Negative photosensitive resin composition, pattern forming method, hardened coating film forming method, interlayer insulating film, surface protective film, and electronic component

Abstract

The invention relates to a negative photosensitive resin composition, a pattern forming method, a hardened film forming method, an interlayer insulating film, a surface protective film, and an electronic component. The purpose of the present invention is to provide a photosensitive resin composition using a polyimide precursor, the photosensitive resin composition being capable of undergoing an imide ring-closure reaction at a low temperature, having excellent stability, and being capable of forming a fine pattern, the photosensitive resin composition being capable of providing resistance to chemicals after curing. Also provided are: a pattern forming method using the photosensitive resin composition; an interlayer insulating film characterized by containing a cured film obtained by curing the photosensitive resin composition; and a semiconductor device. A negative photosensitive resin composition includes (A) a polymer compound having a polyimide precursor structure, (C) a photopolymerization initiator, (D) an organic compound represented by general formula (1), and (E) a solvent. [Chemical Formula 1]

Description

TECHNICAL FIELD

[0001] The present application relates to a negative photosensitive resin composition, a pattern forming method using the same, a hard coat film forming method, an interlayer insulating film, a surface protective film, and an electronic component, which can be developed using an organic solvent. BACKGROUND

[0002] With the miniaturization and high performance of various electronic devices such as personal computers, digital cameras, and mobile phones, further miniaturization, thinning, and high density of semiconductor devices are rapidly increasing. Therefore, it is desirable to develop a photosensitive insulating material that can cope with the increase in substrate area when productivity is improved, and that is fine and has a high aspect ratio on a substrate in high-density mounting technologies such as wafer level packaging or chip size packaging (CSP) or three-dimensional stacking.

[0003] In high-density mounting technologies such as three-dimensional stacking, polyimide films have been effectively used as protective films and interlayer insulating films for photosensitive insulating materials that can form patterns on substrates, and their insulating properties, mechanical strength, adhesion to substrates, and the like have been continuously attracting attention, and development is still vigorous even now.

[0004] Polyimides and the like that form polyimide films have low solubility in solvents, and are therefore used in the state of precursors before imide ring closure, are coated and laminated on a substrate, and are then heated to cyclize the polyimide precursors to form a hardened film, and are thus used as protective films, interlayer insulating films, and the like.

[0005] To date, materials that are precursors of polyimides that can form patterns have been proposed, for example, materials that introduce a photosensitive group into a carboxyl group of a polyamic acid by an ester bond (Patent Literature 1, Patent Literature 2). However, in these proposals, after forming a patterned film, in order to obtain a target polyimide film, imidization treatment at a high temperature exceeding 300°C is necessary, and in order to withstand this high temperature, there are problems such as limitations on the base substrate, oxidation of copper wiring, or the possibility of thermal damage to electronic components and the like.

[0006] Patent Literature 3 discloses a polyimide precursor composition comprising a polyimide precursor, a thermal base generator that generates a base by heat, and a solvent, wherein the aforementioned polyimide precursor is a polyamic acid, and the aforementioned thermal base generator is a neutral compound that thermally decomposes to generate a secondary amine by heating at a temperature of 200°C or less. The secondary amine generated by thermal decomposition promotes imide ring closure, and thus shows that processing at 200°C or less is possible.

[0007] However, for the hardened film using the composition described in Patent Literature 3, there are cases where the corrosion resistance and the drug resistance required for a protective film, an interlayer insulating film, and the like are poor. In addition, there is a problem of storage stability in which the cyclization reaction of the polyimide precursor resin proceeds and gelation occurs during storage of the composition.

[0008] On the other hand, in Patent Literature 4 and Patent Literature 5, a composition in which a polyimide precursor and an imidazole-based imidization catalyst that promotes the imide ring-closing reaction are added is disclosed. However, there is no disclosure of a photosensitive resin composition capable of forming a pattern on a substrate, which is required in high-density mounting technology, nor is there any disclosure of low-temperature imidization. Furthermore, the imidazole-based imidization catalyst described in Patent Literature 4 and Patent Literature 5 has a problem of storage stability in which gelation occurs during storage of the composition, except for N-tert-butoxycarbonylimidazole (N-Boc-imidazole). In addition, if the amount of the imidazole-based imidization catalyst described in Patent Literature 4 and Patent Literature 5 is added, deformation of the pattern (heat flow) caused by heat occurs in the hardening reaction after the pattern formation, fine and high aspect ratio patterns cannot be expected, or the glass transition temperature (Tg.) of the obtained hardened film is reduced, and thus it is not suitable for use in a protective film, an interlayer insulating film, and the like.

[0009] On the other hand, Patent Literature 6 discloses the use of an active esterization agent as a compound capable of performing imidization at a lower temperature, unlike a thermal base generator that generates a base by heating. However, the carbonic acid ester compounds and ester compounds of bis(pentafluorophenyl) carbonate, bis(4-nitrophenyl) carbonate, di(N-succinimidyl) carbonate, and 4-nitrophenyl trifluoroacetate of the active esterization agent shown in Patent Literature 6 have a high decomposition temperature, and it is desirable to more effectively promote the imide ring-closing reaction in the heating step for providing a hardened film.

[0010] In addition, pentafluorophenol and 1-hydroxy-7-azabenzotriazole of the active esterization agent shown in Patent Literature 6 contain a hydroxyl group, and thus there is a problem of deterioration of the storage stability of a photosensitive resin composition containing a polyimide precursor resin.

[0011] On the other hand, Patent Literature 7 discloses the addition of an imide as a compound capable of promoting the imidization reaction. However, the imide compound shown in Patent Literature 7 contains a hydroxyl group and an amino group, and thus it is undeniable that there is a problem of deterioration of the storage stability of a photosensitive resin composition containing a polyimide precursor resin.

[0012] Thus, it is strongly desired to develop a photosensitive resin composition which is a photosensitive resin composition using a polyimide precursor, which has all of the following characteristics without lacking any one of the following characteristics: capable of forming a fine pattern, capable of obtaining a hardened film by heating at a low temperature, the protective film, the interlayer insulating film on which the hardening is performed, having heat resistance in various steps, resistance to various used chemicals, and further, the composition has good storage stability.

[0013] Prior Art Documents

[0014] Patent Documents

[0015] Patent Document 1: Japanese Patent Application Laid-Open No. 49-115541

[0016] Patent Document 2: Japanese Patent Application Laid-Open No. 55-45746

[0017] Patent Document 3: Japanese Patent Application Laid-Open No. 2007-056196

[0018] Patent Document 4: Japanese Patent No. 7436606

[0019] Patent Document 5: Japanese Patent Application Laid-Open No. 2022-159241

[0020] Patent Document 6: Japanese Patent Application Laid-Open No. 2024-19341

[0021] Patent Document 7: Japanese Patent No. 7252020 SUMMARY

[0022] [Problems to be Solved by the Invention]

[0023] The present invention has been achieved in view of the above-described circumstances, and an object of the present invention is to provide a photosensitive resin composition using a polyimide precursor, which is capable of performing an imide ring-closing reaction at a low temperature, has excellent stability of the composition, and is capable of forming a fine pattern. In addition, a pattern forming method using the photosensitive resin composition, an interlayer insulating film constituted by a hardened film of the photosensitive resin composition, a surface protective film, and an electronic component are provided.

[0024] [Means for Solving the Problems]

[0025] That is, in order to solve the above-described problems, a negative photosensitive resin composition is provided in the present invention, which is characterized by containing:

[0026] (A) a high molecular compound having a polyimide precursor structure,

[0027] (C) a photopolymerization initiator,

[0028] (D) an organic compound represented by the following general formula (1), and

[0029] (E) solvent;

[0030] [Chemical Formula 1]

[0031]

[0032] In the formula, T represents any one of the following general formulae (2) to (4), and W represents an alkyl group or an aryl group which can also be substituted with an alkoxy group having 4 to 15 carbon atoms.

[0033] [Chemical Formula 2]

[0034]

[0035] In the formula, V represents a divalent organic group, and * represents a bond.

[0036] [Chemical Formula 3]

[0037]

[0038] In the formula, 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.

[0039] [Chemical Formula 4]

[0040]

[0041] In the formula, Ar represents a substituted or unsubstituted aromatic ring structure, or a heterocyclic structure having a hetero atom, and * represents a bond.

[0042] When the above-mentioned organic compound represented by the general formula (1) is added to a negative photosensitive resin composition including a polyimide precursor structure, the temperature of the hardening reaction, i.e., imide ring closure reaction, of the obtained hardened film can be made to be 200°C or lower.

[0043] In addition, the above-mentioned organic compound represented by the general formula (1) can inhibit the aggregation, i.e., gelation, of a polymeric compound including a polyimide precursor structure with the organic compound by virtue of the protective group of the -(C=O)-O-W group, and can inhibit the deterioration of the storage stability of the photosensitive resin composition.

[0044] At this time, the (A) component is preferably a polymeric compound having a polyimide precursor structure represented by the following general formula (5).

[0045] [Chemical Formula 5]

[0046]

[0047] wherein X is a tetravalent organic group, Y is a divalent organic group, R 1 and R 2 each independently is a hydrogen atom or a monovalent organic group, and R 1 and R 2 at least one of which is a group represented by the following general formula (6).

[0048] [Chemical Formula 6]

[0049]

[0050] wherein M 1 , M 2 and M 3 each independently is a hydrogen atom or an organic group having a carbon number of 1 to 3, and m is an integer of 2 to 10. * indicates a bond.

[0051] From the viewpoint of the film strength of the obtained hardened film, it is preferable that the high molecular compound contain a structural unit of the polyimide precursor.

[0052] Further, it is preferable to include (B) a polymerizable compound having two or more ethylenically unsaturated groups.

[0053] By including a crosslinking agent having two or more photopolymerizable unsaturated bonds in one molecule, the light polymerization-based crosslinking of the (A) component at the exposed portion can be promoted, and the contrast between the exposed portion and the unexposed portion can be improved.

[0054] In this case, it is preferable that W in the general formula (1) of the above (D) component be a t-butyl group.

[0055] In the case where W is a t-butyl group, it indicates a compound in which the oxygen atom of the structure T of the organic compound represented by the above general formula (1) is protected by a t-butyloxycarbonyl (Boc group). The t-butyloxycarbonyl (Boc group) is deprotected in the range of 100°C to 150°C in the heating step of the hardening reaction, and an organic compound that can promote the imide ring-closing reaction can be produced, and thus imidization at 200°C or lower can be performed.

[0056] In this case, it is preferable that W in the general formula (1) of the above (D) component be a benzyl group.

[0057] In the case where W is a benzyl group, it indicates a compound in which the oxygen atom of the structure T of the organic compound represented by the above general formula (1) is protected by a benzyloxycarbonyl protecting group (Z group). The benzyloxycarbonyl protecting group (Z group) is deprotected in the range of 120°C to 190°C in the heating step of the hardening reaction, and an organic compound that can promote the imide ring-closing reaction can be produced, and thus imidization at 200°C or lower can be performed.

[0058] Preferably, the negative photosensitive resin composition of the above-described general formula (2) is of a structure represented by the following general formula (2-1).

[0059] [Chemical Formula 7]

[0060]

[0061] in the formula, * represents a bond. a and R b represent a hydrogen atom, a linear, branched, or cyclic alkyl group having a carbon number of 1 to 15, or an aryl group having a carbon number of 6 to 15, R a and R b may be bonded to each other and form a ring together with the carbon atom to which they are bonded. * represents a bond.

[0062] If the above-described general formula (2) is of a structure represented by the above-described general formula (2-1), the hydroxyl group of the N-hydroxy-imide compound that promotes the imidization reaction is protected by the above-described tert-butyloxycarbonyl (Boc group), benzyloxycarbonyl protecting group (Z group), and thus the storage stability of the photosensitive resin composition containing the polyimide precursor resin can be good.

[0063] Preferably, the negative photosensitive resin composition of the above-described general formula (3) is of a structure represented by the following general formula (3-1) or (3-2).

[0064] [Chemical Formula 8]

[0065]

[0066] in the formula, * represents a bond.

[0067] [Chemical Formula 9]

[0068]

[0069] in the formula, * represents a bond.

[0070] If the above-described general formula (3) is of a structure represented by the above-described general formula (3-1) or (3-2), the hydroxyl group of the 4-nitrophenol, pentafluorophenol, which is an active esterization agent that promotes the imidization reaction, is protected by the above-described tert-butyloxycarbonyl (Boc group), benzyloxycarbonyl protecting group (Z group), and thus the storage stability of the photosensitive resin composition containing the polyimide precursor resin can be good.

[0071] If it is an organic compound including the above-described general formula (3) of a structure represented by the above-described general formula (3-1) or (3-2), from the aspects of the ease of obtaining the raw material, the safety of the compound, the low toxicity, and the like, the following can be listed as further preferable examples.

[0072] Preferably, the negative photosensitive resin composition of the above-described general formula (4) has a structure represented by the following general formula (4-1).

[0073] [Chem. 10]

[0074]

[0075] in the formula, R d represents a linear, branched, or cyclic alkyl group having 1 to 15 carbons which can have a halogen atom, or an aryl group having 6 to 15 carbons, and k represents an integer of 0 to 4. represents a bond.

[0076] If the above-described general formula (4) has a structure represented by the above-described general formula (4-1), the hydroxyl group of 1-hydroxy-benzotriazole which is an active esterization agent for promoting imidization reaction is protected with the t-butoxycarbonyl (Boc group) or benzyloxycarbonyl protecting group (Z group) described above, and the storage stability of the photosensitive resin composition containing the polyimide precursor resin can be made good.

[0077] In addition, relative to 100 parts by mass of the above-described (A) component, preferably 1 to 10 parts by mass of the above-described (D) component is contained.

[0078] When the organic compound of the component (D) is 10 parts by mass or less, the added organic compound does not function as a plasticizer, and the formed pattern does not deform due to heat, that is, does not undergo thermal flow, and the pattern formation is not impaired. In addition, after hardening, the glass transition point (Tg.) of the obtained hardened film is not reduced. The glass transition point (Tg.) of the obtained hardened film is required to be high because of the requirement for heat resistance in the step of manufacturing an electronic part using the interlayer insulating film or surface protective film formed using the obtained hardened film.

[0079] In addition, in the present application, as the (F) thermal crosslinking agent, preferably one or two or more crosslinking agents selected from the group consisting of an amino compound modified with formaldehyde or formaldehyde-alcohol, a phenol compound having 2 or more hydroxymethyl groups or alkoxyhydroxymethyl groups on average in one molecule, a compound in which the hydrogen atom of the hydroxyl group of a polyphenol is substituted with a glycidyl group, a compound in which the hydrogen atom of the hydroxyl group of a polyphenol or the hydroxyl group of a polyol is substituted with a substituent represented by the following formula (F-1), and a compound containing 2 or more nitrogen atoms having a glycidyl group represented by the following formula (F-2) is contained.

[0080] [Chem. 11]

[0081]

[0082] in the formula, the dotted line represents an atomic bond, Rf is a linear, branched, or cyclic alkyl group having 1 to 6 carbons, and c is 1 or 2.

[0083] (F) Component is a component that causes cross-linking reaction in post-hardening after pattern formation of the negative photosensitive resin composition of the present application, and further improves the strength of the hardened product.

[0084] As the above-mentioned negative photosensitive resin composition, it is preferable to further contain (G) an antioxidant.

[0085] By containing the (G) antioxidant, the excessive cross-linking between the (A) components, or between the (A) component and the (B) component at the time of patterning can be inhibited, and the contrast can be improved. In addition, by the rust-preventing effect on metal materials, the oxidation of metals, the reduction of adhesion, and peeling caused by moisture, photo-acid generators, thermal acid generators, and the like from the outside can be inhibited.

[0086] As the above-mentioned negative photosensitive resin composition, it is preferable to further contain (H) a silane compound.

[0087] The negative photosensitive resin composition of the present application preferably contains a metal adhesion improver for improving the adhesion to metal materials used in electrodes, wiring, and the like, and as the metal adhesion improver, a silane compound or the like can be mentioned.

[0088] As the above-mentioned negative photosensitive resin composition, it is preferable to further contain (I) a polymerization inhibitor.

[0089] By containing the (I) polymerization inhibitor, a thermal polymerization inhibitor can be added in order to improve the viscosity and the stability of photosensitivity of the composition solution at the time of storage.

[0090] In addition, the present application provides a pattern formation method, which includes:

[0091] (1) a step of applying the above-mentioned photosensitive resin composition on a substrate to form a photosensitive film;

[0092] (2) then, a step of exposing the photosensitive film to high-energy rays or electron beams with a wavelength of 190 to 500 nm through a photomask after heat treatment; and

[0093] (3) a step of developing using a developing solution of an organic solvent after irradiation.

[0094] Such a pattern formation method of the negative photosensitive resin composition, particularly in the negative photosensitive resin composition in which the above-mentioned high molecular compound containing a polyimide precursor structure as a polymer having a polymerizable unsaturated bonding group is used as the base resin (A), by containing the (D) component organic compound of the present application, the obtained pattern can be hardened without causing shape change, and thus a pattern formation method capable of forming a fine pattern is exhibited.

