Polymer, negative photosensitive resin composition, patterning process, method for forming cured film, interlayer insulating film, surface protective film, and electronic component

Abstract

To provide: a polymer having a polyimide precursor, usable as a base resin for a negative photosensitive resin composition which enables fine pattern formation and high resolution and has excellent mechanical characteristics even when cured at low temperatures; and a negative photosensitive resin composition which includes the polymer, and in patterning, is excellent in resolution and enables fine pattern formation, and has excellent mechanical characteristics even when cured at low temperatures.SOLUTION: A polymer having a polyimide precursor comprises a structural unit represented by the general formula (1) in the figure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymer having a polyimide precursor, a negative photosensitive resin composition, a pattern forming method, a cured film forming method, an interlayer insulating film, a surface protective film, and an electronic component. [Background technology]

[0002] As various electronic devices such as personal computers, digital cameras, and mobile phones become smaller and more powerful, there is a rapidly increasing demand for semiconductor elements to be even smaller, thinner, and more densely packed. Accordingly, the interlayer insulating films and surface protective films of semiconductor elements are required to have superior electrical properties, heat resistance, mechanical properties, etc.

[0003] In high-density packaging technologies such as three-dimensional stacking, photosensitive insulating materials that can be patterned on substrates have long been used as protective coatings or insulating layers, and their insulating properties, mechanical characteristics, and adhesion to substrates have continued to attract attention, and development is still active today.

[0004] Conventionally, photosensitive polyimide-based materials have been proposed that utilize polyamic acid, a precursor of polyimide, such as a material in which a photosensitive group is introduced to the carboxyl group of polyamic acid via an ester bond (Patent Document 1). However, the proposal in Patent Document 1 requires that after forming a patterned film, an imidization treatment be carried out at a high temperature exceeding 300°C to obtain the desired polyimide film. This has the problem of restricting the base substrate to withstand such high temperatures and oxidizing the copper in the wiring.

[0005] Furthermore, compositions containing polymers having structural units derived from ester-containing diamines have been proposed to improve the mechanical strength of cured films (Patent Documents 2 and 3). Patent Document 2 proposes a positive-type photosensitive resin composition containing an ester diamine-containing polybenzoxazole precursor and a naphthoquinone diazide compound, but with regard to lithography properties, only dissolution contrast and sensitivity are described, with no mention of pattern resolution, and there is also room for improvement in the mechanical strength value.

[0006] Patent Document 3 proposes a polyamic acid containing a diamine residue derived from an ester-containing diamine and a flexible diamine, and an acid dianhydride residue, as a diamine residue, and a polyimide formed by ring closure of the polyamic acid. However, there is no mention of a photosensitive resin composition, and there is room for improvement in mechanical strength, particularly elongation.

[0007] As described above, as chips become increasingly dense and highly integrated in the future, it is expected that patterns in the rewiring technology for insulating protective films will become increasingly finer. Therefore, there is a strong demand for photosensitive resin compositions that can realize pattern shapes with high resolution and good rectangularity without impairing the excellent characteristics of the patterns and protective films obtained by heating, such as mechanical properties and adhesion. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 6-342211 [Patent Document 2] Japanese Patent Application Publication No. 2020-152768 [Patent Document 3] Japanese Patent Publication No. 2021-187934 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polymer having a polyimide precursor that can be used as a base resin for a negative-type photosensitive resin composition that can form a fine pattern, obtain high resolution, and have good mechanical properties even when cured at low temperatures. Another object of the present invention is to provide a negative photosensitive resin composition using the above polymer, which has excellent resolution in pattern formation, is capable of forming fine patterns, and has good mechanical properties even when cured at low temperatures. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention provides a polymer having a polyimide precursor, which polymer contains a structural unit represented by the following general formula (1): [ka] (In the formula, X1 is a tetravalent organic group; R1 to R4 may be different or the same and are a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom or a hydrogen atom, at least one of which is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom; L is a divalent linking group; Ra and Rb are each independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group represented by the following general formula (2), and at least one of Ra and Rb is an organic group represented by the following general formula (2).) [ka] (In the formula, the dotted line represents a bond, Rc is a hydrogen atom or an organic group having 1 to 3 carbon atoms, Rd and Re are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10.)

