include, but are not limited to, hindered phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. These (G) antioxidants can be used alone or in combination of two or more.

[0187] Among the specific examples of the antioxidant (G), further examples of hindered phenol-based antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan Ltd., Irganox 1010 (trade name)), thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan Ltd., Irganox 1035 (trade name)), octadecyl [3- (3,5-di-tert-butyl-4-hydroxyphenyl)propionate (BASF Japan Ltd., Irganox 1076 (trade name)), octyl 1-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate (BASF Japan Ltd., Irganox 1135 (trade name)), 4,6-bis(octylthiomethyl-o-cresol) (BASF Japan Ltd., Irganox 1520L), Sumilizer GA80 (Sumitomo Chemical Co., Ltd., trade name), ADK STAB Examples of the antioxidant include AO-20 (manufactured by ADEKA Corporation, trade name), ADK STAB AO-30 (manufactured by ADEKA Corporation, trade name), ADK STAB AO-40 (manufactured by ADEKA Corporation, trade name), ADK STAB AO-50 (manufactured by ADEKA Corporation, trade name), ADK STAB AO-60 (manufactured by ADEKA Corporation, trade name), ADK STAB AO-80 (manufactured by ADEKA Corporation, trade name), ADK STAB AO-330 (manufactured by ADEKA Corporation, trade name), and the hindered phenol-based antioxidants described in WO 2017 / 188153.

[0188] Among the specific examples of the antioxidant (G), further examples of phosphorus-based antioxidants include triphenyl phosphite, tris(methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tris(nonylphenyl) phosphite, tris(octylphenyl) phosphite, tris[decylpoly(oxyethylene) phosphite, tris(cyclohexylphenyl) phosphite, tricyclohexyl phosphite, tri(decyl)thiophosphite, triisodecylthiophosphite, phenyl-bis(2 -ethylhexyl)phosphite, phenyl-diisodecylphosphite, tetradecylpoly(oxyethylene)-bis(ethylphenyl)phosphat, phenyl-dicyclohexylphosphite, phenyl-diisooctylphosphite, phenyl-di(tridecyl)phosphite, diphenyl-cyclohexylphosphite, diphenyl-isooctylphosphite, diphenyl-2-ethylhexylphosphite, diphenyl-isodecylphosphite, diphenyl-cyclohexylphenylphosphite, diphenyl-(tridecyl)thiophosphite, and the like.

[0189] Further specific examples of the (G) antioxidant include sulfur-based antioxidants such as ADK STAB AO-412S (trade name, manufactured by ADEKA CORPORATION), AO-503S (trade name, manufactured by ADEKA CORPORATION), and Sumilizer TP-D (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

[0190] The sulfur-based antioxidant and the phosphorus-based antioxidant are expected to have the effect of decomposing peroxides.

[0191] The content of the (G) antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the polymer (A). A content of 0.1 part by mass or more improves adhesion to metal materials and inhibits peeling. A content of 10 parts by mass or less prevents deterioration of the developability of the composition and the toughness of the cured coating.

[0192] [(H) component] The negative-tone photosensitive resin composition of the present invention preferably further contains (H) a silane compound. The negative-tone photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, etc., and examples of the metal adhesion improver include a silane compound.

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

[0194] The silane compound (H) that can be used here is not particularly limited, but is preferably one having an alkoxysilyl group. Specific examples of suitable compounds 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-isocyanatopropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ ... Examples of suitable silane compounds include aminopropyltriethoxysilane, triethoxysilylpropylethyl carbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, amide group-containing silane compounds described in Japanese Patent No. 6414060, thiourea group-containing silane compounds described in International Publication No. 2016 / 140024 and Japanese Patent No. 5987984, and thiol group-containing silane compounds described in Japanese Patent Laid-Open No. 2017-044964. However, these silane compounds (H) may be used alone or in combination of two or more.

[0195] It is also preferable to use compounds represented by the following formulae (H-1) to (H-7) as the silane coupling agent. [ka]

[0196] The content of the (H) silane compound in the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymer compound having a structural unit of a polyimide precursor used in the negative-type photosensitive resin composition of the present invention. By ensuring that the content is equal to or greater than the above-mentioned lower limit, the adhesion between the cured film and the metal layer after the curing step is good, while by ensuring that the content is equal to or less than the above-mentioned upper limit, the heat resistance and mechanical properties of the cured film after the curing step are good. The (H) silane compound in the metal adhesion improver may be one type, or two or more types. When two or more types are used, it is preferable that the total amount is within the above-mentioned range.

[0197] [Component (I)] In the present invention, it is preferable that the composition further contains (I) a polymerization inhibitor. The (I) polymerization inhibitor can be a thermal polymerization inhibitor to improve the viscosity and photosensitivity stability of the composition solution during storage. Known thermal polymerization inhibitors can be used as long as they do not deviate from the spirit of the present invention. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt. The amount of (I) polymerization inhibitor added to the negative-type photosensitive resin composition of the present invention is preferably in the range of 0.005 to 5 parts by mass per 100 parts by mass of the polymer compound having a structural unit of a polyimide precursor used in the negative-type photosensitive resin composition of the present invention.