[0095] Then, the present application can provide a hardened film forming method characterized by including a step of performing post-hardening by heating the pattern-formed film obtained by the above-described pattern forming method at a temperature of 100 to 300°C.

[0096] By performing such a pattern forming method, the hardening reaction, i.e., imide ring closure reaction, after the pattern formation can be performed at a low temperature.

[0097] In addition, the present application provides an interlayer insulating film that is a hardened film hardened from the above-described negative photosensitive resin composition.

[0098] The hardened film hardened from the photosensitive resin composition of the present application is useful as an interlayer insulating film.

[0099] In addition, the present application provides a surface protective film that is a hardened film hardened from the above-described negative photosensitive resin composition.

[0100] The hardened film hardened from the photosensitive resin composition of the present application is useful as an interlayer insulating film and a surface protective film.

[0101] In addition, the present application provides an electronic component having the above-described interlayer insulating film.

[0102] In addition, the present application provides an electronic component having the above-described surface protective film.

[0103] Such an electronic component is excellent in reliability because it has a protective film (interlayer insulating film or surface protective film) that is excellent in heat resistance, chemical resistance, and insulating properties.

[0104] [Effects of the Invention]

[0105] As described above, according to the present application, it is possible to provide a negative photosensitive resin composition containing a high molecular compound containing a polyimide precursor structure, which can perform an imide ring closure reaction at a low temperature regardless of the molecular structure of the polyimide precursor, is high in storage stability, and can form a fine pattern without causing a change in the shape of the obtained pattern. In addition, the hardened film obtained by hardening after the pattern formation exhibits excellent chemical resistance and is high in glass transition temperature (Tg). DETAILED DESCRIPTION

[0106] As described above, there is a demand for development of a photosensitive resin composition using a polyimide precursor, which can perform an imide ring closure reaction at a low temperature, is excellent in stability of the composition, can form a fine pattern, and can impart chemical resistance after hardening.

[0107] The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that the addition of an organic compound represented by the following general formula (1) to a photosensitive resin composition using a high molecular compound having a polyimide precursor structure enables the realization of a hardening reaction, i.e., imide ring closure reaction, after pattern formation at 200°C or lower, without impairing the formation of a fine pattern.

[0108] In addition, it was found that the obtained hardening film is excellent in drug resistance, and has a high glass transition point (Tg.). In addition, it was further found that the photosensitive resin composition is also excellent in storage stability, and thus the present application was completed.

[0109] That is, the present application provides a negative photosensitive resin composition characterized by comprising:

[0110] (A) a high molecular compound having a polyimide precursor structure,

[0111] (C) a photopolymerization initiator,

[0112] (D) an organic compound represented by the following general formula (1), and

[0113] (E) a solvent;

[0114] [Chemical Formula 12]

[0115]

[0116] In the formula, T represents any one of the following general formulae (2) to (4), and W represents an alkyl group or an aryl group which can also be substituted with an alkoxy group having 4 to 15 carbon atoms.

[0117] [Chemical Formula 13]

[0118]

[0119] In the formula, V represents a divalent organic group, and * represents a bond.

[0120] [Chemical Formula 14]

[0121]

[0122] In the formula, 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.

[0123] [Chemical Formula 15]

[0124]

[0125] wherein Ar represents a substituted or unsubstituted aromatic ring structure, or a heterocyclic ring structure having a hetero atom, and * represents a bond.

[0126] Hereinafter, the present application will be described in detail, but the present application is not limited to these.

[0127] [(A) Component]

[0128] From the viewpoint of the film strength of the obtained hardened film, the polymeric compound of the present application containing a structural unit of a polyimide precursor is preferably a polymeric compound represented by the following formula (5).

[0129] [Chemical Formula 16]

[0130]

[0131] wherein X is a 4-valent organic group, Y is a 2-valent organic group, R 1 and R 2 each independently is a hydrogen atom or a 1-valent organic group, and at least one of R 1 and R 2 is a group represented by the following general formula (6).

[0132] [Chemical Formula 17]

[0133]

[0134] wherein M 1 , M 2 , and M 3 each independently is a hydrogen atom or an organic group having a carbon number of 1 to 3, and m is an integer of 2 to 10. * represents a bond.

[0135] X in the above general formula (5) is a 4-valent organic group, but there is no limitation as long as it is a 4-valent organic group. It is preferably a 4-valent organic group of an alicyclic aliphatic group or an aromatic group having a carbon number of 4 to 40. It is further preferably a 4-valent organic group represented by the following formula (7). In addition, the structure of X can be one kind, or a combination of two or more kinds.

[0136] [Chemical Formula 18]

[0137]

[0138] wherein R e1 , R e2 each independently is a methyl group or a phenyl group, b1 and b2 are integers of 1 to 20, and the dotted line represents an atomic bond.

[0139] 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, and is preferably a divalent organic group having a carbon number of 6 to 40, more preferably a divalent cyclic organic group having 1 to 4 substituted aromatic rings or aliphatic rings, or a divalent aliphatic group having no cyclic structure, or a siloxane group. As a further preferable Y, a structure represented by the following formula (8) or (9) can be given. In addition, the structure of Y can be one, or a combination of two or more.

[0140] [Chemical Formula 19]

[0141]

[0142] In the formula, b3 is an integer of 1 to 20, s1 is an integer of 1 to 40, s2 and s3 are each independently an integer of 0 to 40, and the dotted line represents a bond.

[0143] [Chemical Formula 20]

[0144]

[0145] In the formula, b4 is an integer of 1 to 4, 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.

[0146] R 1 and R 2 in the above general formula (5) 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 a carbon number of 1 to 6, or an organic group represented by the above general formula (6), and at least one of R 1 and R 2 is the organic group represented by the above general formula (6).

[0147] M 1 in the above general formula (6) is not limited as long as it is a hydrogen atom or a monovalent organic group having a carbon number of 1 to 3, and is preferably a hydrogen atom or a methyl group from the viewpoint of the photosensitive properties of the negative photosensitive resin composition.

[0148] M 2 and M 3 in the above general formula (6) are each independently not limited as long as they are a hydrogen atom or a monovalent organic group having a carbon number of 1 to 3, and are preferably a hydrogen atom from the viewpoint of the photosensitive properties of the negative photosensitive resin composition.

[0149] m in the above general formula (6) is an integer of 2 to 10, and is preferably an integer of 2 to 4 from the viewpoint of photosensitivity. Further preferably, m is 2.

[0150] In addition, the high molecular compound of the present application can contain any one or more of the structural units represented by the following general formulae (10) to (12) in addition to the structural unit represented by the above general formula (5).

[0151] [Chemical Formula 21]

[0152]

[0153] In the formula, X1is a 4-valent organic group which is the same as or different from the above X, and Y1is a 2-valent organic group which is the same as or different from the above Y.

[0154] [Chemical Formula 22]

[0155]

[0156] In the formula, X2is a 2-valent organic group, and Y2is a 2-valent organic group which is the same as or different from the above Y.

[0157] [Chemical Formula 23]

[0158]

[0159] In the formula, Y3is a 2-valent organic group which is the same as or different from the above Y, and X3is a 4-valent organic group.

[0160] X1in the above general formula (10) is a 4-valent organic group, and can be the same as or different from the above X, and is not limited as long as it is a 4-valent organic group. It is preferably a 4-valent alicyclic aliphatic group having a carbon number of 4 to 40 or a 4-valent aromatic group having a carbon number of 6 to 40, and can also contain a siloxane skeleton. Further preferably, it is a 4-valent organic group represented by the above formula (7). In addition, the structure of X1may be one kind, or a combination of two or more kinds.

[0161] Y1in the above general formula (10) is a 2-valent organic group, and can be the same as or different from the above Y, and is not limited as long as it is a 2-valent organic group. It is preferably a 2-valent organic group having a carbon number of 6 to 40, and more preferably a 2-valent cyclic organic group containing 1 to 4 aromatic rings or aliphatic rings having a substituent, or a 2-valent aliphatic group having no cyclic structure, or a siloxane group. As a further preferable Y1, a structure represented by the above formula (8) or (9) can be given. In addition, the structure of Y1may be one kind, or a combination of two or more kinds.

[0162] If the resin composition contains a high molecular compound containing a structural unit represented by the above general formula (10), the mechanical strength of the hardened film obtained by forming a pattern, the adhesion to a substrate, and the heat resistance are improved, and thus it is more desirable. In addition, the structural unit (10) does not need to undergo a ring-closing reaction in post-hardening, and thus the hardening reaction temperature can be relatively lowered, and thus it is more desirable.

[0163] X2in the above general formula (11) is a divalent organic group, and there is no limitation as long as it is a divalent organic group. It is preferably a divalent organic group of an aliphatic chain structure having 4 to 40 carbon atoms, a divalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a divalent aromatic group having 6 to 40 carbon atoms. It is further preferably a divalent organic group represented by the following formula (13). In addition, the structure of X2may be one or a combination of two or more.

[0164] [Chemical Formula 24]

[0165]

[0166] in the formula, R a3 each independently is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, b4is an integer of 1 to 30, and the dotted line indicates a bond.

[0167] Y2in the above general formula (11) is a divalent organic group, and can be the same as or different from the above Y, and there is no limitation as long as it is a divalent organic group. It is preferably a divalent organic group having 6 to 40 carbon atoms, a divalent cyclic organic group containing 1 to 4 aromatic rings or aliphatic rings having a substituent, or a divalent aliphatic group not having a cyclic structure, or a siloxane group. It is further preferably a structure represented by the above formula (8) or (9). In addition, the structure of Y2may be one or a combination of two or more.

[0168] Y3in the above general formula (12) is a divalent organic group, and can be the same as or different from the above Y, and there is no limitation as long as it is a divalent organic group. It is preferably a divalent organic group of an aliphatic chain structure having 4 to 40 carbon atoms, a divalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a divalent aromatic group having 6 to 40 carbon atoms. It is further preferably a divalent organic group represented by the above formula (13). In addition, the structure of Y3may be one or a combination of two or more.

[0169] X3in the above general formula (12) is a tetravalent organic group, and is not limited as long as it is a tetravalent organic group, and is preferably a tetravalent organic group having a carbon number of 6 to 40, and more preferably a tetravalent cyclic organic group having 1 to 4 aromatic rings or aliphatic rings having a substituent, or a tetravalent aliphatic group having no cyclic structure, or a siloxane group. As a further preferable X3, a structure represented by the following formula (14) can be given. Further, the structure of X3may be one, or a combination of two or more.

[0170] [Chem. 25]

[0171]

[0172] in the formula, b 12 , b 13 , and b 14 are integers of 1 to 10; b 15 is an integer of 1 to 20, and the dotted line represents a bond of an atom.

[0173] If it is a resin composition containing a polymer having the structural unit represented by the above general formula (12), the mechanical strength, the adhesion to a substrate, and the heat resistance of a hardened film obtained by performing patterning can be improved, and thus it is preferable. Further, in the case where the structure represented by general formula (12) is contained, a ring-closing reaction is not required in post-hardening, and thus the hardening reaction temperature can be relatively lowered, and thus it is preferable.

[0174] The suitable molecular weight of the polymer of the present application is preferably 5,000 to 100,000, and more preferably 7,000 to 50,000. If the molecular weight is 5,000 or more, a composition containing the polymer of the present application can be easily formed into a desired film thickness on a substrate, and if the molecular weight is 100,000 or less, the viscosity of the above-mentioned photosensitive composition does not significantly increase, and a film can be easily formed. In the present application, the weight average molecular weight is measured by GPC at a temperature of 40°C using DMF as an eluent, and is a polystyrene conversion value obtained by gel permeation chromatography (GPC).

[0175] [Method for producing a high molecular compound]

[0176] The high molecular compound contained in the negative photosensitive resin composition of the present application preferably contains a structural unit represented by the following general formula (5).

[0177] [Chem. 26]

[0178]

[0179] in the formula, X is a tetravalent organic group, Y is a divalent organic group, R 1 , and R 2each independently a hydrogen atom or a monovalent organic group, and R 1 and R 2 at least one of which is a group represented by the following general formula (6).

[0180] [Chem. 27]

[0181]

[0182] wherein M1, M2, and M3are each independently a hydrogen atom or an organic group having a carbon number of 1 to 3, and m is an integer of 2 to 10. * represents a bond.

[0183] The polymer containing the structural unit represented by the above 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).

[0184] [Chem. 28]

[0185]

[0186] wherein X, R 1 and R 2 are the same as described above.

[0187] [Chem. 29]

[0188] H2N-Y-NH2 (16)

[0189] wherein Y is the same as described above.

[0190] In the above general formula (15), at least either one of R 1 and R 2 is an organic group represented by the above general formula (6), and the organic group represented by the above general formula (6) can be introduced by reacting a tetracarboxylic acid 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. In this case, the tetracarboxylic acid dianhydride represented by the above general formula (17) becomes the basis of X (for example, the above 4-valent organic group represented by the above formula (7)) in the above general formula (5), and the compound having a terminal hydroxyl group represented by the above general formula (18) can introduce the organic group represented by the above general formula (6).

[0191] [Chem. 30]

[0192]

[0193] wherein X represents a 4-valent organic group, and has the same meaning as X in the above general formula (5).

[0194] [Chem. 31]

[0195]

[0196] in the formula, M 1 , M 2 , M 3 and m are synonymous with M 1 , M 2 , M 3 and m in the above general formula (6).

[0197] As examples of the tetracarboxylic dianhydride represented by the above general formula (17), aromatic acid dianhydrides, alicyclic acid dianhydrides, aliphatic acid dianhydrides, acid dianhydrides containing a siloxane skeleton, and the like can be given.

[0198] Aromatic acid dianhydrides, for example: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-oxyphthalic dianhydride, 2,3,3',4'-oxyphthalic dianhydride, 2,3,2',3'-oxyphthalic dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenyl ketone-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-phenylene bis(trimellitic monoester anhydride), bis(l,3-dioxo-l,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis(4-(3,4-dicarboxyphenoxy)phenyl)fluorene dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 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-bis(trifluoromethyl)pyromellitic dianhydride, 2,2'-bis(trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, or acid dianhydride compounds in which the aromatic rings thereof are substituted with alkyl groups, alkoxy groups, halogen atoms, and the like, and the like, but are not limited to these.

[0199] alicyclic acid dianhydride such as 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride, 1,2,4,5-cyclopentane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cycloheptane tetracarboxylic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic acid dianhydride, 2,3,5-tricarboxy cyclopentyl acetic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid dianhydride, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic acid dianhydride, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic acid dianhydride, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic acid dianhydride, tricyclo[6,3,0,0 2,6 ]undecane-3,5,9,11-tetracarboxylic acid dianhydride, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo[2,2,1]heptane tetracarboxylic acid dianhydride, bicyclo[2,2,1]heptane-5-carboxymethyl-2,3,6-tricarboxylic acid dianhydride, 7-oxabicyclo[2,2,1]heptane-2,4,6,8-tetracarboxylic acid dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic acid dianhydride, tetradecahydroanthracene-1,2,8,9-tetracarboxylic acid dianhydride, 3,3',4,4'-dicyclohexane tetracarboxylic acid dianhydride, 3,3',4,4'-oxobicyclohexane tetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, and "Rikacid" (registered trademark) BT-100 (trade name, Shin Nippon Rikagaku K.K.), and derivatives thereof, or acid dianhydride compounds substituted with aliphatic organic alkyl groups, alkoxy groups, halogen atoms, and the like, but are not limited thereto.

[0200] As the aliphatic acid dianhydride, for example, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-pentanetetracarboxylic acid dianhydride, and derivatives thereof, and the like can be exemplified, but are not limited thereto.

[0201] As the acid dianhydride containing a siloxane skeleton, for example, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 3,3'-(1,1,3,3-tetramethyl-1,3-disiloxanediyl)bis(2,5-dihydrofuran-2,5-dione), and derivatives thereof, and the like can be exemplified, but are not limited thereto.

[0202] These aromatic acid dianhydrides, alicyclic acid dianhydrides, aliphatic acid dianhydrides, and acid dianhydrides containing a siloxane skeleton can be used alone or in combination with two or more.

[0203] M in the above general formula (18) 1 There is no limitation as long as it is a hydrogen atom or a monovalent organic group having a carbon number of 1 to 3, and from the viewpoint of the photosensitive properties of the negative photosensitive resin composition, it is preferable to be a hydrogen atom or a methyl group.

[0204] M in the above general formula (18) 2 and M 3 There is no limitation as long as it is independently a hydrogen atom or a monovalent organic group having a carbon number of 1 to 3, and from the viewpoint of the photosensitive properties of the negative photosensitive resin composition, it is preferable to be a hydrogen atom.

[0205] m in the above general formula (18) is an integer of 2 to 10, and from the viewpoint of the photosensitive properties, it is preferable to be an integer of 2 to 4. More preferably, m is 2.