[0011] Such a polymer has a polymerizable unsaturated bond group in its structural unit, and therefore, when combined with a photoradical initiator (described later), radical polymerization proceeds using radicals generated in exposed areas during pattern formation as an initiator, and the polymer is characterized by being insoluble in a developer. Therefore, a negative-type photosensitive resin composition can be obtained even without adding a new crosslinking agent. Furthermore, since the general formula (1) has a phenyl group having a substituent, appropriate intermolecular interaction is promoted, and the polymer can be used as a base resin for a photosensitive resin composition that has good mechanical properties even when cured at low temperatures.

[0012] In addition, it is preferable that in the polymer, one of R1 and R2 in the general formula (1) is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom, and the other is a hydrogen atom, and R3 and R4 are hydrogen atoms.

[0013] In the case of a photosensitive resin composition using such a polymer, the free rotation of the polymer chain is suppressed by the steric hindrance of the substituent due to the presence of a substituent at the ortho-position of the bonding site, and the intermolecular interaction becomes appropriate, resulting in good mechanical properties even when cured at low temperatures.

[0014] In this case, it is preferable that one of R1 and R2 in the general formula (1) is an aromatic group having 6 to 12 carbon atoms, and the other is a hydrogen atom.

[0015] A photosensitive resin composition using such a polymer will have better mechanical properties even when cured at a low temperature.

[0016] Furthermore, in the polymer, L in the general formula (1) is preferably at least one organic group selected from an oxygen atom, a sulfur atom, an ester group, a carbonyl group, a linear alkylene group having 1 to 15 carbon atoms, and a branched alkylene group having 3 to 15 carbon atoms, and particularly preferably at least one organic group selected from an oxygen atom and an ester group.

[0017] A photosensitive resin composition using such a polymer has good mechanical properties due to the flexibility imparted to the polymer chain.

[0018] Furthermore, the present invention provides a negative photosensitive resin composition comprising: (A) a polymer having a polyimide precursor containing a structural unit represented by the general formula (1), (B) a photoradical initiator, and (E) solvent, The present invention provides a negative photosensitive resin composition comprising:

[0019] As described above, a polymer having a polyimide precursor containing a structural unit represented by the above general formula (1) has a polymerizable unsaturated bond group in the polymer molecule, and therefore, a negative-type photosensitive resin composition can be obtained by combining the polymer with a photoradical initiator.

[0020] It is also preferable that the negative photosensitive resin composition further contains, as component (C), a crosslinking agent having two or more photopolymerizable unsaturated bond groups in one molecule.

[0021] By including a crosslinking agent having two or more photopolymerizable unsaturated bonds in one molecule, crosslinking by photopolymerization in the exposed area can be further promoted, improving the contrast between the exposed and unexposed areas.

[0022] Furthermore, it is preferable that the negative-type photosensitive resin composition further contains, as a thermal crosslinking agent (D), one or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or a formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, a compound in which the hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group, a compound in which the hydrogen atom of a hydroxyl group of a polyhydric phenol or a hydroxyl group of a polyhydric alcohol is substituted with a substituent represented by the following formula (D-1), and a compound containing two or more nitrogen atoms and having a glycidyl group represented by the following formula (D-2). [ka] (In the formula, the dotted line represents a bond, Rf represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.)

[0023] By including component (D), crosslinking with component (A) occurs during post-curing, increasing the crosslink density of the cured film and making it possible to obtain excellent mechanical strength.

[0024] The negative photosensitive resin composition may further contain one or more of (F) a protected amine compound, (G) a thermal acid generator, (H) an antioxidant, and (I) a silane compound.

[0025] Component (F) generates a basic compound during high temperature curing, which acts as a catalyst for the crosslinking reaction and accelerates the curing reaction.

[0026] Component (G) can further improve the mechanical strength, chemical resistance, adhesion, etc. of the resulting pattern or coating by further promoting the crosslinking and curing reaction.

[0027] Component (H) can suppress deterioration of physical properties due to oxidation of the cured film during reliability tests such as high humidity tests and thermal shock tests, and can form a more suitable cured film.

[0028] Component (I) can further improve the adhesion of the resulting pattern or coating to the substrate.

[0029] Furthermore, the present invention provides a pattern forming method, comprising the steps of: (1) a step of applying the above-mentioned negative photosensitive resin composition onto a substrate to form a photosensitive film; (2) heating the photosensitive coating; (3) exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask; and (4) developing using an organic solvent developer; The present invention provides a pattern formation method comprising the steps of:

[0030] Such a pattern formation method uses, as a base resin, a polymer having a polymerizable unsaturated bond group, and such a pattern formation method is capable of forming a fine pattern with excellent resolution and can form a pattern with good mechanical properties even when cured at a low temperature.