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

[0199] (J) Examples of sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylidene. Indanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3- Examples of suitable amines include 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, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, and 2-(p-dimethylaminobenzoyl)styrene. These may be used alone or in combination of, for example, 2 to 5 types.

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

[0201] The negative-type photosensitive resin composition of the present invention preferably further contains a migration inhibitor (K), which can effectively inhibit migration of metal ions derived from the metal layer (metal wiring) into the curable resin composition layer.

[0202] The migration inhibitor (K) is not particularly limited, but examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole are preferably used.

[0203] (K) As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0204] Other examples of migration inhibitors that can be used include the rust inhibitors described in paragraph 0094 of JP-A-2013-01571, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compounds described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116, and 0118 of JP-A-2012-194520, and the compounds described in paragraph 0166 of WO 2015 / 199219.

[0205] Specific examples of the migration inhibitor include the following compounds. [ka]

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

[0207] The migration inhibitor may be one type only, or two or more types may be used. When two or more types of migration inhibitors are used, the total amount thereof is preferably within the above range.

[0208] (L) The surfactant is preferably a nonionic surfactant, such as a fluorine-containing surfactant, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkyl amine oxide, or fluorine-containing organosiloxane compound.

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

[0210] The amount of surfactant (L) added is preferably 0.01 to 0.05 parts by mass per 100 parts by mass of the polymer (A), which has the advantage of improving substrate coatability without impairing patterning performance or the properties of the cured coating.

[0211] [Pattern formation method] Next, a method for forming a pattern using the negative photosensitive resin composition of the present invention will be described. In the present invention, there is provided a pattern forming method, comprising the steps of: (1) A step of applying any one of the photosensitive resin compositions described above onto a substrate to form a photosensitive film; (2) a step of exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask after the heat treatment; (3) After irradiation, developing the film using an organic solvent developer; The present invention provides a pattern forming method comprising the steps of:

[0212] The negative photosensitive resin composition of the present invention can be applied using known lithography techniques. For example, it is applied by spin coating to a substrate on which a pattern such as a silicon wafer, SiO2 substrate, SiN substrate, or copper wiring has been formed, and prebaked at 80 to 130°C for about 50 to 600 seconds to form a resist film having a thickness of 1 to 50 μm, preferably 1 to 30 μm, and more preferably 5 to 20 μm. Next, a mask for forming the desired pattern is held over the resist film, and high-energy rays such as i-rays and g-rays having a wavelength of 190 to 500 nm are irradiated at an exposure dose of 1 to 5,000 mJ / cm. 2 Approximately, preferably 100 to 2,000 mJ / cm 2 The light is irradiated and exposed to light so that the light intensity is approximately 100%.

[0213] Thereafter, development is carried out. The negative photosensitive resin composition of the present invention is preferably developed with an organic solvent. The organic solvent that can be used for suitable organic solvent development can be the same as the solvent used when preparing the photosensitive resin composition of the present invention. For example, ketones such as cyclohexanone and cyclopentanone, and glycols such as propylene glycol monomethyl ether are preferred. Development can be carried out by a conventional method such as a spray method or a puddle method, or by immersion in a developer. Thereafter, washing, rinsing, drying, etc. are carried out as necessary, and a resist film having a desired pattern can be obtained.

[0214] The resulting patterned coating is post-cured using an oven or hot plate at a temperature of 100 to 300°C, preferably 150 to 300°C, and more preferably 180 to 250°C. A post-curing temperature of 100 to 300°C increases the crosslink density of the photosensitive resin composition coating and removes remaining volatile components, which is preferable from the viewpoints of adhesion to the substrate, heat resistance, strength, and electrical properties. The post-curing time can be 10 minutes to 10 hours.

[0215] The cured coating thus obtained has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance, and also has excellent reliability for semiconductor elements using it as a protective coating, particularly in preventing cracking during temperature cycle tests. Therefore, it is suitable for use as a protective coating for electrical and electronic components, semiconductor elements, etc.

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

[0217] The protective coating is effective for applications such as insulating films for semiconductor elements including rewiring, insulating films for multilayer printed circuit boards, solder masks, and coverlay films due to its heat resistance, chemical resistance, and insulating properties.