[0206] Among the compounds represented by the above general formula (18) having a hydroxyl group at the terminal, as preferable compounds, for example, 2-acryloyloxyethanol, 1-acryloyloxy-3-propanol, 2-methacryloyloxyethanol, 1-methacryloyloxy-3-propanol, and the like can be mentioned.

[0207] In addition, R 1 and R 2 may be a linear, branched, or cyclic alkyl group having a carbon number of 1 to 6. As a method of introducing a linear, branched, or cyclic alkyl group having a carbon number of 1 to 6 (i.e., R 1 and R 2 become a linear, branched, or cyclic alkyl group having a carbon number of 1 to 6) into the above general formula (5), a method of simultaneously adding a linear, branched, or cyclic alcohol having a carbon number of 1 to 6 in the reaction of the compound represented by the above general formula (18) having a hydroxyl group at the terminal with tetracarboxylic dianhydride in the presence of a basic catalyst such as pyridine can be mentioned.

[0208] As preferable alcohols that can be used at this time, 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, cyclohexanol, and the like can be mentioned.

[0209] As for the reaction of the tetracarboxylic dianhydride represented by the aforementioned general formula (17) and the compound having a hydroxyl group at the terminal represented by the aforementioned general formula (18), the tetracarboxylic dianhydride represented by the aforementioned general formula (17) and the compound having a hydroxyl group at the terminal represented by the aforementioned general formula (18) are stirred, dissolved and mixed in a reaction solvent in the presence of a basic catalyst such as pyridine at a reaction temperature of 20°C to 50°C for 4 hours to 10 hours, whereby a semi-esterification reaction of the dianhydride is performed, and a solution in which the desired tetracarboxylic diester compound represented by the aforementioned general formula (15) is dissolved in a reaction solvent is obtained.

[0210] The obtained tetracarboxylic diester compound can be separated, or the obtained solution can be directly used for the reaction with a diamine in the next step described below.

[0211] As the reaction solvent described above, a solvent capable of well dissolving the tetracarboxylic diester described above and a polymer having a structural unit of a polyimide precursor obtained by the polycondensation reaction of the tetracarboxylic diester described above and a diamine described above to be performed next can be exemplified, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethyl urea, γ-butyrolactone and the like. In addition, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like can also be used, and specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like can be exemplified. These can be used alone as needed or two or more kinds thereof can be used in mixture.

[0212] As examples of the diamine represented by the above general formula (16), for example, (2-methyl-4-amino)phenyl-4-aminobenzoate, (3-methyl-4-amino)phenyl-4-aminobenzoate, (2-ethyl-4-amino)phenyl-4-aminobenzoate, (3-ethyl-4-amino)phenyl-4-aminobenzoate, (2-propyl-4-amino)phenyl-4-aminobenzoate, (3-propyl-4-amino)phenyl-4-aminobenzoate, (2-isopropyl-4-amino)phenyl-4-aminobenzoate, (3-isopropyl-4-amino)phenyl-4-aminobenzoate, (2-butyl-4-amino)phenyl-4-aminobenzoate, (3-butyl-4-amino)phenyl-4-aminobenzoate, (2-isobutyl-4-amino)phenyl-4-aminobenzoate, (3-isobutyl-4-amino)phenyl-4-aminobenzoate, (2-pentyl-4-amino)phenyl-4-aminobenzoate, (3-pentyl-4-amino)phenyl-4-aminobenzoate, (2-hexyl-4-amino)phenyl-4-aminobenzoate, (3-hexyl-4-amino)phenyl-4-aminobenzoate, (2-methoxy-4-amino)phenyl-4-aminobenzoate, (3-methoxy-4-amino)phenyl-4-aminobenzoate, (2-ethoxy-4-amino)phenyl-4-aminobenzoate, (3-ethoxy-4-amino)phenyl-4-aminobenzoate, (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-4-amino)phenyl-4-aminobenzoate, (3-propylphenoxy-4-amino)phenyl-4-aminobenzoate, (2-methoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (3-methoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (2-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-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-ethylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (3- ethylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (2-propylbenzyloxy-4- amino)phenyl-4-aminobenzoate, (3-propylbenzyloxy-4-amino)phenyl-4- aminobenzoate, (2-methoxybenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-methoxybenzyloxy-4-amino)phenyl-4-aminobenzoate, (2- ethoxybenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-ethoxybenzyloxy- 4-amino)phenyl-4-aminobenzoate, 4-(4-aminophenoxy)-3-methylaniline, 4-(4-aminophenoxy)-2-methylaniline, 4-(4-aminophenoxy)-3- ethylaniline, 4-(4-aminophenoxy)-2-ethylaniline, 4-(4-aminophenoxy)-3- propylaniline, 4-(4-aminophenoxy)-2-propylaniline, 4-(4-aminophenoxy)-3- isopropylaniline, 4-(4-aminophenoxy)-2-isopropylaniline, 4-(4- aminophenoxy)-3-butylaniline, 4-(4-aminophenoxy)-2-butylaniline, 4-(4- aminophenoxy)-3-isobutylaniline, 4-(4-aminophenoxy)-2-isobutylaniline,

[0213] 4-(4-aminophenoxy)-3-pentyl aniline, 4-(4-aminophenoxy)-2-pentyl aniline, 4-(4-aminophenoxy)-3-hexyl aniline, 4-(4-aminophenoxy)-2-hexyl aniline, 4-(4-aminophenoxy)-3-(trifluoromethyl) aniline, 4-(4-aminophenoxy)-2-(trifluoromethyl) aniline, 4-(4-aminophenoxy)-3-methoxy aniline, 4-(4-aminophenoxy)-2-methoxy aniline, 4-(4-aminophenoxy)-3-ethoxy aniline, 4-(4-aminophenoxy)-2-ethoxy aniline, 4-(4-aminophenoxy)-3-propoxy aniline, 4-(4-aminophenoxy)-2-propoxy aniline, 4-(4-aminophenoxy)-3-butoxy aniline, 4-(4-aminophenoxy)-2-butoxy aniline, 4-(4-aminophenoxy)-3-phenyl aniline, 4-(4-aminophenoxy)-2-phenyl aniline, 4-(4-aminophenoxy)-3-methylphenyl aniline, 4-(4-aminophenoxy)-2-methylphenyl aniline, 4-(4-aminophenoxy)-3-ethylphenyl aniline, 4-(4-aminophenoxy)-2-ethylphenyl aniline, 4-(4-aminophenoxy)-3-propylphenyl aniline, 4-(4-aminophenoxy)-2-propylphenyl aniline, 4-(4-aminophenoxy)-3-butylphenyl aniline, 4-(4-aminophenoxy)-2-butylphenyl aniline, 4-(4-aminophenoxy)-3-fluorophenyl aniline, 4-(4-aminophenoxy)-2-fluorophenyl aniline, 4-(4-aminophenoxy)-3-chlorophenyl aniline, 4-(4-aminophenoxy)-2-chlorophenyl aniline, 4-(4-aminophenoxy)-3-bromophenyl aniline, 4-(4-aminophenoxy)-2-bromophenyl aniline, 4-(4-aminophenoxy)-3-methoxyphenyl aniline, 4-(4-aminophenoxy)-2-methoxyphenyl aniline, 4-(4-aminophenoxy)-3-ethoxyphenyl aniline, 4-(4-aminophenoxy)-2-ethoxyphenyl aniline, 4-(4-aminophenoxy)-3-(phenylethyl)phenyl aniline, 4-(4-aminophenoxy)-2-(phenylethyl)phenyl aniline, 4-(4-aminophenoxy)-3-naphthylphenyl aniline, 4-(4-aminophenoxy)-2-naphthylphenyl aniline, 4-(4-aminophenoxy)-3-benzylphenyl aniline, 4-(4-aminophenoxy)-2-benzylphenyl aniline, 4-((4-aminophenyl)thio)-3-methylaniline, 4-((4-aminophenyl)thio)-2-methylaniline, 4-((4-aminophenyl)thio)-3-ethylaniline, 4-((4-aminophenyl)thio)-2-ethylaniline, 4-((4-aminophenyl)thio)-3-propylaniline, 4-((4-aminophenyl)thio)-2-propylaniline, 4-((4-aminophenyl)thio)-3-isopropylaniline, 4-((4-aminophenyl)thio)-2-isopropylaniline,4-((4-aminophenyl)sulfanyl)-3-ethyl aniline, 4-((4-aminophenyl)sulfanyl)-2-ethyl aniline, 4-((4-aminophenyl)sulfanyl)-3-propyl aniline, 4-((4-aminophenyl)sulfanyl)-2-propyl aniline, 4-((4-aminophenyl)sulfanyl)-3-isopropyl aniline, 4-((4-aminophenyl)sulfanyl)-2-isopropyl aniline, 4-((4-aminophenyl)sulfanyl)-3-butyl aniline, 4-((4-aminophenyl)sulfanyl)-2-butyl aniline, 4-((4-aminophenyl)sulfanyl)-3-isobutyl aniline, 4-((4-aminophenyl)sulfanyl)-2-isobutyl aniline, 4-((4-aminophenyl)sulfanyl)-3-(trifluoromethyl)aniline, 4-((4-aminophenyl)sulfanyl)-2-(trifluoromethyl)aniline, 4-((4-aminophenyl)sulfanyl)-3-methoxy aniline, 4-((4-aminophenyl)sulfanyl)-2-methoxy aniline, 4-((4-aminophenyl)sulfanyl)-3-ethoxy aniline, 4-((4-aminophenyl)sulfanyl)-2-ethoxy aniline, 4-((4-aminophenyl)sulfanyl)-3-propoxy aniline, 4-((4-aminophenyl)sulfanyl)-2-propoxy aniline, 4-((4-aminophenyl)sulfanyl)-3-isopropoxy aniline, 4-((4-aminophenyl)sulfanyl)-2-isopropoxy aniline, 4-((4-aminophenyl)sulfanyl)-3-butoxy aniline, 4-((4-aminophenyl)sulfanyl)-2-butoxy aniline, 4-((4-aminophenyl)sulfanyl)-3-phenyl aniline, 4-((4-aminophenyl)sulfanyl)-2-phenyl aniline, 4-((4-aminophenyl)sulfanyl)-3-naphthyl aniline, 4-((4-aminophenyl)sulfanyl)-2-naphthyl aniline, 4-((4-aminophenyl)sulfanyl)-3-methoxyphenyl aniline, 4-((4-aminophenyl)sulfanyl)-2-methoxyphenyl aniline, 4-((4-aminophenyl)methyl)-3-methylaniline, 4-((4-aminophenyl)methyl)-2-methylaniline, 4-((4-aminophenyl)methyl)-3-ethylaniline, 4-((4-aminophenyl)methyl)-2-ethylaniline, 4-((4-aminophenyl)methyl)-3-propylaniline, 4-((4-aminophenyl)methyl)-2-propylaniline, 4-((4-aminophenyl)methyl)-3-isopropylaniline, 4-((4-aminophenyl)methyl)-2-isopropylaniline, 4-((4-aminophenyl)methyl)-3-butanilaniline, 4-((4-aminophenyl)methyl)-2-butanilaniline, 4-((4-aminophenyl)methyl)-3-isobutanilaniline, 4-((4-aminophenyl)methyl)-2-isobutanilaniline, 4-((4-aminophenyl)methyl)-3-(trifluoromethyl)aniline, 4-((4-aminophenyl)methyl)-2-(trifluoromethyl)aniline, 4-((4-aminophenyl)methyl)-3-methoxy aniline, 4-((4-aminophenyl)methyl)-2-methoxy aniline, 4-((4-aminophenyl)methyl)-3-ethoxy aniline, 4-((4-aminophenyl)methyl)-2-ethoxy aniline, 4-((4-aminophenyl)methyl)-3-propoxy aniline, 4-((4-aminophenyl)methyl)-2-propoxy aniline, 4-((4-aminophenyl)methyl)-3-isopropoxy aniline, 4-((4-aminophenyl)methyl)-2-isopropoxy aniline,4-((4-aminophenyl)methyl)-3-butoxyaniline, 4-((4-aminophenyl)methyl)-2-butoxyaniline, 4-((4-aminophenyl)methyl)-3-phenylaniline, 4-((4-aminophenyl)methyl)-2-phenylaniline, 4-((4-aminophenyl)methyl)-3-naphthylaniline, 4-((4-aminophenyl)methyl)-2-naphthylaniline, 4-((4-aminophenyl)methyl)-3-methoxyphenylaniline, 4-((4-aminophenyl)methyl)-2-methoxyphenylaniline, (4-amino-2-methylphenyl)(4-aminophenyl) methanone, (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, (4-amino-2-(methoxyphenyl)phenyl)(4-aminophenyl) methanone, but not limited to these.

[0214] Here, the high molecular compound containing the polyimide precursor having the structural unit represented by the above general formula (5) can be obtained, for example, by reacting the tetracarboxylic acid diester compound represented by the above general formula (15) with the diamine represented by the above general formula (16) in the presence of a condensing agent. That is, the tetracarboxylic acid diester compound represented by the above general formula (15) is used in the reaction in a state of being dissolved in the above reaction solvent, and in this reaction solution, a known dehydration condensing agent (for example, dicyclohexyl carbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and the like) is added and mixed at ice cold, and after the tetracarboxylic acid diester compound represented by the above general formula (15) is made into a polyanhydride, a substance obtained by dissolving or dispersing the diamine represented by the above general formula (16) in another solvent is added dropwise thereto, and the polycondensation is performed, whereby the high molecular compound containing the polyimide precursor having the structural unit represented by the above general formula (2) can be obtained.

[0215] In addition, as another method of obtaining a high molecular compound having a polyimide precursor including a structural unit represented by the above general formula (5) by reacting a tetracarboxylic acid diester compound represented by the above general formula (15) with a diamine compound represented by the above general formula (16), a method in which the tetracarboxylic acid diester compound represented by the above general formula (15) is converted into an acid chloride using a chlorinating agent such as thionyl chloride or dichlorooxalic acid, and reacted with a diamine represented by the above general formula (16) can be exemplified.

[0216] In the reaction in which the above tetracarboxylic acid diester is converted into an acid chloride using a chlorinating agent, a basic compound can be used. As the basic compound, for example, pyridine, 4-dimethylaminopyridine, triethylamine, or the like can be used.

[0217] Then, the obtained acid chloride of the tetracarboxylic acid diester is reacted with a diamine represented by the above general formula (16) in the presence of a basic catalyst, whereby a target high molecular compound having a polyimide precursor including a structural unit represented by the above general formula (5) can be obtained. At this time, as the basic catalyst, pyridine, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, or the like can be exemplified.

[0218] In the method of producing a polymer having a polyimide precursor, the solvent used in the method via an acid chloride is preferably a solvent that sufficiently dissolves a tetracarboxylic acid diester and its acid chloride, more preferably a solvent that more sufficiently dissolves a polymer of a polyimide precursor obtained by polycondensation of a tetracarboxylic acid diester and its acid chloride with a diamine, and the same solvent as the above solvent can be used. Specifically, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethyl urea, hexamethylphosphoric triamide, γ-butyrolactone, or the like can be exemplified. In addition, in addition to a polar solvent, a ketone, an ester, a lactone, an ether, a halogenated hydrocarbon, a hydrocarbon, or the like can be used. For example, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichloroethane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, or the like can be exemplified. These organic solvents can be used alone or in combination of two or more.

[0219] In addition, as described above, the high molecular compound having a polyimide precursor used in the negative photosensitive resin composition of the present application can include a structural unit represented by the above general formula (10) in addition to the structural unit represented by the above general formula (5).

[0220] [Chem. 32]

[0221]

[0222] wherein X1and Y1are the same as described above.

[0223] The polymer containing the structural unit represented by the aforementioned 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, the tetracarboxylic dianhydride represented by the following general formula (19) is reacted with the diamine represented by the following general formula (20) to synthesize an amic acid, and then chemical imidization, imidization by dehydration using heat, are performed, whereby a polymer containing the structural unit (10) can be obtained.

[0224] The aforementioned structural unit (10) can be manufactured by dissolving a diamine in a high-boiling and highly polar solvent such as γ-butyrolactone or N-methyl-2-pyrrolidone, adding an acid anhydride, and performing a reaction at 0°C to 80°C, preferably 10°C to 50°C, to produce an amic acid, and then performing an imidization reaction by, for example, adding acetic anhydride and pyridine in chemical imidization, and adding a non-polar solvent such as xylene and heating to 100°C to 200°C, preferably 130°C to 180°C, in imidization by dehydration using heat, while removing water from the reaction system.

[0225] [Chem. 33]

[0226]

[0227] wherein X1is the same as described above.

[0228] [Chem. 34]

[0229] H2N-Y1-NH2 (20)

[0230] wherein Y1is the same as described above.

[0231] As the tetracarboxylic dianhydride represented by the aforementioned general formula (19), examples shown in the aforementioned tetracarboxylic dianhydride represented by the general formula (17) can be cited as ideal examples.