[0031] Furthermore, the present invention provides a method for forming a cured coating, which includes a step of heating and post-curing the patterned coating obtained by the above-mentioned pattern formation method at a temperature of 100 to 300°C.

[0032] In such a method for forming a cured coating, an imide ring-closure reaction occurs in the structural units of the polyimide precursor in the polymer of the present invention, resulting in a very stable film of polyimide resin, making it possible to form a cured coating (pattern) with good mechanical properties.

[0033] The present invention also provides an interlayer insulating film or a surface protective film, which is characterized by comprising a cured film obtained by curing the above-mentioned negative photosensitive resin composition.

[0034] The cured coating obtained by curing the negative-type photosensitive resin composition of the present invention has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance to alkaline stripping solutions and the like, and also has excellent reliability for semiconductor elements using the cured coating as a protective coating. Therefore, the cured coating is suitable as a protective coating (interlayer insulating film or surface protective film) for electrical / electronic components, semiconductor elements, etc.

[0035] The present invention also provides an electronic component comprising the above-mentioned interlayer insulating film or surface protective film.

[0036] Such protective coatings (interlayer insulating films or surface protective films) are effective as insulating films for semiconductor elements, including rewiring applications, insulating films for multilayer printed circuit boards, and the like, due to their heat resistance, chemical resistance, and insulating properties, and can be used to produce electronic components with excellent reliability. [Effects of the Invention]

[0037] As described above, the present invention can provide a polymer having a polyimide precursor that can be used as a base resin for a negative-type photosensitive resin composition that can form a fine pattern with high resolution and has good mechanical properties even when cured at low temperatures. Furthermore, a negative photosensitive resin composition using the above polymer can be provided, which has excellent resolution in pattern formation, is capable of forming a fine pattern, and has good mechanical properties even when cured at low temperatures. DETAILED DESCRIPTION OF THE INVENTION

[0038] As described above, there has been a demand for a polymer that can be used as a base resin for a photosensitive resin composition that can form a fine pattern, can obtain high resolution, and has good mechanical properties even when cured at low temperatures.

[0039] As a result of intensive research to achieve the above object, the present inventors have found that when a polymer having a polyimide precursor containing a structural unit represented by the following general formula (1) is used as a base resin of a photosensitive resin composition, it can be used to produce a negative-type photosensitive resin composition that can be developed with an organic solvent, and that the pattern obtained using the negative-type photosensitive resin composition is fine and has a good pattern shape.

[0040] Furthermore, it was found that when a photosensitive resin composition containing the above-mentioned polyimide-containing polymer as a base resin is used to form a pattern and then heated at low temperature, the resulting protective coating has excellent mechanical strength and adhesion. That is, it was found that a cured coating having a pattern formed using a photosensitive resin composition containing the above-mentioned polymer having the structural unit as a base resin is excellent as a protective coating for electrical and electronic components and an insulating protective coating, and this led to the completion of the present invention. In this specification, electrical and electronic components are also collectively referred to as "electronic components."

[0041] That is, the present invention is a polymer having a polyimide precursor containing a structural unit represented by the following general formula (1). [ka] (In the formula, X1 is a tetravalent organic group; R1 to R4 may be different or the same and are a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom or a hydrogen atom, at least one of which is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom; L is a divalent linking group; Ra and Rb are each independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group represented by the following general formula (2), and at least one of Ra and Rb is an organic group represented by the following general formula (2).) [ka] (In the formula, the dotted line represents a bond, Rc is a hydrogen atom or an organic group having 1 to 3 carbon atoms, Rd and Re are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10.)

[0042] The present invention will be described in detail below, but the present invention is not limited thereto.

[0043] [(A) Polymer] The polymer of the present invention is a polymer having a polyimide precursor, and contains a structural unit represented by the following general formula (1). [ka] (In the formula, X1 is a tetravalent organic group; R1 to R4 may be different or the same and are a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom or a hydrogen atom, at least one of which is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom; L is a divalent linking group; Ra and Rb are each independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group represented by the following general formula (2), and at least one of Ra and Rb is an organic group represented by the following general formula (2).) [ka] (In the formula, the dotted line represents a bond, Rc is a hydrogen atom or an organic group having 1 to 3 carbon atoms, Rd and Re are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10.)