[0218] Furthermore, the present invention provides an electronic component having the above interlayer insulating film or the above surface protective film. Such electronic components have excellent reliability because they have a protective coating (interlayer insulating film or surface protective film) that is heat-resistant, chemical-resistant, and insulating. [Example]

[0219] The present invention will be specifically explained below by showing synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

[0220] I. Synthesis of polymer compounds In the synthesis examples of the polymer compounds used in the negative-type photosensitive resin composition of the present invention, the chemical structural formulas and names of the compounds used are shown below. [ka] ODA 4,4'-diaminodiphenyl ether s-ODPA 3,3',4,4'-oxydiphthalic dianhydride s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride

[0221] [Synthesis Example 1] Synthesis of tetracarboxylic acid diester compound (X-1) In a 3 L flask equipped with a stirrer and thermometer, 100 g (322 mmol) of 3,3',4,4'-oxydiphthalic 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 and stirred at room temperature. 83.8 g (644 mmol) of hydroxyethyl methacrylate (HEMA) was added dropwise, followed by stirring at room temperature for 24 hours. The reaction was then quenched by adding 370 g of 10% aqueous hydrochloric acid solution dropwise under ice cooling. 800 g of 4-methyl-2-pentanone was added to the reaction mixture, and the organic layer was separated and washed six times with 600 g of water. The solvent in the resulting organic layer was evaporated to yield 180 g of tetracarboxylic acid diester compound (X-1) with the following structure. [ka]

[0222] [Synthesis Example 2] Synthesis of tetracarboxylic acid diester compound (X-2) In Synthesis Example 1, 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA) was replaced with 94.8 g (322 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), and the rest was the same as in Synthesis Example 1, to obtain 172 g of a tetracarboxylic acid diester compound (X-2) having the following structure. [ka]

[0223] [Synthesis Example 3] Synthesis of polyimide precursor (A-1) In a 1 L flask equipped with a stirrer and thermometer, 44.0 g (77.1 mmol) of (X-1) and 176 g of N-methyl-2-pyrrolidone were added and stirred at room temperature to dissolve. Next, 18.8 g (158.1 mmol) of thionyl chloride was added dropwise under ice cooling, maintaining the reaction solution temperature below 10°C. After the addition, the mixture was stirred for 2 hours under ice cooling. Next, a solution of 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 under ice cooling, maintaining the reaction solution temperature below 10°C. After the addition, the mixture was returned to room temperature, and the reaction solution was added dropwise to 3 L of stirring water. The precipitate was filtered, washed appropriately, and dried under reduced pressure at 40°C for 48 hours to obtain polyimide precursor (A-1). The molecular weight of this polymer was measured by GPC using DMF as an eluent at a temperature of 40°C, and the weight average molecular weight was 24,000 in terms of polystyrene.

[0224] [Synthesis Example 4] Synthesis of polyimide precursor (A-2) Polyimide precursor (A-2) was obtained in the same manner as in Synthesis Example 3, except that 42.8 g (77.1 mmol) of (X-2) was used instead of (X-1). The molecular weight of this polymer was measured by GPC at 40°C using DMF as the eluent, and the weight-average molecular weight, calculated as polystyrene, was 23,000.

[0225] II.(D) Component organic compound The compounds used in the synthesis examples of the organic compound (D) used in the negative photosensitive resin composition of the present invention are shown below. (D-2) N-Hydroxyphthalimide (D-3) N-hydroxy-5-norbornene-2,3-dicarboximide (D-4) N-Hydroxytetrachlorophthalimide (D-5) N,N'-Dihydroxypyromellitimide (D-6) 4-Nitrophenol (D-7) Pentafluorophenol (D-8) 1-Hydroxybenzotriazole (D-9) 1-Hydroxy-6-(trifluoromethyl)benzotriazole

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

[0227] [Synthesis Example 6] Synthesis of N-(tert-butoxycarbonyloxy)-tetrachlorophthalimide (D-4-1) In Synthesis Example 5, (D-3) N-hydroxy-5-norbornene-2,3-dicarboximide was replaced with (D-4) N-hydroxytetrachlorophthalimide (7.52 g), and the reaction was carried out in the same manner to obtain N-(tert-butoxycarbonyloxy)-tetrachlorophthalimide (D-4-1) having the following structure (7.15 g, yield 71.5%). [ka] (D-4-1) N-(tert-butoxycarbonyloxy)-tetrachlorophthalimide

[0228] [Synthesis Example 7] Synthesis of N,N'-di(tert-butoxycarbonyloxy)pyromellitimide (D-5-1) In Synthesis Example 5, (D-3) N-hydroxy-5-norbornene-2,3-dicarboximide was replaced with (D-5) N,N'-dihydroxypyromellitimide 6.18 g, and di-tert-butyl dicarbonate 13.10 g (60.0 mmol) was used, and the reaction was carried out in the same manner to obtain N,N'-di(tert-butoxycarbonyloxy)pyromellitimide (D-5-1) of the following structure (9.03 g, yield 70.1%). [ka] (D-5-1) N,N'-Di(tert-butoxycarbonyloxy)pyromellitimide