[0232] As the diamine represented by the aforementioned general formula (20), examples shown in the aforementioned diamine represented by the general formula (16) can be cited as ideal examples.

[0233] In addition, as described above, the high-molecular compound having a polyimide precursor used in the negative photosensitive resin composition of the present application can contain, in addition to the structural unit represented by the aforementioned general formula (5), a structural unit represented by the following general formula (11).

[0234] [Chem. 35]

[0235]

[0236] In the formula, X2 and Y2 are the same as those above.

[0237] Polymers containing the structural units shown in general formula (11) above can be obtained by performing the same reaction steps as those for structural unit (5) above. That is, they can be obtained by reacting a dicarboxylic acid compound shown in general formula (21) below with a dehydrating condensing agent, converting it to an acyl chloride using a chlorinating agent, and then reacting it with a diamine shown in general formula (22) above.

[0238] [Chemistry 36]

[0239]

[0240] In the formula, X2 is the same as above.

[0241] [Chemistry 37]

[0242] H2N-Y2-NH2 (22)

[0243] In the formula, Y2 is the same as above.

[0244] Examples of dicarboxylic acid compounds represented by the above general formula (21) include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, and pimelic acid. , 2,2,6,6-tetramethyl pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid Acid, eicosanedioic acid, hexadecanedioic acid, docosanedioic acid, triposanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, hexadecanedioic acid, diglycolic acid, etc.

[0245] Further, as the dicarboxylic acid compound having an aromatic ring, for example, 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'-dicarboxybenzamide, 1,4-phenylene diacetic acid, bis(4-carboxyphenyl) sulfide, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-carboxyphenyl)tetraphenyl disiloxane, bis(4-carboxyphenyl)tetramethyldisiloxane, bis(4-carboxyphenyl) sulfone, bis(4-carboxyphenyl) methane, 5-tert-butyl isophthalic acid, 5-bromo isophthalic acid, 5-fluoro isophthalic acid, 5-chloro isophthalic acid, 2,2-bis-(p-carboxyphenyl)propane, 2,6-naphthalene dicarboxylic acid, and the like, but are not limited to these. In addition, they can be used alone or in combination.

[0246] As the diamine represented by the aforementioned general formula (22), the examples represented by the aforementioned general formula (16) can be cited as ideal examples.

[0247] Further, as described above, the polymer compound having a polyimide precursor used in the negative photosensitive resin composition of the present application can contain, in addition to the structural unit represented by the aforementioned general formula (5), a structural unit represented by the following general formula (12).

[0248] [Chemical Formula 38]

[0249]

[0250] In the formula, X3and Y3are the same as described above.

[0251] As to the polymer containing the structural unit represented by the aforementioned general formula (12), a dicarboxylic acid compound represented by the following general formula (23) is subjected to a reaction in the presence of a dehydration condensing agent, a reaction for converting into an acid chloride using a chlorinating agent, and then reacted with a dihydroxy diamine compound represented by the following general formula (24), whereby a hydroxy amide (polyoxazole precursor) is synthesized, and then an oxazole ring is formed by a heating dehydration step, whereby a polymer containing the structural unit represented by the aforementioned general formula (12) can be obtained.

[0252] [Chemical Formula 39]

[0253]

[0254] In the formula, Y3is the same as described above.

[0255] [Chemical Formula 40]

[0256]

[0257] wherein X3 is the same as described above.

[0258] As the dicarboxylic acid compound represented by the above general formula (23), examples shown in the dicarboxylic acid compound represented by the above general formula (21) can be cited as ideal examples.

[0259] The dihydroxydiamine compound represented by the above general formula (24) is, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl 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, and the like, but is not limited thereto. In addition, they can be used alone or in combination.

[0260] (Molecular weight of polymer and introduction of end-capping agent)

[0261] The preferable molecular weight of the above high molecular compound is preferably 5,000 to 100,000, more preferably 7,000 to 50,000. If the molecular weight is 5,000 or more, the negative photosensitive resin composition of the present application using the above polymer is easily formed into a desired film thickness on a substrate, and if the molecular weight is 100,000 or less, the viscosity of the above negative photosensitive resin composition becomes moderate, and film formation is not problematic.

[0262] As the end-capping agent that reacts with a diacid anhydride, monoamine, monohydric alcohol, and the like can be cited. In addition, as the end-capping agent that reacts with a diamine, acid anhydride, monocarboxylic acid, monoacyl chloride compound, monoactive ester compound, dicarbonic acid ester, vinyl ether, and the like can be cited. In addition, by reacting the end-capping agent, various organic groups can be introduced as terminal groups.

[0263] Monamines which can be used as capping agents for the acid anhydride group-terminated, such as aniline, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8- aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1- hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3- aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2- hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5- aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1- amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7- aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1- carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2- aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2- carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4- aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2- aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6- aminonicotinic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6- aminosalicylic acid, 2,4-dioxy-6-amino-sym-triazine (ammelide), 2-aminobenzoic acid, 3- aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3- aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6- dihydroxyprimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8- mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8- aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6- aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4- aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2- aminonaphthalene, 1-amino-7-mercaptonaphthalene, 2-mercapto-7- aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5- aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3- aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6- dimercapto-primidine, 2-aminothiophenol, 3-aminothiophenol, 4- aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2,4-5-Diethynylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-aminonaphthalene, 3,5-Diethynyl The following are examples of fluoroaniline, but not limited to: 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7-diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-aminonaphthalene, 4,8-diethynyl-2-aminonaphthalene, 4-fluoroaniline, 3-fluoroaniline, 2-fluoroaniline, 2,4-difluoroaniline, 3,4-difluoroaniline, 2,4,6-trifluoroaniline, 2,3,4-trifluoroaniline, pentafluoroaniline, etc. They can be used alone or in combination with two or more.

[0264] On the other hand, examples of monohydric alcohols that can be used as end-capping agents for anhydride groups include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, 2-nonanol, 1-decanol, 2-decanol, 1-undecanol, 2-undecanol, 1-dodecanool, 2-dodecanool, 1-tridecanol, 2-tridecanol, 1-tetradecanool, 2-tetradecanool, 1-pentadecanol, 2-pentadecanol, 1-hexadecanool, 2-hexadecanool, 1-heptadecanool, 2-heptadecanool, 1-octadecanool, 2-octadecanool, 1-nonadecanol, 2-nonadecanol, 1-eicosyl-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, isononol, 3,7-dimethyl-3-octanol, 2,4-dimethyl-1-heptanol, 2-heptylidene undecylol, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol 1-methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, cyclopentanol, cyclohexanol, monohydroxymethylcyclopentane, monohydroxymethyldicyclopentane, monohydroxymethyltricyclodecane, norborneol, pinoresinol, etc., but not limited to these. In addition, they can be used individually or in combination with two or more.

[0265] As the acid anhydride, monocarboxylic acid, monoacyl chloride compound, and monoactive ester compound used as the capping agent for the amino terminal, there are mentioned phthalic anhydride, maleic anhydride, naphthalene-2, 6-dicarboxylic anhydride, cyclohexane dicarboxylic anhydride, 3-hydroxyphthalic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid, 8-ethynyl-2-naphthoic acid, and the like monocarboxylic acids and monoacyl chloride compounds obtained by acyl chlorination of the carboxyl group thereof, and monoacyl chloride compounds obtained by acyl chlorination of only one carboxyl group of terephthalic acid, phthalic acid, maleic acid, cyclohexane dicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2, 3-dicarboxylic acid, 1, 2-dicarboxynaphthalene, 1, 3-dicarboxynaphthalene, 1, 4-dicarboxynaphthalene, 1, 5-dicarboxynaphthalene, 1, 6-dicarboxynaphthalene, 1, 7-dicarboxynaphthalene, 1, 8-dicarboxynaphthalene, 2, 3-dicarboxynaphthalene, 2, 6-dicarboxynaphthalene, 2, 7-dicarboxynaphthalene, and the like dicarboxylic acids, and monoactive ester compounds obtained by reaction of the monoacyl chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2, 3-dicarboximide.

[0266] As the dicarboxylic acid ester compound used as the capping agent for the amino terminal, there are mentioned di-t-butyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, diethyl dicarbonate, and the like.

[0267] As the vinyl ether compound used as the capping agent for the amino terminal, there are mentioned butyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, t-butyl vinyl ether, benzyl vinyl ether, and the like.

[0268] As other compounds used as capping agents for amino terminals, benzoyl chloride, fluorenylmethyl chloroformate, 2,2,2-trichloroethyl chloroformate, t-butyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, benzyl chloroformate, allyl chloroformate, ethyl chloroformate, isopropyl chloroformate, and the like chloroformates, butyl isocyanate, 1-naphthyl isocyanate, octadecyl isocyanate, phenyl isocyanate, and the like isocyanate compounds, methanesulfonyl chloride, p-toluenesulfonyl chloride, and the like can be exemplified.

[0269] The introduction ratio of the capping agent having an anhydride group is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, and further preferably 5 to 20 mol% with respect to the total amount of the tetracarboxylic dianhydride component and the dicarboxylic acid component. The introduction ratio of the capping agent having an amino group is preferably in the range of 0.1 to 100 mol%, particularly preferably 5 to 90 mol% with respect to the diamine component. In addition, a plurality of different terminal groups can be introduced by allowing a plurality of capping agents to react.

[0270] [(D) component]

[0271] Next, an organic compound represented by the following general formula (1) of the (D) component of the present application is described.

[0272] [Chemical Formula 41]

[0273]

[0274] In the formula, T represents any one of the following general formulae (2) to (4), and W represents an alkyl group or an aryl group which can also be substituted with an alkoxy group having 4 to 15 carbon atoms.

[0275] [Chemical Formula 42]

[0276]

[0277] In the formula, V represents a divalent organic group, and * represents a bond.

[0278] [Chemical Formula 43]

[0279]

[0280] In the formula, 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.

[0281] [Chemical Formula 44]

[0282]

[0283] wherein Ar represents a substituted or unsubstituted aromatic ring structure, or a heterocyclic ring structure having a hetero atom, and * represents a bond.

[0284] wherein the above general formula (2) is preferably a structure represented by the following general formula (2-1).

[0285] [Chemical Formula 45]

[0286]

[0287] wherein R a and R b represent 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, and R a and R b may be bonded to each other and form a ring together with the carbon atom to which they are bonded. * represents a bond.

[0288] The above general formula (2) in the above general formula (1) as the component (D) is a desirable example of an organic compound or structure represented by the above general formula (2) or (2-1), and examples thereof include the structures of the following general formulae (2-2) and (2-3).

[0289] [Chemical Formula 46]

[0290]

[0291] wherein * represents a bond.

[0292] [Chemical Formula 47]

[0293]

[0294] wherein * represents a bond.

[0295] Next, an organic compound in which T in the above general formula (1) as the component (D) includes a structure represented by the following general formula (3) will be described.

[0296] [Chemical Formula 48]

[0297]

[0298] 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 in the case where Q is a halogen atom, and represents 1 in the case where Q is a nitro group. * represents a bond.

[0299] T in the above general formula (1) as the component (D) is preferably a structure represented by the following general formula (3-4) as the above general formula (3).

[0300] [Chemical Formula 49]

[0301]

[0302] in the formula, * represents a bond.

[0303] Further, the above general formula (3) is preferably a structure represented by the following formula (3-1) or (3-2).

[0304] [Chemical Formula 50]

[0305]

[0306] in the formula, * represents a bond.

[0307] [Chemical Formula 51]

[0308]

[0309] in the formula, * represents a bond.

[0310] (D) In the above general formula (1) of the component, T represented by the above general formula (3) is an organic compound represented by the following general formula (3-1) or (3-2), which can be cited as a further preferable example from the viewpoints of easiness in obtaining a raw material, safety of the compound, less toxicity, and the like.

[0311] If the above general formula (3) is a structure represented by the above general formula (3-1) or (3-2), the hydroxyl group of 4-nitrophenol, pentafluorophenol, which is an active esterification agent for promoting an imidization reaction, is protected with a tert-butyloxycarbonyl (Boc group) or a benzyloxycarbonyl protecting group (Z group) as described above, and it is possible to make the storage stability of a photosensitive resin composition containing a polyimide precursor resin good.

[0312] Then, an 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) is described.

[0313] [Chemical Formula 52]

[0314]

[0315] in the formula, Ar represents a substituted or unsubstituted aromatic ring structure or a heterocyclic structure having a hetero atom, and * represents a bond.

[0316] (D) In the above general formula (1) of the component, T, as a preferable structure of the above general formula (4), the following general formula (4-2) can be cited.

[0317] [Chemical Formula 53]

[0318]

[0319] in the formula, * represents a bond.

[0320] Further, in the above formula (1) of the component (D), T represented by the above formula (4) is preferably a structure represented by the following formula (4-1).

[0321] [Chemical Formula 54]

[0322]

[0323] in the formula, R d represents a linear, branched, or cyclic alkyl group having 1 to 15 carbons which can have a halogen atom, or an aryl group having 6 to 15 carbons, and k represents an integer of 0 to 4. * represents a bond.

[0324] As T in the above formula (1) of the component (D), a specific structure represented by the above formula (4-1) can be specifically exemplified by a structure represented by the following formula (4-3).

[0325] [Chemical Formula 55]

[0326]

[0327] in the formula, * represents a bond.

[0328] As T in the above formula (1) of the component (D), a structure represented by the above formula (4-3), an organic compound, is further preferable from the viewpoint of easiness in obtaining a raw material, and the viewpoint of the storage stability of the negative photosensitive resin composition of the present application containing the organic compound not easily deteriorating.

[0329] Next, W in the above formula (1) of the component (D) will be described. W in the above formula (1) of the component (D) is preferably a tert-butyl group. When W is a tert-butyl group, it represents a compound in which an organic group represented by formula (1) is protected with a tert-butyloxycarbonyl group (N-Boc group). The tert-butyloxycarbonyl group (N-Boc group) is deprotected in the range of 100°C to 150°C in the heating step of the hardening reaction, and an active esterification agent which is a hydroxyl compound capable of promoting the imide ring closure reaction is generated, and thus imidization at 200°C or lower can be performed.

[0330] Further, in this case, W in formula (1) of the component (D) is preferably a benzyl group. When W is a benzyl group, it represents a compound in which an organic compound represented by the above formula (1) is protected with a benzyloxycarbonyl protecting group (Z group). The benzyloxycarbonyl protecting group (Z group) is deprotected in the range of 120°C to 190°C in the heating step of the hardening reaction, and an active esterification agent which is a hydroxyl compound capable of promoting the imide ring closure reaction is generated, and thus imidization at 200°C or lower can be performed.

[0331] More desirable organic compounds represented by the above formula (1) can be exemplified by the following compounds.

[0332] [Chemical Formula 56]

[0333]

[0334] [Chemical Formula 57]

[0335]

[0336] The above organic compound as the (D) component of the negative-type photosensitive resin composition of the present application can preferably be used from the viewpoint of being able to easily obtain the organic compound or a raw material of the organic compound.

[0337] The above organic compound represented by the general formula (1) can be obtained, for example, by the method shown in the following reaction formula, but is not limited thereto.

[0338] [Chemical Formula 58]

[0339]

[0340] In the formula, T and W are the same as described above. A is a halogen atom or a group represented by the following formula (27).

[0341] [Chemical Formula 59]

[0342]

[0343] Here, the dotted line represents an atomic bond. W is the same as described above.

[0344] More specifically, when T of the above general formula (1) of the organic compound as the (D) component is the above general formula (2) or (2-1), it can be obtained by the method shown in the following reaction formula.

[0345] [Chemical Formula 60]

[0346]

[0347] In the formula, V, W, and A are the same as described above.

[0348] [Chemical Formula 61]

[0349]

[0350] In the formula, W, A, R a and R b are the same as described above.

[0351] Further, more specifically, when T of the above general formula (1) of the organic compound as the component (D) is the above general formula (3), (3-1) or (3-2), it can be obtained by the method shown in the following reaction formula.

[0352] [Chemical Formula 62]

[0353]

[0354] In the formula, Q, W and A are the same as described above.

[0355] [Chemical Formula 63]

[0356]

[0357] In the formula, Q, W and A are the same as described above.

[0358] [Chemical Formula 64]

[0359]

[0360] In the formula, W and A are the same as described above.

[0361] Further, more specifically, when T of the above general formula (1) of the organic compound as the component (D) is the above general formula (4), (4-1) or (4-2), it can be obtained by the method shown in the following reaction formula.

[0362] [Chemical Formula 65]

[0363]

[0364] In the formula, Ar, W, A are the same as described above.

[0365] [Chemical Formula 66]

[0366]

[0367] In the formula, W, A are the same as described above.

[0368] The organic compound of the above general formula (1) as the (D) component of the negative photosensitive resin composition of the present application, when the organic compound is one in which W represents a benzyl group, can be obtained by the reaction of the above general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4), and (25-4-1) of the hydroxyl compound of the above general formula (1) having a structure of T in the above reaction formula with a benzyloxy carbonyl halide (compound in which A of formula (26) in the above reaction formula represents a halogen atom, and W represents a benzyl group), or the reaction of the above general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4), and (25-4-1) of the hydroxyl compound of the above general formula (1) having a structure of T in the above reaction formula with a dibenzyl carbonate (compound in which A of formula (26) in the above reaction formula represents formula (27), and W represents a benzyl group).