[0044] X1 in the above general formula (1) is a tetravalent organic group, but is not limited thereto as long as it is a tetravalent organic group. Preferably, it is a tetravalent alicyclic aliphatic group having 4 to 40 carbon atoms or a tetravalent aromatic group having 6 to 40 carbon atoms, and may contain a siloxane skeleton. More preferably, it is a tetravalent organic group represented by the following formula (3). Furthermore, the structure of X1 may be one type or a combination of two or more types. [ka] (In the formula, R a1 , R a2 are each independently a methyl group or a phenyl group, q1 and q2 are integers of 1 to 20, and the dotted lines represent bonds.

[0045] In the general formula (1), at least one of R1 to R4 is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom; preferably, one of R1 and R2 is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom, and the other is a hydrogen atom; R3 and R4 are hydrogen atoms; more preferably, one of R1 and R2 is a group selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, a phenoxy group having 6 to 10 carbon atoms, a benzyl group having 7 to 10 carbon atoms, and a benzyloxy group having 7 to 10 carbon atoms, and the other is a hydrogen atom; and R3 and R4 are hydrogen atoms. Even more preferably, one of R1 and R2 is a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom, and the other is a hydrogen atom; and R3 and R4 are hydrogen atoms.

[0046] Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, and hexyl. Examples of alkoxy groups having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentoxy. Examples of aromatic groups having 6 to 12 carbon atoms include phenyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, butylphenyl, fluorophenyl, chlorophenyl, bromophenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, diethoxyphenyl, aminophenyl, nitrophenyl, cyanophenyl, phenethyl, phenylpropyl, phenylamino, diphenylamino, biphenyl, and naphthyl. Examples of phenoxy groups having 6 to 10 carbon atoms include methylphenoxy, ethylphenoxy, propylphenoxy, dimethylphenoxy, diethylphenoxy, methoxyphenoxy, ethoxyphenoxy, and dimethoxyphenoxy. Examples of benzyl groups having 7 to 10 carbon atoms include benzyl, methylbenzyl, ethylbenzyl, propylbenzyl, dimethylbenzyl, diethylbenzyl, methoxybenzyl, ethoxybenzyl, dimethoxybenzyl, diethoxybenzyl, aminobenzyl, nitrobenzyl, and cyanobenzyl. Examples of benzyloxy groups having 7 to 10 carbon atoms include benzyloxy, methylbenzyloxy, ethylbenzyloxy, propylbenzyloxy, dimethylbenzyloxy, diethylbenzyloxy, methoxybenzyloxy, and ethoxybenzyloxy.

[0047] Of the above, aromatic groups having 6 to 12 carbon atoms, phenoxy groups having 6 to 10 carbon atoms, benzyl groups having 7 to 10 carbon atoms, and benzyloxy groups having 7 to 10 carbon atoms are preferred, aromatic groups having 6 to 12 carbon atoms are more preferred, and phenyl groups, methylphenyl groups, dimethylphenyl groups, ethylphenyl groups, and diethylphenyl groups are even more preferred. Such organic groups are thought to suppress the free rotation of polymer chains due to their bulkiness, thereby suppressing the packing effect between molecules and ensuring appropriate intermolecular interactions, thereby improving the mechanical properties of the cured coating, particularly the elongation at break.

[0048] In the general formula (1), L is a divalent linking group and is not particularly limited. Preferably, L is any one of an oxygen atom, a sulfur atom, an ester group, a carbonyl group, a linear alkylene group having 1 to 15 carbon atoms, and a branched alkylene group having 3 to 15 carbon atoms. More preferably, L is an oxygen atom or an ester group. Such organic groups promote intermolecular interactions through hydrogen bonding and the like, and also interact with the substrate, resulting in good mechanical properties and adhesion to the substrate even when cured at low temperatures.

[0049] In the general formula (1), Ra and Rb each independently represent a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group represented by the general formula (2), and at least one of Ra and Rb is an organic group represented by the general formula (2).

[0050] Rc in the above general formula (2) is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but is preferably a hydrogen atom or a methyl group from the viewpoint of the photosensitive properties of the negative photosensitive resin composition.

[0051] Rd and Re in the general formula (2) are not limited as long as they are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but are preferably a hydrogen atom from the viewpoint of the photosensitive properties of the negative photosensitive resin composition.

[0052] In the above general formula (2), m is an integer of 2 to 10, and from the viewpoint of photosensitivity, it is preferably an integer of 2 to 4. More preferably, m is 2.