[0229] [Synthesis Example 8] Synthesis of tert-butyl-4-nitrophenyl carbonate (D-6-1) The same reaction was carried out in Synthesis Example 5, except that (D-3) N-hydroxy-5-norbornene-2,3-dicarboximide was replaced with (D-6) 4-nitrophenol (3.48 g), to obtain tert-butyl-4-nitrophenyl carbonate (D-6-1) having the following structure (5.31 g, yield 88.8%). [ka] (D-6-1) tert-butyl-4-nitrophenyl carbonate

[0230] [Synthesis Example 9] Synthesis of tert-butyl-2,3,4,5,6-pentafluorophenyl carbonate (D-7-1) In Synthesis Example 5, (D-3) N-hydroxy-5-norbornene-2,3-dicarboximide was replaced with (D-7) pentafluorophenol 4.60 g, and the reaction was carried out in the same manner to obtain tert-butyl-2,3,4,5,6-pentafluorophenyl carbonate (D-7-1) having the following structure (5.34 g, yield 75.2%). [ka] (D-7-1) tert-butyl-2,3,4,5,6-pentafluorophenyl carbonate

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

[0232] [Synthesis Example 11] Synthesis of 1-(tert-butoxycarbonyloxy)-6-(trifluoromethyl)benzotriazole (D-9-1) In Synthesis Example 5, (D-3) N-hydroxy-5-norbornene-2,3-dicarboximide was replaced with (D-9) 1-hydroxy-6-(trifluoromethyl)benzotriazole 5.08 g, and the reaction was carried out in the same manner to obtain 1-(tert-butoxycarbonyloxy)-6-(trifluoromethyl)benzotriazole (D-9-1) having the following structure (5.17 g, yield 68.2%). [ka] (D-9-1) 1-(tert-butoxycarbonyloxy)-6-(trifluoromethyl)benzotriazole

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

[0234] [Synthesis Example 13] Synthesis of N-(benzyloxycarbonyloxy)-5-norbornene-2,3-dicarboximide (D-3-2) In Synthesis Example 12, (D-2) N-hydroxyphthalimide was replaced with (D-3) N-hydroxy-5-norbornene-2,3-dicarboximide (4.48 g), and the reaction was carried out in the same manner to obtain N-(benzyloxycarbonyloxy)-5-norbornene-2,3-dicarboximide (D-3-2) having the following structure (6.18 g, yield 78.9%). [ka] (D-3-2) N-(benzyloxycarbonyloxy)-5-norbornene-2,3-dicarboximide

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

[0236] [Synthesis Example 15] Synthesis of N,N'-di(benzyloxycarbonyloxy)pyromellitimide (D-5-2) In Synthesis Example 12, (D-2) N-hydroxyphthalimide was replaced with (D-5) N,N'-dihydroxypyromellitimide (6.18 g), and the reaction was carried out in the same manner with 10.23 g (60.0 mmol) of benzyl chloroformate to obtain N,N'-di(benzyloxycarbonyloxy)pyromellitimide (D-5-2) of the following structure (7.52 g, yield 58.4%). [ka] (D-5-2) N,N'-Di(benzyloxycarbonyloxy)pyromellitimide

[0237] [Synthesis Example 16] Synthesis of benzyl-4-nitrophenyl carbonate (D-6-2) The reaction was carried out in the same manner as in Synthesis Example 12, except that (D-2) N-hydroxyphthalimide was replaced with (D-6) 4-nitrophenol (3.48 g), to obtain benzyl-4-nitrophenyl carbonate (D-6-2) having the following structure (5.85 g, yield 85.6%). [ka] (D-6-2) Benzyl-4-nitrophenyl carbonate

[0238] [Synthesis Example 17] Synthesis of tert-butyl-2,3,4,5,6-pentafluorophenyl carbonate (D-7-2) The reaction was carried out in the same manner as in Synthesis Example 12, except that (D-2) N-hydroxyphthalimide was replaced with (D-7) pentafluorophenol (4.60 g), to obtain tert-butyl-2,3,4,5,6-pentafluorophenyl carbonate (D-7-2) having the following structure (4.77 g, yield 60.0%). [ka] (D-7-2) tert-butyl-2,3,4,5,6-pentafluorophenyl carbonate

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

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

[0241] The (D-1-1) N-(tert-butoxycarbonyloxy) succinimide represented by the following structural formula was a commercially available reagent (Fujifilm, Wako Pure Chemical Industries, Ltd.). [ka] (D-1-1) N-(tert-butoxycarbonyloxy)succinimide

[0242] Also, the compound represented by the following structural formula: (D-2-1) N-(tert-butoxycarbonyloxy)phthalimide (D-1-2) N-(benzyloxycarbonyloxy)succinimide Commercially available reagents (Tokyo Chemical Industry Co., Ltd.) were used. [ka] (D-2-1) N-(tert-butoxycarbonyloxy)phthalimide [ka] (D-1-2) N-(benzyloxycarbonyloxy)succinimide