[0369] The organic compound of the above general formula (1) as the (D) component of the negative photosensitive resin composition of the present application, when the organic compound is one in which W represents a benzyl group, can be obtained by the reaction of the above general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4), and (25-4-1) of the hydroxyl compound of the above general formula (1) having a structure of T in the above reaction formula with a benzyloxy carbonyl halide (compound in which A of formula (26) in the above reaction formula represents a halogen atom, and W represents a benzyl group), or the reaction of the above general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4), and (25-4-1) of the hydroxyl compound of the above general formula (1) having a structure of T in the above reaction formula with a dibenzyl carbonate (compound in which A of formula (26) in the above reaction formula represents formula (27), and W represents a benzyl group).

[0370] The organic compound of the above general formula (1) as the (D) component of the negative photosensitive resin composition of the present application, when the organic compound is one in which W represents a benzyl group, can be obtained by the reaction of the above general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4), and (25-4-1) of the hydroxyl compound of the above general formula (1) having a structure of T in the above reaction formula with a benzyloxy carbonyl halide (compound in which A of formula (26) in the above reaction formula represents a halogen atom, and W represents a benzyl group), or the reaction of the above general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4), and (25-4-1) of the hydroxyl compound of the above general formula (1) having a structure of T in the above reaction formula with a dibenzyl carbonate (compound in which A of formula (26) in the above reaction formula represents formula (27), and W represents a benzyl group).

[0371] The reaction to obtain the organic compound of the above general formula (1) as the (D) component of the negative photosensitive resin composition of the present application, in the case where the above general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4), and (25-4-1) of the hydroxyl compound having the T structure of the above general formula (1) in the above reaction formula is used with a halogenated carbonate, can be carried out by sequentially or simultaneously adding the above hydroxyl compound, the corresponding halogenated carbonate such as benzyl chlorocarbonate, 4-methoxybenzyl chlorocarbonate, a base such as triethylamine, pyridine, 2,6-lutidine, N,N-dimethylaniline, and the like, in a solvent such as dichloromethane, acetonitrile, diethyl ether, tetrahydrofuran, N,N-dimethylformamide, toluene, hexane, and the like, with cooling or heating, and the like, as necessary.

[0372] The reaction to obtain the organic compound of the above general formula (1) as the (D) component of the negative photosensitive resin composition of the present application, in the case where the above general formula (25), (25-2), (25-2-1), (25-3), (25-3-1), (25-3-2), (25-4), and (25-4-1) of the hydroxyl compound having the T structure of the above general formula (1) in the above reaction formula is used with a halogenated carbonate, can be carried out by sequentially or simultaneously adding the above hydroxyl compound, the corresponding halogenated carbonate such as benzyl chlorocarbonate, 4-methoxybenzyl chlorocarbonate, a base such as triethylamine, pyridine, 2,6-lutidine, N,N-dimethylaniline, and the like, in a solvent such as dichloromethane, acetonitrile, diethyl ether, tetrahydrofuran, N,N-dimethylformamide, toluene, hexane, and the like, with cooling or heating, and the like, as necessary.

[0373] The amount of the halogenated carbonate, the carbonate diester represented by (26) in the above reaction formula varies depending on the conditions, and for example, it is preferably 1.0 to 5.0 moles, and particularly preferably 1.0 to 2.0 moles, relative to 1 mole of the starting material of the above hydroxyl compound. The amount of the base varies depending on the conditions, and for example, it is preferably 0 to 5.0 moles, and particularly preferably 0 to 2.0 moles, relative to 1 mole of the starting material of the above hydroxyl compound. The reaction time, from the viewpoint of the yield, is expected to be completed by tracking the reaction by gas chromatography (GC), silica gel thin layer chromatography (TLC), and the like, and is usually about 0.5 to 24 hours. The organic compound of the above general formula (1) as the (D) component of the negative photosensitive resin composition of the present application can be obtained from the reaction mixture by a general aqueous treatment, and can be refined by following a conventional method such as distillation, chromatography, recrystallization, and the like, as necessary. Alternatively, sometimes the salt generated in the reaction can be separated by filtration, or the reaction solution can be directly subjected to refinement, without performing the aqueous post-treatment.

[0374] On the other hand, it is preferable that the organic compound of component (D) is contained in an amount of 1 to 10 parts by mass relative to 100 parts by mass of the aforementioned component (A). If the organic compound of component (D) is less than 10 parts by mass, the added organic compound of component (D) does not function as a plasticizer, does not cause thermal deformation, i.e., thermal flow, of the formed pattern, and does not impair the pattern formation. In addition, after curing, the glass transition point (Tg.) of the obtained cured film is not reduced. The glass transition point (Tg.) of the obtained cured film is required to be high because of the requirement for heat resistance in the step of manufacturing an electronic part using the obtained interlayer insulating film or surface protective film.

[0375] The negative photosensitive resin composition of the present application is composed of:

[0376] A negative photosensitive resin composition comprising:

[0377] (A) a high molecular compound having a polyimide precursor structure,

[0378] (C) a photopolymerization initiator,

[0379] (D) an organic compound represented by general formula (1), and

[0380] (E) a solvent.

[0381] The (A) high molecular compound having a polyimide precursor structure and the (D) organic compound represented by general formula (1) have been described above. Then, the (C) photopolymerization initiator will be described.

[0382] [(C) component]

[0383] As the (C) photopolymerization initiator, a compound conventionally used as a photopolymerization initiator for UV curing can be arbitrarily selected. For example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methylbenzophenone, dibenzyl ketone, benzophenone derivatives such as fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropio- phenone, 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone; benzil, benzil derivatives such as benzoin, benzoin methyl ether; oxime compounds such as 1-phenyl-1,2-butanedione-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-diphenylpropanetone-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetone-2-(O-benzoyl)oxime; N-aryl glycines such as N-phenylglycine; peroxides such as benzoyl peroxide; and aromatic bisimidazoles are preferable, but the present application is not limited to these. In addition, one of these compounds can be used alone or two or more of these compounds can be used in combination. Among the above (C) photopolymerization initiators, oxime compounds are more preferable from the viewpoint of sensitivity.

[0384] The blending amount of the (C) photopolymerization initiator is preferably 2 to 15 parts by mass, and more preferably 3 to 10 parts by mass, relative to 100 parts by mass of the polymer having a structural unit of a polyimide precursor of the present application based on the (A) base resin, from the viewpoint of sensitivity. By blending 0.1 parts by mass or more of the (C) photopolymerization initiator relative to 100 parts by mass of the (A) base resin, the sensitivity of the photosensitive resin composition is excellent, and on the other hand, by blending 20 parts by mass or less, the thick film curing property of the photosensitive resin composition is excellent.

[0385] [(E) component]

[0386] Next, the (E) solvent of the negative photosensitive resin composition of the present application will be described.

[0387] The solvent (E) is not particularly limited as long as it dissolves the base resin (A), the photopolymerization initiator (C), and the organic compound represented by the general formula (1) (D). Examples of the solvent (E) include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; 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, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, and γ-butyrolactone. One or more of these solvents can be used. In particular, ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, or a mixture thereof is preferred.

[0388] The amount of the solvent (E) is preferably 50 to 2,000 parts by mass, and particularly preferably 100 to 1,000 parts by mass, relative to 100 parts by mass of the total amount of the base resin (A) and the photopolymerization initiator (C).

[0389] [(B) Component]

[0390] Further, the negative photosensitive resin composition of the present application preferably contains (B) a polymerizable compound having two or more ethylenic unsaturated groups.

[0391] By including a crosslinking agent having two or more photopolymerizable unsaturated bonds in one molecule, as described above, the crosslinking of the (A) component based on photopolymerization at the exposed portion is promoted, and the contrast between the exposed portion and the unexposed portion is improved.

[0392] As the (B) polymerizable compound having 2 or more ethylenic unsaturated groups, a (meth)acrylic compound is preferable, and examples thereof include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate (number of ethylene glycol units: 2 to 20), polyethylene glycol dimethacrylate (number of ethylene glycol units: 2 to 20), poly(l,2-propylene glycol) diacrylate, poly(l,2-propylene glycol) dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolpropane tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, glycerol diacrylate, glycerol dimethacrylate, methylene bisacrylamide, N-hydroxymethyl acrylamide, ethylene glycol glycidyl ether-methacrylic acid adduct, glycerol glycidyl ether-acrylic acid adduct, bisphenol A glycidyl ether-acrylic acid adduct, bisphenol A glycidyl ether-methacrylic acid adduct, N,N'-bis(2-methacryloyloxyethyl)urea, and the like, but are not limited thereto.

[0393] The (B) polymerizable compound having 2 or more ethylenic unsaturated groups is preferably blended in a range of 1 to 100 parts by mass, and more preferably in a range of 3 to 50 parts by mass, relative to 100 parts by mass of the high molecular compound having a structural unit of a polyimide precursor of the present application. If the range of 1 to 100 parts by mass is deviated, the target effect is sometimes not obtained, or a bad influence on the development property is caused. Also, as the comonomer, one kind of compound can be used, or a plurality of kinds can be used in mixture.

[0394] [(F) Component]

[0395] The negative photosensitive resin composition of the present application can further contain, as the thermal crosslinking agent (F) component, one or two or more kinds of crosslinking agents selected from the group consisting of a formaldehyde or formaldehyde-alcohol-modified amino condensate, a phenol compound having 2 or more hydroxymethyl groups or alkoxyhydroxymethyl groups in one molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyphenol is substituted with a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyphenol or a hydroxyl group of a polyol is substituted with a substituent represented by the following formula (F-1), and a compound containing 2 or more nitrogen atoms having a glycidyl group represented by the following formula (F-2).

[0396] [Chemical Formula 67]

[0397]

[0398] wherein the dotted line indicates a bond of an atom, Rf is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and c is 1 or 2.

[0399] As the above-mentioned melamine condensate modified with formaldehyde or formaldehyde-alcohol, for example, a melamine condensate modified with formaldehyde or a urea condensate modified with formaldehyde or formaldehyde-alcohol can be given.

[0400] To prepare the melamine condensate modified with formaldehyde or formaldehyde-alcohol, for example, first, a melamine monomer is subjected to a hydroxymethylation and modification with formalin according to a known method, or further subjected to an alkoxylation and modification with an alcohol to obtain a modified melamine represented by the following general formula (23). Also, as the above-mentioned alcohol, a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms is preferable.

[0401] [Chem. 68]

[0402]

[0403] wherein R5, which can be the same or different, is a hydroxymethyl group, an alkoxymethyl group containing an alkoxyl group having 1 to 4 carbon atoms, or a hydrogen atom, but at least one is a hydroxymethyl group or the above-mentioned alkoxymethyl group.

[0404] As the above-mentioned R5, for example, a hydroxymethyl group, an alkoxymethyl group such as a methoxymethyl group, an ethoxymethyl group, and the like, and a hydrogen atom can be given.

[0405] As the above-mentioned modified melamine represented by the general formula (23), specifically, trimethoxymethyl monohydroxymethyl melamine, dimethoxymethyl monohydroxymethyl melamine, trihydroxymethyl melamine, hexahydroxymethyl melamine, hexamethoxymethyl melamine, and the like can be given. Then, the above-mentioned modified melamine represented by the general formula (23) or a polymer thereof (for example, an oligomer such as a dimer, a trimer, and the like) is subjected to an addition condensation polymerization with formaldehyde until a desired molecular weight is obtained according to a conventional method to obtain a melamine condensate modified with formaldehyde or formaldehyde-alcohol.

[0406] Further, the above-mentioned urea condensate modified with formaldehyde or formaldehyde-alcohol is prepared, for example, according to a known method by modifying a urea condensate having a desired molecular weight with formaldehyde by hydroxymethylation, or further modifying it with an alcohol by alkoxylation.

[0407] As the above-mentioned urea condensate modified with formaldehyde or formaldehyde-alcohol, for example, a methoxymethylated urea condensate, an ethoxymethylated urea condensate, a propoxymethylated urea condensate, and the like can be given.

[0408] Also, one or two or more of these modified melamine condensates and modified urea condensates can be used in mixture.

[0409] Then, as a phenol compound having 2 or more hydroxymethyl groups or alkoxyhydroxymethyl groups on average in 1 molecule, for example, (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethyl bisphenol A, compounds represented by the following formulae (F-3) to (F-8), and the like can be exemplified.

[0410] [Chemical Formula 69]

[0411]

[0412] Further, the above crosslinking agent can be used alone or in combination with two or more kinds.

[0413] On the other hand, as a compound in which the hydrogen atoms of the hydroxyl groups of a polyhydric alcohol are substituted with epoxypropyl groups, for example, a compound obtained by reacting the hydroxyl groups of bisphenol A, tris(4-hydroxyphenyl)methane, 1,1,1-tris(4-hydroxyphenyl)ethane with epichlorohydrin in the presence of a base. As a desirable example of a compound in which the hydrogen atoms of the hydroxyl groups of a polyhydric phenol are substituted with epoxypropyl groups, compounds represented by the following formulae (F-9) to (F-15) can be exemplified.

[0414] [Chemical Formula 70]

[0415]

[0416] In the formula, d is 2 ≤ d ≤ 3.

[0417] Further, as a compound other than the above formulae (F-9) to (F-15), preferable examples can include Epiclon 850-S, Epiclon HP-4032, Epiclon HP-7200, Epiclon HP-820, Epiclon HP-4700, Epiclon EXA-4710, Epiclon HP-4770, Epiclon EXA-859CRP, Epiclon EXA-4880, Epiclon EXA-4850, Epiclon EXA-4816, Epiclon EXA-4822 (all of which are trade names, manufactured by Dainippon Ink and Chemicals, Incorporated), RIKARESIN BPO-20E, RIKARESIN BEO-60E (both of which are trade names, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4000S, EP-4000L (all of which are trade names, manufactured by ADEKA Corporation), jER828EL, YX7105 (both of which are trade names, manufactured by Mitsubishi Chemical Corporation), and the like.

[0418] One or two of these compounds that replace the hydrogen atom of the hydroxyl group of the polyhydric phenol with a propylene oxide group (compounds that replace the hydrogen atom of the hydroxyl group of the polyhydric phenol with a propylene group) can be used as the crosslinking agent.

[0419] As a compound that replaces the hydrogen atom of the hydroxyl group of the polyhydric phenol with a substituent represented by the following formula (F-1), a compound represented by the following formula (F-16) that contains two or more of the substituents can be given.

[0420] [Chemical Formula 71]

[0421]

[0422] In the formula, the dotted line indicates a bond.

[0423] [Chemical Formula 72]

[0424]

[0425] In the formula, e is 1 ≤ e ≤ 3.

[0426] Further, as a compound other than the aforementioned formula (F-9) to formula (F-16), ideal examples can 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, ARON OXETANE series manufactured by Toagosei Co., Ltd., and the like.

[0427] On the other hand, as a compound that contains two or more of a nitrogen atom having a propylene oxide group represented by the following formula (F-2), a compound represented by the following formula (F-17) can be given.

[0428] [Chemical Formula 73]

[0429]

[0430] In the formula, the dotted line indicates a bond, Rf is a linear, branched, or cyclic alkyl group having a carbon number of 1 to 6, and c is 1 or 2.

[0431] [Chemical Formula 74]

[0432]

[0433] In the formula, L represents a linear, branched, or cyclic alkylene group having a carbon number of 2 to 12, or a divalent aromatic group. Also, L here is used only in the above formula.

[0434] As the compound represented by the above formula (F-17), for example, a compound represented by the following formula (F-18) to (F-21) can be given.

[0435] [Chemical Formula 75]

[0436]

[0437] On the other hand, as the compound containing two or more nitrogen atoms having a glycidyl group represented by the above formula (F-2), a compound represented by the following formula (F-22) or (F-23) can be preferably used.

[0438] [Chemical Formula 76]

[0439]

[0440] These compounds containing two or more nitrogen atoms having a glycidyl group represented by the above formula (F-2) can be used as one or two kinds as the crosslinking agent.

[0441] The strain of the epoxy ring is large, the reactivity is high, the oxetane ring is basic, and it is easy to bond with an acid. It is reported that the reactivity of cationic polymerization is significantly improved by combining an oxetanyl group on the epoxy group.

[0442] (F) component is a component that causes crosslinking reaction in post-hardening after pattern formation of the negative photosensitive resin composition of the present application, and further improves the strength of the hardened product. From the viewpoint of photo-hardening property and heat resistance, the weight average molecular weight of such (F) component is preferably 150 to 10,000, particularly preferably 200 to 3,000.

[0443] In the negative photosensitive resin composition of the present application, the blending amount of the (F) component is preferably 0.5 to 100 parts by mass, particularly preferably 1 to 80 parts by mass, with respect to 100 parts by mass of the (A) component.