[0053] Furthermore, the polymer of the present invention may further contain, in addition to the structural unit represented by the above general formula (1), one or more structural units represented by the following general formulae (4) to (7). [ka] (In the formula, X2 is a tetravalent organic group that is the same as or different from X1, X3 is a divalent organic group, and Ra and Rb are the same as those defined above.) [ka] (In the formula, X4 is a tetravalent organic group that may be the same as or different from X1, and X5 is a divalent organic group that may be the same as or different from X3.) [ka] (In the formula, X6 is a divalent organic group, and X7 is a divalent organic group that is the same as or different from X3.) [ka] (In the formula, X8 is a divalent organic group that may be the same as or different from X6, and X9 is a tetravalent organic group.)

[0054] X2 in the general formula (4) above is a tetravalent organic group, but may be the same as or different from X1 above, and is not limited as long as it is a tetravalent organic group. Preferably, it is a tetravalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a tetravalent aromatic group having 6 to 40 carbon atoms, and may contain a siloxane skeleton. More preferably, it is a tetravalent organic group represented by the formula (3) above. Furthermore, the structure of X2 may be one type or a combination of two or more types.

[0055] X3 in the general formula (4) above is a divalent organic group, and is not limited as long as it is a divalent organic group, but is preferably a divalent organic group having 6 to 40 carbon atoms, and more preferably a divalent cyclic organic group containing 1 to 4 substituted aromatic or aliphatic rings, or a divalent aliphatic group without a cyclic structure, or a siloxane group. More preferred X3 includes structures represented by the following formulas (8) and (9). Furthermore, the structure of X3 may be one type or a combination of two or more types. [ka] (wherein q9 is an integer of 1 to 20, s1 is an integer of 1 to 40, s 2、 Each s3 is independently an integer of 0 to 40, and the dotted line represents a bond.

[0056] [ka] (In the formula, q 10 is an integer from 1 to 4, and R a4 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 q 10 When is 2 or more, R a4 may be the same or different, and q 11 is an integer from 1 to 40, and the dotted lines represent bonds.

[0057] A resin composition containing a polymer including a structural unit represented by the general formula (4) has a polymerizable unsaturated bond group in the structural unit, and therefore, in pattern formation, in addition to the structural unit represented by the general formula (1), radical polymerization proceeds in the exposed area, making the polymer insoluble in a developer, thereby improving the resolution in a negative photosensitive resin composition, which is preferable.

[0058] X4 in the general formula (5) above is a tetravalent organic group, which may be the same as or different from X1 above, and is not limited as long as it is a tetravalent organic group. Preferably, it is a tetravalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a tetravalent aromatic group having 6 to 40 carbon atoms, and may contain a siloxane skeleton. More preferably, it is a tetravalent organic group represented by the formula (3) above. Furthermore, the structure of X4 may be one type or a combination of two or more types.

[0059] X5 in the general formula (5) above is a divalent organic group, which may be the same as or different from X3 above. While there are no particular limitations on the divalent organic group, it is preferably a divalent organic group having 6 to 40 carbon atoms, and more preferably a divalent cyclic organic group containing 1 to 4 substituted aromatic or aliphatic rings, or a divalent aliphatic group without a cyclic structure, or a siloxane group. More preferred examples of X5 include structures represented by the formulas (8) and (9) above. Furthermore, the structure of X5 may be one type or a combination of two or more types.

[0060] Resin compositions containing a polymer containing the structural unit represented by the general formula (5) are preferred because they can improve the mechanical strength, adhesion to the substrate, and heat resistance of the cured film obtained by pattern formation. Furthermore, the structural unit (5) is preferred because it does not require a ring-closing reaction during post-curing, allowing for a relatively lower curing reaction temperature.

[0061] X6 in the above general formula (6) is a divalent organic group, and is not limited as long as it is a divalent organic group. Preferably, it is a divalent organic group having an aliphatic chain length structure of 4 to 40 carbon atoms, a divalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a divalent aromatic group having 6 to 40 carbon atoms. More preferably, it is a divalent organic group represented by the following formula (10). Furthermore, the structure of X6 may be one type or a combination of two or more types. [ka] (In the formula, R a3are each independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, q3 is an integer of 1 to 30, and the dotted line represents a bond.