[0243] III. Imide ring closure temperature 100 parts by weight of the polymer compound (A-1) synthesized above, 5 parts by weight of the organic compounds (D-1-1) to (D-9-2) of component (D) obtained as shown in Table 1 (Example 1) to (Example 18) below, and 4.0 parts by weight of photopolymerization initiator (C-1): N-1919 manufactured by ADEKA Corporation were dissolved in a solvent of gamma-butyrolactone (hereinafter referred to as GBL). The solution was then microfiltered using a 1.0 μm Teflon (registered trademark) filter to prepare a negative-tone photosensitive resin composition. A comparative example was also prepared without the organic compound of component (D). Next, 5 mL of the resulting composition solution was dispensed onto a silicon substrate, and the substrate was rotated to coat the solution, i.e., by spin coating. The substrate was then pre-baked on a hot plate at 100°C for 3 minutes. The rotation speed during coating was adjusted so that the final film thickness after pre-baking would be 0.9 μm to 1.2 μm. The coated composition film on the silicon substrate was subjected to full-surface exposure to i-rays at an exposure dose of 600 mJ using a Nikon i-ray stepper NSR-2205i11. The resulting cured film was heated from 100°C to 250°C in 10°C increments for 1 hour, and then the infrared absorption intensity at each temperature was measured using the FT-IR described below. The resulting cured film was also heated at 300°C for 1 hour, and the absorption intensity was measured in the same manner. FT-IR Nicolet iN10 MX (ThermoFisher Scientific)

[0244] In the composition film, when the ring-closure reaction of the polymer compound of the polyimide precursor to polyimide progresses, a new C-N bond is formed, and the 1379 cm band, which is derived from the C-N stretching motion, appears in the IR spectrum. -1 On the other hand, the CC double bond of the benzene ring remains unchanged after imidization, and therefore the 1552 cm absorption band, which is due to the CC stretching motion of the benzene ring, is observed in the IR spectrum. -1 The absorption intensity of the CC stretching motion of the benzene ring at 1552 cm remains unchanged. -1 The absorption intensity at 1379 cm originating from the C-N stretching motion was used as an internal standard. -1 The absorption intensity of the imidization reaction can be expressed as the degree of progress of the ring-closure reaction to imide at each temperature, i.e., the imidization rate, according to the following formula (30): Then, the degree of progress of imidization at each temperature can be compared relatively.

number

[0245] The imidization ratio of the cured film after heating at 300°C for 1 hour, calculated by the above formula (30), indicates that the ring-closure reaction of the polyimide precursor polymer compound to polyimide has completely progressed. When the imidization ratio of the cured film calculated by varying the temperature becomes equal to the imidization ratio of the film cured at 300°C, that temperature can be indicated as the temperature at which the imide ring-closure reaction of the polyimide precursor in the composition film can be completely carried out.

[0246] In the cured films of the photosensitive resin compositions in which the component (D) organic compounds (D-1-1) to (D-9-2) were added to Examples 1 to 18 in Table 1 below, the lowest temperature at which the cured film reached the imidization rate after heating at 300°C for 1 hour was shown as the imide ring-closure temperature of the composition film.

[0247] [Table 1]

[0248] As shown in Table 1 above, the organic compound (D) of the present invention can promote the imidization reaction of a polymer compound containing a polyimide precursor structure, and can carry out an imide ring-closing reaction at low temperatures, i.e., 200°C or lower.

[0249] IV. Preparation of Photosensitive Resin Composition Using the polymeric compounds containing the polyimide precursors obtained in Synthesis Examples 3 and 4 above as the base resin, resin compositions were prepared with the organic compound (D) of the present invention procured above in the compositions and amounts shown in Tables 2 to 5, equivalent to 35 mass% resin. The mixture was then stirred, mixed, and dissolved, followed by microfiltration through a 1.0 μm Teflon (registered trademark) filter to obtain a photosensitive resin composition. In the tables, GBL for the solvent represents γ-butyrolactone.

[0250] [Table 2]

[0251] [Table 3]

[0252] [Table 4]

[0253] [Table 5]

[0254] Photosensitive resin compositions 1 to 18 and 21 to 23 (Examples 19 to 39) shown in Tables 2 to 4 relate to the above-mentioned negative photosensitive resin compositions of the present invention. Comparative photosensitive resin compositions 24 to 32 (Comparative Example 2 to Comparative Example 10) shown in Table 5 relate to negative photosensitive resin compositions to which an unprotected organic compound has been added, unlike the organic compound in which a hydroxy compound, which is an active esterifying agent such as the organic compound used in the negative photosensitive resin composition of the present invention described above, is protected with a tert-butoxycarbonyl group (N-Boc group) or protected with a benzyloxycarbonyl protecting group (Z group).