[0444] [(G) component]

[0445] The negative photosensitive resin composition of the present application preferably further contains a (G) antioxidant. By containing the (G) component, the excessive crosslinking of the (A) component with each other or the (A) component with the (B) component at the time of patterning can be suppressed, and the contrast can be improved. In addition, by the rust-preventing effect on metal materials, the oxidation of the metal, the reduction of adhesion, and peeling that accompany the oxidation of the metal caused by moisture, a photoacid generator, a thermal acid generator, and the like from the outside can be suppressed.

[0446] If specific examples of the (G) antioxidant that can be used here are exemplified, a hindered phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant can be preferably exemplified. However, it is not limited to these. In addition, these (G) antioxidants can be used alone or in combination with two or more kinds.

[0447] In the specific examples of the above-mentioned (G) antioxidant, when a hindered phenol-based antioxidant is further exemplified, there can be mentioned pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan, Inc., Irganox 1010 (trade name)), thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan, Inc., Irganox 1035 (trade name)), octadecyl [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan, Inc., Irganox 1076 (trade name)), 1-octyl 3,5-di-tert-butyl-4-hydroxy-hydrocinnamate (manufactured by BASF Japan, Inc., Irganox 1135 (trade name)), 4,6-bis(octylthiomethyl-o-cresol) (BASF Japan, Inc., Irganox 1520L), Sumilizer GA80 (manufactured by Sumitomo Chemical Co., Ltd., trade name), ADK STAB AO-20 (manufactured by ADEKA Co., Ltd., trade name), ADK STAB AO-30 (manufactured by ADEKA Co., Ltd., trade name), ADK STAB AO-40 (manufactured by ADEKA Co., Ltd., trade name), ADK STAB AO-50 (manufactured by ADEKA Co., Ltd., trade name), ADK STAB AO-60 (manufactured by ADEKA Co., Ltd., trade name), ADK STAB AO-80 (manufactured by ADEKA Co., Ltd., trade name), ADK STAB AO-330 (manufactured by ADEKA Co., Ltd., trade name), a hindered phenol-based antioxidant described in International Publication No. 2017 / 188153, and the like.

[0448] In the specific examples of the above-mentioned (G) antioxidant, when a phosphorus-based antioxidant is further exemplified, there can be mentioned triphenyl phosphite, tris(methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tris(nonylphenyl) phosphite, tris(octylphenyl) phosphite, tridecyl poly(oxyethylene) phosphite, tris(cyclohexylphenyl) phosphite, tricyclohexyl phosphite, tris(decyl) thiophosphite, tris(isodecyl) thiophosphite, phenyl-bis(2-ethylhexyl) phosphite, phenyl-diisodecyl phosphite, tetradecyl poly(oxyethylene)-bis(ethylphenyl) phosphite, phenyl-dicyclohexyl phosphite, phenyl-diisooctyl phosphite, phenyl-di(tridecyl) phosphite, diphenyl-cyclohexyl phosphite, diphenyl-isooctyl phosphite, diphenyl-2-ethylhexyl phosphite, diphenyl-isodecyl phosphite, diphenyl-cyclohexylphenyl phosphite, diphenyl-(tridecyl) thiophosphite, and the like.

[0449] As specific examples of the above-mentioned (G) antioxidant, when a sulfur-based antioxidant is further exemplified, ADK STAB AO-412S (manufactured by ADEKA KK, trade name), AO-503S (manufactured by ADEKA KK, trade name), Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd., trade name), and the like can be given.

[0450] The sulfur-based antioxidant and the phosphorus-based antioxidant can be expected to have a decomposing effect on peroxide.

[0451] In addition, the content of the (G) antioxidant is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass, with respect to 100 parts by mass of the polymer of the (A) component. By having a content of 0.1 parts by mass or more, adhesion to a metal material can be improved, and peeling can be suppressed. In addition, by having a content of 10 parts by mass or less, the developability of the composition and the toughness of the hardened film are not deteriorated.

[0452] [(H) component]

[0453] The negative photosensitive resin composition of the present application preferably further contains a (H) silane compound. The negative photosensitive resin composition of the present application preferably contains a metal adhesion improver for improving adhesion to a metal material used in an electrode, a wiring, or the like, and as the metal adhesion improver, a silane compound or the like can be given.

[0454] As examples of the silane compound, the compounds described in paragraph 0167 of International Publication No. 2015-199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication No. 2011-080992, the compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and the compounds described in paragraph 0055 of International Publication No. 2014-097594 can be given. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358, it is preferable to use two or more different silane coupling agents.

[0455] The (H) silane compound that can be used here is not particularly limited, and is preferably one having an alkoxysilyl group. In addition, the following preferred specific examples are shown. γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, bis(2-hydroxyethyl)-3- aminopropyl-triethoxysilane, γ-aminopropyltrimethoxysilane, γ- aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, bis(2-hydroxyethyl)-3- aminopropyltriethoxysilane, triethoxysilylpropylethylcarbamate, 3- (triethoxysilyl)propyl succinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3- triethoxysilyl-N-(l,3-dimethylbutylidene)propylamine, a silane compound containing an amide group described in Japanese Patent No. 6414060, a silane compound containing a thioureido group described in International Publication No. 2016 / 140024 and Japanese Patent No. 5987984, a silane compound containing a mercaptan group described in Japanese Patent Application Publication No. 2017-044964, and the like. However, these are not limiting. Furthermore, one of these (H) silane compounds can be used alone or two or more of these (H) silane compounds can be used in combination.

[0456] Also, the silane coupling agent is preferably a compound represented by the following formulae (H-1) to (H-7).

[0457] [Chemical Formula 77]

[0458]

[0459] The content of the (H) silane compound of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and further preferably in the range of 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymer having a structural unit of a polyimide precursor used in the negative photosensitive resin composition of the present application. By being equal to or greater than the lower limit of the foregoing range, the adhesion of the hardened film after the hardening step to the metal film becomes good, and by being equal to or less than the upper limit of the foregoing range, the heat resistance and mechanical properties of the hardened film after the hardening step become good. The (H) silane compound of the metal adhesion improver can be only one, or two or more. In the case of using two or more, the total amount is preferably in the foregoing range.

[0460] [(I) component]

[0461] In the present application, it is preferable to further contain (I) a polymerization inhibitor. As (I) a polymerization inhibitor, in order to improve the viscosity of the composition solution at the time of storage, the stability of photosensitivity, a thermal polymerization inhibitor can be added. As the thermal polymerization inhibitor, known thermal polymerization inhibitors can be used as long as the gist of the present application is not violated. As an example, mention can be made of hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, and the like. The amount of (I) a polymerization inhibitor added in the negative photosensitive resin composition of the present application is preferably in the range of 0.005 to 5 parts by mass with respect to 100 parts by mass of the high molecular compound having a structural unit of a polyimide precursor used in the negative photosensitive resin composition of the present application.

[0462] [Others]

[0463] In addition, the negative photosensitive resin composition of the present application can further contain components other than (A) a polymer having a polyimide precursor structure, (C) a photopolymerization initiator, and (D) an organic compound represented by general formula (1). As the other components, mention can be made of (J) a sensitizer, (K) a migration inhibitor, (L) a surfactant, and the like.

[0464] As the (J) sensitizer, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal) cyclopentanone, 2,6-bis(4'-diethylaminobenzal) cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminobenzal indanone, p-dimethylaminobenzal indanone, 2-(p-dimethylaminophenyl)styryl)benzothiazole, 2-(p-dimethylaminophenyl)vinyl)benzothiazole, 2-(p-dimethylaminophenyl)vinyl)isothiazolocinoline, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethyloxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethyloxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyl diethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene can be given. They can be used alone or in combination of, for example, 2 to 5 kinds.

[0465] Further, the blending amount of the (J) sensitizer is preferably set to 0.05 parts by mass to 20 parts by mass, more preferably to 0.1 parts by mass to 10 parts by mass, with respect to 100 parts by mass of the polymer of the (A) component.

[0466] The negative photosensitive resin composition of the present application preferably further contains a (K) migration inhibitor. By containing the migration inhibitor, migration of metal ions from the metal layer (metal wiring) into the hardening resin composition layer can be effectively inhibited.

[0467] The migration inhibitor (K) is not particularly limited, and examples include compounds having a heterocyclic ring (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, and 6H-pyran ring), thiourea-based compounds, and compounds having a mercapto group, hindered phenol-based compounds, salicylic acid derivative-based compounds, and hydrazide derivative-based compounds. Particularly preferably, a triazole-based compound such as 1,2,4-triazole or benzotriazole, or a tetrazole-based compound such as 1H-tetrazole or 5-phenyltetrazole is used.

[0468] As the migration inhibitor (K), an ion-trapping agent that traps anions such as halide ions can also be used.

[0469] As other migration inhibitors, the antirust agent described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Publication No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015 / 199219, and the like can be used.

[0470] As specific examples of the migration inhibitor, the following compounds can be given.

[0471] [Chemical Formula 78]

[0472]

[0473] In the case where the negative-type photosensitive resin composition of the present application has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and further more preferably 0.1 to 1.0% by mass, relative to 100 parts by mass of the high molecular compound having a structural unit of a polyimide precursor used in the negative-type photosensitive resin composition of the present application.

[0474] The migration inhibitor can be only one kind, or two or more kinds. In the case where the migration inhibitor is two or more kinds, the total amount is preferably within the above range.

[0475] As the surfactant (L), a nonionic surfactant is preferable, and examples include fluorine-based surfactants, and specifically, perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkyl amine oxide, fluorine-containing organosiloxane-based compounds, and the like.

[0476] They can use commercially available products, for example, Fluorad "FC-4430" (Sumitomo 3M (K.K.), Surflon "S-141" and "S-145" (both by Asahi Glass (K.K.)), Unidyne "DS-401", "DS-4031", and "DS-451" (all by Daikin Industries (K.K.)), Megafac "F-8151" (DIC (K.K.)), "X-70-093" (Chiba Flour Industries (K.K.)), and the like. Among them, Fluorad "FC-4430" (Sumitomo 3M (K.K.)) and "X-70-093" (Chiba Flour Industries (K.K.)) are preferable.

[0477] In addition, the blending amount of the (L) surfactant is preferably 0.01 to 0.05 parts by mass with respect to 100 parts by mass of the polymer of the (A) component. When in this range, there is an advantage that the coatability to the substrate can be improved without impairing the patterning performance and the characteristics of the hardened film.

[0478] [Pattern forming method]

[0479] Then, a pattern forming method of the negative photosensitive resin composition of the present application will be described.

[0480] In the present application, a pattern forming method is provided, characterized by comprising:

[0481] (1) a step of applying the photosensitive resin composition of any one of the above on a substrate to form a photosensitive material film;

[0482] (2) then, a step of exposing the photosensitive material film to high-energy rays or electron beams with a wavelength of 190 to 500 nm through a photomask after heat treatment; and

[0483] (3) a step of developing using a developing solution of an organic solvent after irradiation.

[0484] The negative photosensitive resin composition of the present application can be performed using a known photolithography technique, for example, can be applied to a silicon wafer or a SiO2 substrate, a SiN substrate, or a substrate on which a pattern of a copper wire or the like is formed, using a spin coating method, and pre-baking is performed under conditions of 80°C to 130°C for 50 seconds to 600 seconds or so, to form a resist film with a thickness of 1 μm to 50 μm, preferably 1 μm to 30 μm, and further preferably 5 μm to 20 μm. Then, a mask for forming a target pattern is shielded on the above resist film, and high-energy rays with a wavelength of 190 to 500 nm, such as i-rays or g-rays, are irradiated so that the exposure amount becomes 1 to 5,000 mJ / cm 2 2,000 mJ / cm 2 2,000 mJ / cm

[0485] Then, development is performed. The above-mentioned negative photosensitive resin composition of the present application is suitable for organic solvent development. As the organic solvent which can be used for the ideal organic solvent development, the solvent used when the photosensitive resin composition of the present application is prepared can be used. For example, ketones such as cyclohexanone, cyclopentanone, and further glycols such as propylene glycol monomethyl ether are preferable. The development can be performed by a general method such as a spraying method, an immersion method, and the like, and immersion in a developing solution. Then, as necessary, washing, rinsing, drying, and the like are performed, and a resist film having a desired pattern can be obtained.

[0486] In addition, the obtained film having a pattern is subjected to post-hardening using an oven, a hot plate, at a temperature of 100 to 300°C, preferably 150 to 300°C, and further preferably 180 to 250°C. If the post-hardening temperature is 100 to 300°C, the cross-linking density of the film of the photosensitive resin composition can be increased, and the remaining volatile components can be removed, which is preferable in terms of adhesion to a substrate, heat resistance or strength, and further electrical properties. Moreover, the post-hardening time can be set to 10 minutes to 10 hours.

[0487] The thus obtained hardened film is excellent in adhesion to a substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance, and is also excellent in reliability as a protective film for a semiconductor element, and in particular, can prevent the generation of cracks during a temperature cycle test, and is suitable for use as a protective film for an electrical / electronic part, a semiconductor element, and the like.

[0488] That is, the present application provides an interlayer insulating film or a surface protective film composed of a hardened film hardened from the above-mentioned negative photosensitive resin composition.

[0489] The above-mentioned protective film is effective in an insulating film for a semiconductor element including a rewiring application, an insulating film for a multilayer printed board, a solder resist film, a cover film application, and the like, due to its heat resistance, chemical resistance, and insulating properties.

[0490] Further, the present application provides an electronic part having the above-mentioned interlayer insulating film or the above-mentioned surface protective film.

[0491] Such an electronic part is excellent in reliability due to the provision of a protective film (interlayer insulating film or surface protective film) having heat resistance, chemical resistance, and insulating properties.

[0492] [Examples]

[0493] Hereinafter, the present application will be specifically described using synthesis examples, examples, and comparative examples, but the present application is not limited to the following examples.

[0494] I. Synthesis of a high molecular compound

[0495] The chemical structural formula and name of the compound used in the following synthesis example of the high molecular compound used in the negative photosensitive resin composition of the present application are shown below.

[0496] [Chemical Formula 79]

[0497]

[0498] ODA 4,4'-oxydianiline

[0499] s-ODPA 3,3',4,4'-oxydiphthalic dianhydride

[0500] s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride

[0501] [Synthesis Example 1] Synthesis of tetracarboxylic diester compound (X-1)

[0502] In a 3L flask equipped with a stirrer and a thermometer, 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA) 100 g (322 mmol), triethylamine 65.2 g (644 mmol), N,N-dimethyl-4-aminopyridine 39.3 g (322 mmol), γ-butyrolactone 400 g were added, and while stirring at room temperature, hydroxyethyl methacrylate (HEMA) 83.8 g (644 mmol) was added dropwise, followed by stirring at room temperature for 24 hours. Then, 10% aqueous hydrochloric acid solution (370 g) was added dropwise at ice cold to terminate the reaction. To the reaction solution, 4-methyl-2-pentanone 800 g was added, and after separating the organic layer, it was washed with water 600 g six times. The solvent of the obtained organic layer was distilled off to obtain tetracarboxylic diester compound (X-1) 180 g of the following structure.

[0503] [Chemical Formula 80]

[0504]

[0505] [Synthesis Example 2] Synthesis of tetracarboxylic diester compound (X-2)

[0506] In Synthesis Example 1, 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA) was replaced with 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) 94.8 g (322 mmol), and otherwise, tetracarboxylic diester compound (X-2) 172 g of the following structure was obtained in the same formulation.

[0507] [Chemical Formula 81]

[0508]

[0509] [Synthesis Example 3] Synthesis of polyimide precursor (A-1)

[0510] In a 1 L flask equipped with a stirrer and a thermometer, 44.0 g (77.1 mmol) of (X-1) and 176 g of N-methyl-2-pyrrolidone were added and dissolved by stirring at room temperature. Then, 18.8 g (158.1 mmol) of thionyl chloride was added dropwise under ice cooling so that the temperature of the reaction solution was kept below 10°C, and after the completion of the dropwise addition, stirring was continued for 2 hours under ice cooling. Then, a solution in which 14.4 g (71.7 mmol) of 4,4'-diaminodiphenyl ether (ODA) and 25.0 g (316.2 mmol) of pyridine were dissolved in 70 g of N-methyl-2-pyrrolidone was added dropwise under ice cooling so that the temperature of the reaction solution was kept below 10°C. After the completion of the dropwise addition, the temperature was returned to room temperature, and the reaction solution was added dropwise with stirring in 3 L of water, and the precipitate was separated by filtration, washed with water, and dried under reduced pressure at 40°C for 48 hours, to thereby obtain a polyimide precursor (A-1). The molecular weight of the polymer was measured by GPC using DMF as an eluent at a temperature of 40°C, and the result was a weight average molecular weight of 24,000 in terms of polystyrene.

[0511] [Synthesis Example 4] Synthesis of a polyimide precursor (A-2)

[0512] A polyimide precursor (A-2) was obtained by the same method as described above, except that (X-1) 42.8 g (77.1 mmol) in Synthesis Example 3 was replaced by (X-2). The molecular weight of the polymer was measured by GPC using DMF as an eluent at a temperature of 40°C, and the result was a weight average molecular weight of 23,000 in terms of polystyrene.