[0255] In Table 5, the compounds in which the hydroxy compound, which is the active esterifying agent in the comparative photosensitive resin compositions 24 to 32 (Comparative Examples 2 to 10), is not protected are (D-2) to (D-9) used in the above Synthesis Examples 5 to 19, and (D-1) is N-hydroxysuccinimide.

[0256] Comparative photosensitive resin composition 33 (Comparative Example 11) is a composition in which the organic compound used in the negative photosensitive resin composition of the present invention described above is not added.

[0257] In Tables 2 to 5, the details of the polymerizable compound (B-1) having a group containing two or more ethylenically unsaturated groups, the photopolymerization initiator (C-1), the thermal crosslinking agents (F-1), (F-2), the antioxidant (G-1), the silane compound (H-1), and the polymerization inhibitor (I-1) are as follows: Parts by weight have the same meaning as parts by mass.

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

[0259] Polymerizable compound (B-1) having a group containing two or more ethylenically unsaturated groups: tetraethylene glycol dimethacrylate

[0260] Thermal crosslinker (F-1): [ka]

[0261] Thermal crosslinker (F-2): Epoxy resin: ADEKA Corporation EP4000L

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

[0263] Silane Compound (H-1): Aminosilane coupling agent: KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.

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

[0265] V. Pattern Formation 5 mL of each of the above photosensitive resin compositions 1 to 18 and 21 to 23, and comparative photosensitive resin compositions 24 to 33 was dispensed onto a silicon substrate, and then the substrate was rotated, i.e., spin coating was used to apply the composition so that the film thickness would be 5 μm after heating for post-curing, which is performed after pattern formation. That is, the rotation speed during application was adjusted based on the consideration that the film thickness would decrease after the post-curing step. Next, the film was prebaked on a hot plate at 100°C for 3 minutes. Then, i-line exposure and pattern formation were performed using a Nikon i-line stepper NSR-2205i11. In pattern formation, a mask for a positive pattern or a negative pattern was used as appropriate, depending on the photosensitive resin composition used. The mask had a pattern capable of forming 20 μm holes in a 1:1 vertical / horizontal arrangement, with 10 μm intervals from 50 μm to 20 μm, 5 μm from 20 μm to 10 μm, and 1 μm from 10 μm to 1 μm.

[0266] In the development process, cyclopentanone was used as the developer. For organic solvent development, spray development was performed once for 1 minute with each organic solvent, followed by rinsing with isopropyl alcohol.

[0267] The resulting pattern on the substrate was then post-cured in an oven at 200° C. for 2 hours while purging with nitrogen.

[0268] Next, each substrate was cut out so that the shape of the resulting hole pattern could be observed, and the hole pattern shape was observed using a scanning electron microscope (SEM). The diameter of the smallest opening hole at a film thickness of 5 μm after post-curing was determined, and the pattern shape was evaluated. These results, along with the sensitivity at which the smallest pattern could be formed, are shown in Tables 2 to 5.

[0269] The hole pattern shape was evaluated according to the following criteria, and the evaluation results are shown in Tables 2 to 5. Good: The hole was observed to be rectangular or tapered (the dimension of the top of the hole was larger than the dimension of the bottom). Poor: Reverse tapered shape (the dimensions of the top of the hole are smaller than the dimensions of the bottom), overhang shape (the top of the hole protrudes), significant film loss, or residue at the bottom of the hole.

[0270] VI. Storage stability In the pattern formation described above, the photosensitive resin composition was similarly applied by dispensing 5 mL of the composition onto a silicon substrate and then rotating the substrate, followed by pre-baking on a hot 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 and after storage were compared, 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 aging - film thickness after aging) / film thickness before aging} × 100 The calculated film thickness change rate was evaluated according to the following evaluation criteria.

[0271] Excellent: A composition in which the film thickness varies by less than 10% before and after storage. Good: A composition in which the film thickness varies by 10% or more and less than 15% before and after storage. Poor: Composition in which the film thickness before and after storage varies by 15% or more. Not estimable: Composition in which the composition solution gelled after 3 weeks and a film could not be formed. The evaluation results are shown in Tables 2 to 5. The smaller the film thickness change rate, the more excellent the storage stability of the curable resin composition. It is also preferable that the composition solution remains stable without any change.

[0272] VII. Chemical resistance In the pattern formation described above, the photosensitive resin composition was similarly applied by dispensing 5 mL of the composition onto a silicon substrate and then rotating the substrate, followed by pre-baking on a hot plate at 100°C for 3 minutes. Next, a full-surface exposure without pattern formation was carried out using a Nikon i-line stepper NSR-2205i11 at an exposure dose of 600 mJ. Thereafter, the resulting film on the substrate was post-cured in an oven at 200° C. for 2 hours while purging with nitrogen.

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

[0274] Excellent: The change in film thickness was less than 3.0 μm. Good: The change in film thickness was 3.0 μm or more and less than 5.0 μm. Poor: The change in film thickness was 5.0 μm or more.

[0275] As shown in the results in Tables 2 to 5, the negative photosensitive resin composition containing the organic compound of the present invention is excellent in resolution performance, and is also excellent in storage stability and chemical resistance.

[0276] On the other hand, it was found that when a negative-tone photosensitive resin composition containing a compound other than the organic compound of the present invention was used, the storage stability was poor. That is, as shown by the storage stability results of comparative photosensitive resin compositions 24 to 32 (Comparative Examples 2 to 10), it was found that, unlike organic compounds in which a hydroxy compound, an active esterifying agent such as the organic compound of the present invention, is protected with a tert-butoxycarbonyl group (N-Boc group) or an organic compound protected with a benzyloxycarbonyl protecting group (Z group), the storage stability of a negative-tone photosensitive resin composition to which an unprotected organic compound was added was poor.

[0277] Comparative photosensitive resin composition 33 (Comparative Example 11) is a composition that does not contain the organic compound used in the negative-tone photosensitive resin composition of the present invention. The chemical resistance of the cured film of this composition was inferior to that of the composition containing the nitrogen-containing organic compound of the present invention. This is thought to be because, as mentioned above, the imide ring-closure temperature of the composition not containing the nitrogen-containing organic compound of the present invention is high at 230°C, and complete imidization was not achieved under the conditions of 200°C for 2 hours using an oven in this evaluation, and the chemical resistance that is an advantage of polyimide was not exhibited.

[0278] The present specification includes the following aspects. [1]: A negative photosensitive resin composition, (A) a polymer compound having a polyimide precursor structure, (C) a photopolymerization initiator; (D) an organic compound represented by the following general formula (1): (E) a solvent; A negative photosensitive resin composition comprising: [ka] (In the formula, T represents any one of the structures of the following general formulae (2) to (4), and W represents an alkyl group or an aryl group which may be substituted with an alkoxy group having 4 to 15 carbon atoms.) [ka] (In the formula, V represents a divalent organic group, and * represents a bond.) [ka] (wherein Q represents a halogen atom or a nitro group, and R C 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 of 3 to 5 when Q is a halogen atom, and represents 1 when Q is a nitro group. * represents a bond. [ka] (In the formula, Ar represents a substituted or unsubstituted aromatic ring structure or a heterocyclic ring structure having a heteroatom, and * represents a bond.) [2]: The negative photosensitive resin composition according to [1], wherein the component (A) is a polymer compound having a polyimide precursor structure represented by the following general formula (5): [ka] (wherein X is a tetravalent organic group, Y is a divalent organic group, and R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and R 1 and R 2 At least one of the above is a group represented by the following general formula (6): [ka] (In the formula, M 1 , M 2 and M 3 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10. * represents a bond. [3]: The negative photosensitive resin composition according to [1] or [2], characterized in that it contains (B) a polymerizable compound having two or more ethylenically unsaturated groups. [4]: The negative photosensitive resin composition according to any one of [1] to [3], wherein W in the general formula (1) of the component (D) is a tert-butyl group. [5]: The negative photosensitive resin composition according to any one of [1] to [3], wherein W in the general formula (1) of the component (D) is a benzyl group. [6]: The negative photosensitive resin composition according to any one of [1] to [5], wherein the general formula (2) is a structure represented by the following general formula (2-1): [ka] (In the formula, R a and R brepresents 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; R a and R b may be bonded to each other to form a ring together with the carbon atoms to which they are attached. * indicates a bond.) [7]: The negative photosensitive resin composition according to any one of [1] to [5], wherein the general formula (3) is a structure represented by the following formula (3-1) or (3-2): [ka] (In the formula, * represents a bond.) [ka] (In the formula, * represents a bond.) [8]: The negative photosensitive resin composition according to any one of [1] to [5], wherein the general formula (4) is a structure represented by the following general formula (4-1): [ka] (In the formula, R d represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms which may have a halogen atom, or an aryl group having 6 to 15 carbon atoms, and k represents an integer of 0 to 4. * represents a bond. [9]: The negative photosensitive resin composition according to any one of [1] to [8], characterized in that it contains 1 to 10 parts by mass of the component (D) per 100 parts by mass of the component (A).

[10] : The negative photosensitive resin composition according to any one of [1] to [9], characterized in that (F) the thermal crosslinking agent comprises one or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol or a hydroxyl group of a polyhydric alcohol is substituted with a substituent represented by the following formula (F-1), and a compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (F-2). [ka] (In the formula, the dotted line represents a bond, Rf represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and c represents 1 or 2.)

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

[10] , further comprising (G) an antioxidant.

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

[11] , further comprising (H) a silane compound.

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

[12] , further comprising (I) a polymerization inhibitor.