[0513] II. (D) Component Organic Compound

[0514] In the synthesis example of the (D) component organic compound used in the negative photosensitive resin composition of the present application, the compounds used are shown below.

[0515] (D-2) N-hydroxyphthalimide

[0516] (D-3) N-hydroxy-5-norbornene-2,3-dicarboxylic imide

[0517] (D-4) N-hydroxytetrachlorophthalimide

[0518] (D-5) N,N'-dihydroxyphthalimide

[0519] (D-6) 4-nitrophenol

[0520] (D-7) pentafluorophenol

[0521] (D-8) 1 -hydroxybenzotriazole

[0522] (D-9) 1 -hydroxy-6-(trifluoromethyl)benzotriazole

[0523] [Synthesis Example 5] Synthesis of N-(tert-butoxycarbonyloxy)-5-norbornene-2,3-dicarboxylic imide (D-3-1)

[0524] In a 300 ml flask equipped with a reflux condenser, a stirrer, and a thermometer, 62 mg (0.51 mmol) 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. This was added to a 100 mL solution of acetonitrile of 4.48 g (25.0 mmol) of (D-3) N-hydroxy-5-norbornene-2,3-dicarboxylic imide. Then, it was stirred for 12 hours at 25°C. After the reaction was completed, the reaction solution was poured into 200 mL of cold water, and the organic layer was extracted with 30 mL of ethyl acetate three times. The organic layer was further washed with 50 mL of cold water three times, and then dried over magnesium sulfate, followed by concentration under reduced pressure, and crystallization using petroleum ether to obtain N-(tert-butoxycarbonyloxy)-5-norbornene-2,3-dicarboxylic imide (D-3-1) of the following structure (5.31 g, yield 76.0%).

[0525] [Chem. 82]

[0526]

[0527] (D-3-1) N-(tert-butoxycarbonyloxy)-5-norbornene-2,3-dicarboxylic imide

[0528] [Synthesis Example 6] Synthesis of N-(tert-butoxycarbonyloxy)-tetrachlorophthalic imide (D-4-1)

[0529] (D-3) N-hydroxy-5-norbornene-2,3-dicarboxylic imide in Synthesis Example 5 was replaced with (D-4) N-hydroxy tetrachlorophthalic imide 7.52 g, and the reaction was carried out in the same manner to obtain N-(tert-butoxycarbonyloxy)-tetrachlorophthalic imide (D-4-1) of the following structure (7.15 g, yield 71.5%).

[0530] [Chem. 83]

[0531]

[0532] (D-4-1) N-(tert-butoxycarbonyloxy)-tetrachlorophthalic imide

[0533] [Synthesis Example 7] Synthesis of N,N'-di(tert-butoxycarbonyloxy)pyromellitic imide (D-5-1)

[0534] (D-3) N-hydroxy-5-norbornene-2,3-dicarboxamide in Synthetic Example 5 was replaced with (D-5) N,N'-dihydroxyphthalimide 6.18 g, and di-tert-butyl dicarbonate 13.10 g (60.0 mmol) was set, and the reaction was carried out in the same manner to obtain N,N'-di(tert-butoxycarbonyloxy)phthalimide (D-5-1) (9.03 g, 70.1% yield) of the following structure.

[0535] [Chem. 84]

[0536]

[0537] (D-5-1) N,N'-di(tert-butoxycarbonyloxy)phthalimide

[0538] [Synthesis Example 8] Synthesis of tert-butyl-4-nitrophenyl carbonate (D-6-1)

[0539] (D-3) N-hydroxy-5-norbornene-2,3-dicarboxamide in Synthetic Example 5 was replaced with (D-6) 4-nitrophenol 3.48 g, and the reaction was carried out in the same manner to obtain tert-butyl-4-nitrophenyl carbonate (D-6-1) (5.31 g, 88.8% yield) of the following structure.

[0540] [Chem. 85]

[0541]

[0542] (D-6-1) tert-butyl-4-nitrophenyl carbonate

[0543] [Synthesis Example 9] Synthesis of tert-butyl-2,3,4,5,6-pentafluorophenyl carbonate (D-7-1)

[0544] (D-3) N-hydroxy-5-norbornene-2,3-dicarboxamide in Synthetic Example 5 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) (5.34 g, yield 75.2%) of the following structure.

[0545] [Chem. 86]

[0546]

[0547] (D-7-1) tert-butyl-2,3,4,5,6-pentafluorophenyl carbonate

[0548] [Synthesis Example 10] Synthesis of 1-(tert-butoxycarbonyloxy)-benzotriazole (D-8-1)

[0549] (D-3) N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide in Synthetic Example 5 was replaced with (D-8) 1-hydroxybenzotriazole 3.38 g, and the reaction was carried out in the same manner to obtain 1-(tert-butoxycarbonyloxy)-benzotriazole (D-8-1) (4.06 g, 69.0% yield) of the following structure.

[0550] [Chem. 87]

[0551]

[0552] (D-8-1) 1-(tert-butoxycarbonyloxy)-benzotriazole

[0553] [Synthesis Example 11] Synthesis of 1-(tert-butoxycarbonyloxy)-6-(trifluoromethyl)benzotriazole (D-9-1)

[0554] (D-3) N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide in Synthetic Example 5 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) (5.17 g, yield 68.2%) of the following structure.

[0555] [Chem. 88]

[0556]

[0557] (D-9-1) 1-(tert-butoxycarbonyloxy)-6-(trifluoromethyl)benzotriazole

[0558] [Synthesis Example 12] Synthesis of N-(benzyloxycarbonyloxy)phthalimide (D-2-2)

[0559] In a 300 ml flask equipped with a reflux condenser, a stirrer, and a thermometer, 4.26 g (25.0 mmol) of benzyl chloroformate was added dropwise to a mixed solution of 51 mg (0.51 mmol) of triethylamine, and 8.17 g (50.0 mmol) of (D-2) N-hydroxyphthalimide, 70 g of tetrahydrofuran at 0°C, and then stirred at 50°C for 20 hours. After the completion of the reaction, the reaction solution was poured into 200 mL of cold water, and the organic layer was extracted with 30 mL of ethyl acetate three times. The organic layer was further washed with 50 mL of cold water three times, and dried with magnesium sulfate, and then concentrated under reduced pressure, and crystallized using petroleum ether to obtain N-(benzyloxycarbonyloxy)-phthalimide (D-2-2) (6.03 g, yield 81.2%) of the following structure.

[0560] [Chem. 89]

[0561]

[0562] (D-2-2) N-(benzyloxycarbonyloxy)-phthalimide

[0563] [Synthesis Example 13] Synthesis of N-(benzyloxycarbonyloxy)-5-norbornene-2,3-dicarboxylic imide (D-3-2)

[0564] (D-2) N-hydroxyphthalimide in the synthesis example 12 to (D-3) N-hydroxy-5-norbornene-2,3-dicarboxylic imide 4.48 g, and the reaction was carried out in the same manner to obtain N-(benzyloxycarbonyloxy)-5-norbornene-2,3-dicarboxylic imide (D-3-2) of the following structure (6.18 g, yield 78.9 %).

[0565] [Chem. 90]

[0566]

[0567] (D-3-2) N-(benzyloxycarbonyloxy)-5-norbornene-2,3-dicarboxylic imide

[0568] [Synthesis Example 14] Synthesis of N-(benzyloxycarbonyloxy)-tetrachlorophthalimide (D-4-2)

[0569] (D-2) N-hydroxyphthalimide in the synthesis example 12 to (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) of the following structure (6.78 g, yield 62.3 %).

[0570] [Chem. 91]

[0571]

[0572] (D-4-2) N-(benzyloxycarbonyloxy)-tetrachlorophthalimide

[0573] [Synthesis Example 15] Synthesis of N,N'-di(benzyloxycarbonyloxy)pyromellitic imide (D-5-2)

[0574] (D-2) N-hydroxyphthalimide in the synthesis example 12 to (D-5) N,N'-dihydroxypyromellitic imide 6.18 g, and the reaction was carried out in the same manner with benzyl chloroformate 10.23 g (60.0 mmol) to obtain N,N'-di(benzyloxycarbonyloxy)pyromellitic imide (D-5-2) of the following structure (7.52 g, yield 58.4 %).

[0575] [Chem. 92]

[0576]

[0577] (D-5-2) N,N'-Bis(benzyloxycarbonyloxy)phthalimide

[0578] [Synthesis Example 16] Synthesis of benzyloxy-4-nitrophenyl carbonate (D-6-2)

[0579] (D-2) N-hydroxyphthalimide in Synthesis Example 12 was replaced with (D-6) 4-nitrophenol 3.48 g, and the reaction was carried out in the same manner to obtain benzyloxy-4-nitrophenyl carbonate (D-6-2) of the following structure (5.85 g, yield 85.6%).

[0580] [Chem. 93]

[0581]

[0582] (D-6-2) Benzyloxy-4-nitrophenyl carbonate

[0583] [Synthesis Example 17] Synthesis of benzyloxy-2,3,4,5,6-pentafluorophenyl carbonate (D-7-2)

[0584] (D-2) N-hydroxyphthalimide in Synthesis Example 12 was replaced with (D-7) pentafluorophenol 4.60 g, and the reaction was carried out in the same manner to obtain benzyloxy-2,3,4,5,6-pentafluorophenyl carbonate (D-7-2) of the following structure (4.77 g, yield 60.0%).

[0585] [Chem. 94]

[0586]

[0587] (D-7-2) Benzyloxy-2,3,4,5,6-pentafluorophenyl carbonate

[0588] [Synthesis Example 18] Synthesis of 1-(benzyloxycarbonyloxy)-benzotriazole (D-8-2)

[0589] (D-2) N-hydroxyphthalimide in Synthesis Example 12 was replaced with (D-8) 1-hydroxybenzotriazole 3.38 g, and the reaction was carried out in the same manner to obtain 1-(benzyloxycarbonyloxy)-benzotriazole (D-8-2) of the following structure (4.13 g, yield 61.3%).

[0590] [Chem. 95]

[0591]

[0592] (D-8-2) 1-(Benzyloxycarbonyloxy)-benzotriazole

[0593] [Synthesis Example 19] Synthesis of 1-(benzyloxycarbonyloxy)-6- (trifluoromethyl)benzotriazole (D-9-2)

[0594] (D-2) N-hydroxyphthalimide in Synthesis Example 12 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-(benzyloxycarbonyloxy)-6-(trifluoromethyl)benzotriazole (D-9-2) of the following structure (5.43 g, yield 64.4%).

[0595] [Chemical 96]

[0596]

[0597] (D-9-2) 1-(benzyloxycarbonyloxy)-6-(trifluoromethyl)benzotriazole

[0598] Further, (D-1-1) N-(tert-butoxycarbonyloxy)succinimide shown in the following structural formula was used as a commercially available reagent (Fuji Photo Film and Otsuka Pharmaceutical Co., Ltd.).

[0599] [Chemical 96]

[0600]

[0601] (D-1-1) N-(tert-butoxycarbonyloxy)succinimide

[0602] Further, (D-1-1) N-(tert-butoxycarbonyloxy)succinimide shown in the following structural formula was used as a commercially available reagent (Fuji Photo Film and Otsuka Pharmaceutical Co., Ltd.).

[0603] (D-2-1) N-(tert-butoxycarbonyloxy)phthalimide

[0604] (D-1-2) N-(benzyloxycarbonyloxy)succinimide

[0605] A commercially available reagent (Tokyo Chemical Industry Co., Ltd.) was used.

[0606] [Chemical 96]

[0607]

[0608] (D-2-1) N-(tert-butoxycarbonyloxy)phthalimide

[0609] [Chemical 96]

[0610]

[0611] (D-1-2) N-(benzyloxycarbonyloxy)succinimide

[0612] III. Imide ring closure temperature

[0613] In the above, 100 parts by weight of the synthetic high molecular compound (A-1), 5 parts by weight of the organic compound (D-1-1) to (D-9-2) of the component (D) shown in Table 1 (Example 1) to (Example 18) obtained above, and 4.0 parts by weight of the photopolymerization initiator (C-1): N-1919 manufactured by ADEKA (K.K.) were dissolved in γ-butyrolactone (hereinafter referred to as GBL) as a solvent. Then, microfiltration was performed using a 1.0-μm Teflon (registered trademark) filter, and a negative photosensitive resin composition was prepared. In addition, a composition in which the organic compound of the component (D) was not added was prepared as a comparative example.

[0614] Then, 5 mL of the obtained composition solution was dispensed onto a silicon substrate, and coating was performed by rotating the substrate, that is, by a spin coating method. Then, pre-baking at 100°C for 3 minutes was performed on a hot plate. The rotation speed at the time of coating was adjusted so that the final film thickness after pre-baking would be 0.9 μm to 1.2 μm.

[0615] With respect to the composition film on the coated silicon substrate, whole-surface exposure using i-rays was performed at an exposure amount of 600 mJ using an i-ray stepper NSR-2205i11 manufactured by Nikon Corporation.

[0616] After the obtained hardened film was heated at every 10°C interval for 1 hour from 100°C to 250°C, the absorption intensity obtained by infrared spectroscopy at each temperature was measured using the following FT-IR. Also, after the obtained hardened film was heated at 300°C for 1 hour, the absorption intensity was similarly measured.

[0617] FT-IR Nicolet iN10 MX (Thermo Fisher Scientific, Inc.)

[0618] In the composition film, if the high molecular compound of the polyimide precursor undergoes ring closure reaction to polyimide, a C-N bond is newly formed, and thus the absorption intensity at 1379 cm -1 from C-N stretching motion in the IR spectrum increases. On the other hand, since the C-C double bond of the benzene ring does not change after imidization, the absorption intensity at 1552 cm -1 from C-C stretching motion of the benzene ring in the IR spectrum does not change. The absorption intensity at 1552 cm -1 from C-C stretching motion of the benzene ring serves as an internal standard, and the absorption intensity at 1379 cm -1 from C-N stretching motion can be expressed as the degree of ring closure reaction to imide, that is, the imidization rate at each temperature, by the following formula (30). Also, the degree of imidization at each temperature can be compared relatively.

[0619] [Formula 1]

[0620]

[0621] The imidization rate of the hardened film after heating at 300°C for 1 hour, calculated by the aforementioned formula (30), can be set as the ring-closing reaction of the polymeric compound of the polyimide precursor to polyimide has been completely performed. In the case where the imidization rate of the hardened film calculated by changing the temperature is equal to the imidization rate of the hardened film at the aforementioned 300°C, the aforementioned temperature can be indicated as the temperature that can completely perform the imidization ring-closing reaction of the polyimide precursor of the composition film.

[0622] In the hardened film of the photosensitive resin composition in which the (D) component organic compound (D-1-1) to (D-9-2) of the following Table 1 was added in (Example 1) to (Example 18) below, the lowest temperature equal to the imidization rate of the hardened film after heating at 300°C for 1 hour was indicated as the imidization ring-closing temperature of the composition film.

[0623] [Table 1]

[0624] (D) component organic compound Imide ring closure temperature Example 1 D-1-1 190℃ Example 2 D-2-1 190℃ Example 3 D-3-1 190℃ Example 4 D-4-1 190℃ Example 5 D-5-1 190℃ Example 6 D-6-1 180℃ Example 7 D-7-1 200℃ Example 8 D-8-1 200℃ Example 9 D-9-1 200℃ Example 10 D-1-2 190℃ Example 11 D-2-2 190℃ Example 12 D-3-2 190℃ Example 13 D-4-2 190℃ Example 14 D-5-2 190℃ Example 15 D-6-2 180℃ Example 16 D-7-2 200℃ Example 17 D-8-2 200℃ Example 18 D-9-2 200℃ Comparative Example 1 No (D) component organic compound 230℃

[0625] As shown in the above Table 1, the (D) component organic compound of the present application can promote the imidization reaction of the polymeric compound containing the polyimide precursor structure, and can perform the imidization ring-closing reaction at a low temperature, i.e., 200°C or less.

[0626] IV. Preparation of Photosensitive Resin Composition

[0627] The polymeric compound containing the polyimide precursor obtained in the above Synthesis Example 3 to Synthesis Example 4 was used as a base resin, and the (D) component organic compound of the present application prepared above was prepared into a resin composition of 35 mass% in terms of resin in the composition and blending amount described in Table 2 to Table 5. Then, after stirring, mixing, and dissolving, microfiltration was performed by a Telflon (registered trademark) 1.0 μm filter to obtain a photosensitive resin composition. In the table, GBL of the solvent indicates γ-butyrolactone.

[0628] [Table 2]

[0629]

[0630] [Table 3]

[0631]

[0632]

[0633] [Table 4]

[0634]

[0635] [Table 5]

[0636]

[0637]

[0638] The photosensitive resin compositions 1 to 18, 21 to 23 (Examples 19 to 39) shown in Tables 2 to 4 are negative photosensitive resin compositions according to the present application.