[14] : A pattern forming method, (1) A step of applying the photosensitive resin composition according to any one of [1] to

[13] onto a substrate to form a photosensitive film; (2) a step of exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask after the heat treatment; (3) After irradiation, developing the film using an organic solvent developer; A pattern forming method comprising the steps of:

[15] : A method for forming a cured film, comprising a step of post-curing the patterned film obtained by the pattern formation method according to

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

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

[13] .

[17] : A surface protection film characterized by being a cured coating film obtained by curing the negative photosensitive resin composition according to any one of [1] to

[13] .

[18] : An electronic component characterized by having the interlayer insulating film according to

[16] .

[19] : An electronic component having the surface protective film according to

[17] .

[0279] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. A negative photosensitive resin composition, (A) a polymer compound having a polyimide precursor structure, (C) a photopolymerization initiator, (D) an organic compound represented by the following general formula (1): (E) a solvent; A negative photosensitive resin composition comprising: 【Chemistry 1】 (In the formula, T represents any one of the structures of the following general formulae (2) to (4), and W represents an alkyl group or an aryl group which may be substituted with an alkoxy group having 4 to 15 carbon atoms.) 【Chemistry 2】 (In the formula, V represents a divalent organic group, and * represents a bond.) 【Transformation 3】 (wherein Q represents a halogen atom or a nitro group, R Ｃ 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 of 3 to 5 when Q is a halogen atom, and represents 1 when Q is a nitro group. * represents a bond. 【Chemistry 4】 (In the formula, Ar represents a substituted or unsubstituted aromatic ring structure or a heterocyclic ring structure having a heteroatom, and * represents a bond.)

2. 2. The negative photosensitive resin composition according to claim 1, wherein the component (A) is a polymer compound having a polyimide precursor structure represented by the following general formula (5): 【Transformation 5】 (wherein X is a tetravalent organic group, Y is a divalent organic group, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of the above is a group represented by the following general formula (6): 【Transformation 6】 (In the formula, M １ , M ２ and M ３ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10. * represents a bond.

3. 2. The negative photosensitive resin composition according to claim 1, further comprising (B) a polymerizable compound having two or more ethylenically unsaturated groups.

4. 2. The negative photosensitive resin composition according to claim 1, wherein W in the general formula (1) of the component (D) is a tert-butyl group.

5. 2. The negative photosensitive resin composition according to claim 1, wherein W in the general formula (1) of the component (D) is a benzyl group.

6. 2. The negative photosensitive resin composition according to claim 1, wherein the general formula (2) is a structure represented by the following general formula (2-1): 【Transformation 7】 (In the formula, R ａ and R ｂ 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; R ａ and R ｂ may be bonded to each other to form a ring together with the carbon atoms to which they are attached. * indicates a bond.)

7. 2. The negative photosensitive resin composition according to claim 1, wherein the general formula (3) is a structure represented by the following formula (3-1) or (3-2): 【Transformation 8】 (In the formula, * indicates a bond.) 【Chemistry 9】 (In the formula, * indicates a bond.)

8. 2. The negative photosensitive resin composition according to claim 1, wherein the general formula (4) is a structure represented by the following general formula (4-1): 【Chemistry 10】 (In the formula, R ｄ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms which may have a halogen atom, or an aryl group having 6 to 15 carbon atoms, and k represents an integer of 0 to 4. * represents a bond.

9. 2. The negative photosensitive resin composition according to claim 1, wherein the component (D) is contained in an amount of 1 to 10 parts by mass per 100 parts by mass of the component (A).

10. The negative photosensitive resin composition according to claim 1, characterized in that it contains, as a thermal crosslinking agent (F), one or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or a formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol or a hydroxyl group of a polyhydric alcohol is substituted with a substituent represented by the following formula (F-1), and a compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (F-2): 【Chemistry 11】 (In the formula, the dotted lines represent bonds, Rf represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and c represents 1 or 2.)

11. 2. The negative photosensitive resin composition according to claim 1, further comprising (G) an antioxidant.

12. 2. The negative photosensitive resin composition according to claim 1, further comprising (H) a silane compound.

13. 2. The negative photosensitive resin composition according to claim 1, further comprising (I) a polymerization inhibitor.

14. A pattern formation method, comprising: (1) a step of applying the photosensitive resin composition according to any one of claims 1 to 13 onto a substrate to form a photosensitive film; (2) a step of exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask after the heat treatment; (3) a step of developing the exposed film using an organic solvent developer; A pattern forming method comprising the steps of:

15. A method for forming a cured film, comprising the step of heating and post-curing the patterned film obtained by the pattern formation method according to claim 14 at a temperature of 100 to 300°C.

16. An interlayer insulating film, which is a cured film obtained by curing the negative photosensitive resin composition according to claim 1 .

17. A surface protection film, which is a cured coating film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 13.

18. An electronic component comprising the interlayer insulating film according to claim 16.

19. An electronic component comprising the surface protection film according to claim 17.

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