[0639] The comparative photosensitive resin compositions 24 to 32 (Comparative Examples 2 to 10) shown in Table 5 are negative photosensitive resin compositions to which an unprotected organic compound is added, the aforementioned unprotected organic compound being different from the organic compound used in the negative photosensitive resin composition according to the present application in that a hydroxyl compound to be an active esterification agent is protected with a tert-butoxycarbonyl group (N-Boc group) or is protected with a benzyloxycarbonyl protecting group (Z group).

[0640] In Table 5, the compound of the comparative photosensitive resin compositions 24 to 32 (Comparative Examples 2 to 10) which is an unprotected hydroxyl compound to be an active esterification agent is (D-2) to (D-9) used in the aforementioned Synthesis Examples 5 to 19, and (D-1) is N-hydroxysuccinimide.

[0641] The comparative photosensitive resin composition 33 (Comparative Example 11) is a composition to which no organic compound used in the negative photosensitive resin composition according to the present application is added.

[0642] In Tables 2 to 5, the details of the polymerizable compound having two or more ethylenic unsaturated groups (B-1), the photopolymerization initiator (C-1), the thermal crosslinking agent (F-1), (F-2), the antioxidant (G-1), the silane compound (H-1), and the polymerization inhibitor (I-1) are as described below. In addition, parts by weight is the same meaning as parts by mass.

[0643] Photopolymerization initiator (C-1): N-1919 manufactured by ADEKA Co., Ltd.

[0644] Polymerizable compound having two or more ethylenic unsaturated groups (B-1): tetraethylene glycol dimethacrylate

[0645] Thermal crosslinking agent (F-1):

[0646] [Chemical 100]

[0647]

[0648] Thermal crosslinking agent (F-2):

[0649] Epoxy resin: EP4000L manufactured by ADEKA Co., Ltd.

[0650] Antioxidant (G-1):

[0651] Hindered phenol-based antioxidant: Sumilizer GA-80 manufactured by Sumitomo Chemical Co., Ltd.

[0652] Silane compound (H-1):

[0653] Amino silane coupling agent: KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.

[0654] Polymerization inhibitor (I-1): 2-nitroso-1-naphthol (reagent: Tokyo Chemical Industry Co., Ltd.)

[0655] V. Pattern formation

[0656] After 5 mL of the above-described photosensitive resin compositions 1 to 18 and 21 to 23, and comparative photosensitive resin compositions 24 to 33 was dispensed on a silicon substrate, coating was performed by rotating the substrate, that is, by a spin coating method, in a manner such that the film thickness after post-hardening performed after pattern formation became 5 μm. That is, the film thickness reduction after the post-hardening step was preliminarily investigated, and the rotation speed at the time of coating was adjusted.

[0657] Then, pre-baking was performed at 100°C for 3 minutes on a hot plate. Then, i-ray exposure and pattern formation were performed using an i-ray stepper NSR-2205i11 manufactured by Nikon Corporation. In the pattern formation, a positive pattern mask and a negative pattern mask were appropriately used in conjunction with the photosensitive resin composition. The mask had a pattern capable of forming holes arranged in a 1:1 aspect ratio of 20 μm, and was capable of forming hole patterns at intervals of every 10 μm from 50 μm to 20 μm, every 5 μm from 20 μm to 10 μm, and every 1 μm from 10 μm to 1 μm.

[0658] In the development step, cyclopentanone was used as a developing solution. Organic solvent development was performed by spraying each organic solvent for 1 minute, and then rinsing with isopropyl alcohol.

[0659] Then, the obtained substrate was post-hardened using an oven at 200°C for 2 hours while being purged with nitrogen.

[0660] Then, each substrate was cut out in a manner such that the shape of the obtained hole pattern could be observed, and the hole pattern shape was observed using a scanning electron microscope (SEM). The aperture of the smallest open hole in the film thickness of 5 μm after post-hardening was found, and the shape of the pattern was evaluated. These results, together with the sensitivity with which the smallest pattern could be formed, are shown in Tables 2 to 5.

[0661] Further, the pattern shape of the hole was evaluated according to the following criteria, and the evaluation results are shown in Tables 2 to 5.

[0662] Good: The hole was observed to be rectangular or a right conical shape (a shape in which the size of the upper portion of the hole is larger than that of the bottom portion).

[0663] Poor: An inverted taper shape (a shape in which the size of the upper portion of the hole is smaller than that of the bottom portion), a hanging sub shape (a shape in which the upper portion of the hole protrudes), a significant film reduction, or a residue observed at the bottom portion of the hole was observed.

[0664] VI. Storage stability

[0665] In the above pattern formation, 5 mL of the described photosensitive resin composition was dispensed onto a silicon substrate, and then the substrate was rotated to uniformly coat the photosensitive resin composition, and then pre-baking was performed at 100°C for 3 minutes on a hot plate. The film thickness after the pre-baking was recorded, and the solution of the photosensitive resin composition was stored at room temperature for 3 weeks.

[0666] After 3 weeks, a film was formed under the same conditions and at the same rotation speed, and the film thickness was measured. The film thickness before storage was compared with the film thickness after storage, and the storage stability was evaluated as follows.

[0667] The film thickness change rate was calculated by the following formula.

[0668] Film thickness change rate (%) = {(film thickness before the elapse of time - film thickness after the elapse of time) / film thickness before the elapse of time} x 100

[0669] The calculated film thickness change rate was evaluated according to the following evaluation criteria.

[0670] Excellent: A composition in which the variation in the film thickness before and after storage is less than 10%.

[0671] Good: A composition in which the variation in the film thickness before and after storage is 10% or more and less than 15%.

[0672] Poor: A composition in which the variation in the film thickness before and after storage is 15% or more.

[0673] Not evaluated: A composition in which the composition solution gelled after 3 weeks and could not form a film.

[0674] The evaluation results are shown in Tables 2 to 5. The smaller the above film thickness change rate, the more excellent the storage stability of the hardening composition can be said to be. In addition, it is preferable that the composition solution be stable without change.

[0675] VII. Drug resistance

[0676] In the above pattern formation, 5 mL of the described photosensitive resin composition was dispensed onto a silicon substrate, and then the substrate was rotated to apply the composition uniformly, and then pre-baked at 100°C for 3 minutes on a hot plate. Then, using an i-ray stepper NSR-2205i11 manufactured by Nikon Corporation, a full-area exposure was performed without pattern formation by i-ray exposure at an exposure amount of 600 mJ.

[0677] Then, the film on the obtained substrate was subjected to post-hardening at 200°C for 2 hours using an oven while being purged with nitrogen.

[0678] The obtained hardened film was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.

[0679] Chemical solution: a mixture of dimethyl sulfoxide (DMSO) and a 25 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) at 90:10 (mass ratio)

[0680] Evaluation conditions: the resin layer was immersed in the above chemical solution at 75°C for 15 minutes, and the change in film thickness was compared, and the amount of change in the hardened film was measured. The evaluation was performed according to the following evaluation criteria, and the evaluation results are described together in Tables 2 to 5. It can be said that the smaller the amount of change in film thickness, the more excellent the chemical resistance of the obtained hardened film (resin layer).

[0681] Good: the amount of change in film thickness was 3.0 μm or more and less than 5.0 μm.

[0682] Good: the amount of change in film thickness was 3.0 μm or more and less than 5.0 μm.

[0683] Poor: the amount of change in film thickness was 5.0 μm or more.

[0684] As shown in the results of Tables 2 to 5, it was found that the negative photosensitive resin composition containing the organic compound of the present application is excellent in resolution performance. Furthermore, it was found that the storage stability and chemical resistance are also excellent.

[0685] On the other hand, it was found that the storage stability is poor when a negative photosensitive resin composition containing a compound other than the organic compound of the present application is used. That is, as shown in the results of comparing the storage stability of the photosensitive resin compositions 24 to 32 (Comparative Examples 2 to 10), it was found that the storage stability of the negative photosensitive resin composition to which an organic compound not protected is added is poor, unlike the organic compound of the present application in which a hydroxyl compound as an active esterification agent is protected with a tert-butoxycarbonyl group (N-Boc group), or unlike an organic compound protected with a benzyloxycarbonyl protecting group (Z group).

[0686] The comparative photosensitive resin composition 33 (Comparative Example 11) is a composition to which no organic compound used in the negative photosensitive resin composition of the present application is added. The hardening film of this composition has poor chemical resistance compared to the composition containing the nitrogen-containing compound of the present application. This is considered to be because, as described above, the imide ring-closing temperature of the composition not containing the nitrogen-containing organic compound of the present application is as high as 230°C, and complete imidization cannot be achieved under the conditions of 200°C for 2 hours in an oven used in this evaluation, and the chemical resistance as a polyimide cannot be exhibited.

[0687] The present specification contains the following aspects.

[0688] [1] A negative photosensitive resin composition characterized by containing:

[0689] (A) a high molecular compound having a polyimide precursor structure,

[0690] (C) a photopolymerization initiator,

[0691] (D) an organic compound represented by the following general formula (1), and

[0692] (E) a solvent;

[0693] [Chemical Formula 101]

[0694]

[0695] In the formula, T represents any one of the following general formulas (2) to (4), and W represents an alkyl group or an aryl group which can also be substituted with an alkoxy group having 4 to 15 carbon atoms.

[0696] [Chemical Formula 102]

[0697]

[0698] In the formula, V represents a divalent organic group, and * represents a bond.

[0699] [Chemical Formula 103]

[0700]

[0701] In the formula, 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.

[0702] [Chemical Formula 104]

[0703]

[0704] wherein Ar represents a substituted or unsubstituted aromatic ring structure, or a heterocyclic ring structure having a hetero atom, and * represents a bond.

[0705] [2] The negative photosensitive resin composition according to [1], wherein the (A) component is a high molecular compound having a polyimide precursor structure represented by the following general formula (5),

[0706] [Chemical Formula 105]

[0707]

[0708] wherein X is a tetravalent organic group, Y is a divalent organic group, R 1 and R 2 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R 1 and R 2 is a group represented by the following general formula (6).

[0709] [Chemical Formula 106]

[0710]

[0711] wherein M 1 , M 2 , and M 3 each independently represent a hydrogen atom or an organic group having a carbon number of 1 to 3, m is an integer of 2 to 10, and * represents a bond.

[0712] [3] The negative photosensitive resin composition according to [1] or [2], wherein (B) a polymerizable compound having two or more ethylenically unsaturated groups is contained.

[0713] [4] The negative photosensitive resin composition according to any one of [1] to [3], wherein W in the general formula (1) of the (D) component is a tert-butyl group.

[0714] [5] The negative photosensitive resin composition according to any one of [1] to [3], wherein W in the general formula (1) of the (D) component is a benzyl group.

[0715] [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),

[0716] [Chemical Formula 107]

[0717]

[0718] wherein R a and R b represent a hydrogen atom, a linear, branched, or cyclic alkyl group having a carbon number of 1 to 15, or an aryl group having a carbon number of 6 to 15, and Ra and R b may be bonded to each other and, together with the carbon atom to which they are bonded, form a ring, and * represents a bond.

[0719] [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),

[0720] [Chemical Formula 108]

[0721]

[0722] in the formula, * represents a bond.

[0723] [Chemical Formula 109]

[0724]

[0725] in the formula, * represents a bond.

[0726] [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),

[0727] [Chemical Formula 110]

[0728]

[0729] in the formula, R d represents a linear, branched, or cyclic alkyl group having a halogen atom with a carbon number of 1 to 15, or an aryl group with a carbon number of 6 to 15, k represents an integer of 0 to 4, and * represents a bond.

[0730] [9] The negative photosensitive resin composition according to any one of [1] to [8], wherein 1 to 10 parts by mass of the (D) component is contained with respect to 100 parts by mass of the (A) component.

[0731]

[10] The negative photosensitive resin composition according to any one of [1] to [9], wherein, as the (F) thermal crosslinking agent, a substance containing one or two or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or a formaldehyde-alcohol, a phenol compound having two or more hydroxymethyl groups or alkoxyhydroxymethyl groups on average in one molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyphenol is substituted with a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyphenol or a hydroxyl group of a polyol 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),

[0732] [Chemical Formula 111]

[0733]

[0734] in the formula, the dotted line indicates a bond of an atom, Rf is a linear, branched, or cyclic alkyl group having 1 to 6 carbons, and c is 1 or 2.

[0735]

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

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

[0736]

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

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

[0737]

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

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

[0738]

[14] A pattern forming method characterized by comprising:

[0739] (1) a step of applying the photosensitive resin composition according to any one of [1] to

[13] on a substrate to form a photosensitive material coating film;

[0740] (2) then, a step of exposing the photosensitive material coating film to high-energy rays having a wavelength of 190 to 500 nm or an electron beam through a photomask after heat treatment; and

[0741] (3) a step of developing the exposed film using a developing solution of an organic solvent.

[0742]

[15] A hardened film forming method characterized by comprising a step of post-hardening a film having a pattern obtained by the pattern forming method according to

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

[0743]

[16] An interlayer insulating film characterized by being a hardened film of the negative photosensitive resin composition according to any one of [1] to

[13] .

[0744]

[17] A surface protective film characterized by being a hardened film of the negative photosensitive resin composition according to any one of [1] to

[13] .

[0745]

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

[16] .

[0746]

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

[17] .

[0747] Further, the present application is not limited to the above-described embodiments. The above-described embodiments are examples, and technical solutions having substantially the same configuration as the technical idea described in the claims of the present application and exerting the same effects are all included in the technical scope of the present application.

Claims

1. A negative photosensitive resin composition, characterized by comprising: (A) Polymer compounds with polyimide precursor structures (C) Photopolymerization initiator, (D) Organic compounds represented by the following general formula (1), and (E) Solvent; In the formula, T represents any structure in the following general formulas (2) to (4), and W represents an alkyl or aryl group that can also be substituted by an alkoxy group having 4 to 15 carbon atoms. In the formula, V represents a divalent organic group, and * represents a bond. In the formula, Q represents a halogen atom or a nitro group, and R... C This indicates a hydrogen atom, a straight-chain, branched, or cyclic alkyl group with 1 to 15 carbon atoms, or an aryl group with 6 to 15 carbon atoms. 'n' represents an integer from 3 to 5 when Q is a halogen atom, and 1 when Q is a nitro group. * indicates a bond. In the formula, Ar represents a substituted or unsubstituted aromatic ring structure, or a heterocyclic structure with heteroatoms, and * represents a bond.

2. The negative photosensitive resin composition according to claim 1, wherein, The component (A) is a polymeric compound having the structure of a polyimide precursor as shown in the following general formula (5). In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R... 1 and R 2 Each is independently a hydrogen atom or a monovalent organic group, and R 1 and R 2 At least one of them is a group represented by the following general formula (6), In the formula, M 1 M 2 and M 3 Each is an independent hydrogen atom or an organic group with 1 to 3 carbon atoms, m is an integer from 2 to 10, and * indicates a bond.

3. The negative photosensitive resin composition according to claim 1, wherein, (B) Polymer compounds having two or more vinyl unsaturated groups.

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

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

6. The negative photosensitive resin composition according to claim 1, wherein, The general formula (2) is the structure shown in the following general formula (2-1). In the formula, R a and R b R represents a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms. a and R b They can also bond to each other and form rings together with the carbon atoms they are bonded to; * indicates a bond.

7. The negative photosensitive resin composition according to claim 1, wherein, The general formula (3) is the structure shown in formula (3-1) or (3-2) below. In the formula, * represents a bond. In the formula, * represents a bond.

8. The negative photosensitive resin composition according to claim 1, wherein, The general formula (4) is the structure shown in the following general formula (4-1). In the formula, R d The alkyl group with 1 to 15 carbon atoms can be a straight-chain, branched, or cyclic alkyl group or an aryl group with 6 to 15 carbon atoms, k represents an integer from 0 to 4, and * represents a bond.

9. The negative photosensitive resin composition according to claim 1, wherein, The component (D) contains 1 to 10 parts by mass relative to 100 parts by mass of component (A).

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

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

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

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

14. A method for forming a pattern, characterized by: include: (1) The step of coating a photosensitive resin composition according to any one of claims 1 to 13 onto a substrate to form a photosensitive film; (2) Then, after heat treatment, the photosensitive film is exposed to high-energy rays or electron beams with wavelengths of 190–500 nm through a photomask; and (3) After irradiation, the step of developing with an organic solvent developer.

15. A method for forming a hardened film, characterized in that, This includes the step of heating and post-curing a patterned film obtained by the patterning method according to claim 14 at a temperature of 100 to 300°C.

16. An interlayer insulating film, characterized in that, It is a hardened film formed by curing the negative photosensitive resin composition according to any one of claims 1 to 13.

17. A surface protective film, characterized in that, It is a hardened film formed by curing the negative photosensitive resin composition according to any one of claims 1 to 13.

18. An electronic component, characterized in that, It has an interlayer insulating film as described in claim 16.

19. An electronic component, characterized in that, It has the surface protective film according to claim 17.

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