[0062] X7 in the general formula (6) above is a divalent organic group, which may be the same as or different from X3 above, and is not limited as long as it is a divalent organic group. It is preferably a divalent organic group having 6 to 40 carbon atoms, and is a divalent cyclic organic group containing 1 to 4 substituted aromatic or aliphatic rings, or a divalent aliphatic group or siloxane group without a cyclic structure. More preferred examples include structures represented by the formulas (8) and (9) above. Furthermore, the structure of X7 may be one type or a combination of two or more types.

[0063] Resin compositions containing a polymer containing a structural unit represented by the general formula (6) are preferred because they can improve the mechanical properties such as elongation of the cured coating obtained by patterning, as well as the adhesion to the substrate.

[0064] X8 in the above general formula (7) is a divalent organic group, which may be the same as or different from X6 above, and is not limited as long as it is a divalent organic group. Preferably, it is a divalent organic group having an aliphatic chain length structure of 4 to 40 carbon atoms, a divalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a divalent aromatic group having 6 to 40 carbon atoms. More preferably, it is a divalent organic group represented by the above formula (10). Furthermore, the structure of X8 may be one type or a combination of two or more types.

[0065] X9 in the above general formula (7) is a tetravalent organic group, and is not limited as long as it is a tetravalent organic group, but is preferably a tetravalent organic group having 6 to 40 carbon atoms, and more preferably a tetravalent cyclic organic group containing 1 to 4 substituted aromatic or aliphatic rings, or a tetravalent aliphatic group without a cyclic structure, or a siloxane group. More preferred X9 includes a structure represented by the following formula (11). Furthermore, the structure of X9 may be one type or a combination of two or more types. [ka] (In the formula, q 12 , q 13 , and q 14 is an integer between 1 and 10, and q 15 is an integer from 1 to 20, and the dotted lines represent bonds.

[0066] Resin compositions containing a polymer containing a structural unit represented by the general formula (7) are preferred because they can improve the mechanical strength, adhesion to the substrate, and heat resistance of the cured film obtained by pattern formation. Furthermore, when the structure represented by the general formula (7) is included, it is preferable because a ring-closing reaction is not required during post-curing, and the curing reaction temperature can be relatively lowered.

[0067] The polymer of the present invention preferably has a molecular weight of 5,000 to 100,000, more preferably 7,000 to 50,000. When the molecular weight is 5,000 or more, it becomes easy to form a film of a desired thickness on a substrate from a photosensitive resin composition containing the polymer of the present invention. When the molecular weight is 100,000 or less, the viscosity of the photosensitive resin composition becomes appropriate, and there is no problem in film formation. In the present invention, the weight average molecular weight is a polystyrene-equivalent value determined by gel permeation chromatography (GPC).

[0068] [Polymer manufacturing method] The polymer of the present invention is a polymer having a polyimide precursor, and contains a structural unit represented by the following general formula (1). [ka] (In the formula, X1, R1 to R4, Ra, Rb, and L are the same as above.) The polymer containing the structural unit represented by the general formula (1) can be obtained by reacting a tetracarboxylic acid diester compound represented by the following general formula (12) with a diamine represented by the following general formula (13). [ka] (In the formula, X1, Ra, and Rb are the same as above.) [ka] (In the formula, R1 to R4 and L are the same as above.)

[0069] In the above general formula (12), at least one of Ra and Rb is an organic group represented by the above general formula (2), and the organic group represented by the above general formula (2) can be introduced by reacting a tetracarboxylic dianhydride represented by the following general formula (14) with a compound having a terminal hydroxyl group represented by the following general formula (15) in the presence of a basic catalyst such as pyridine. Here, the tetracarboxylic dianhydride represented by the following general formula (14) is the source of X1 in the above general formula (1) (for example, the tetravalent organic group represented by the above formula (3)), and the compound having a terminal hydroxyl group represented by the following general formula (15) can introduce the organic group represented by the above general formula (2). [ka] (wherein X1 is the same as above.) [ka] (In the formula, Rc, Rd, Re, and m are the same as above.)

[0070] Suitable examples of the tetracarboxylic acid dianhydride represented by the above general formula (14) include aromatic acid dianhydrides, alicyclic acid dianhydrides, aliphatic acid dianhydrides, and siloxane skeleton-containing acid dianhydrides.

[0071] Examples of aromatic acid dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-terphenyltetracarboxylic dianhydride, 3,3',4,4'-oxyphthalic dianhydride, 2,3,3',4'-oxyphthalic dianhydride, 2,3,2',3'-oxyphthalic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, benzophenone, benzophenone, benzophenone-3,3',4,4'- ... Diazepam-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1,4-(3,4-dicarboxyphenoxy)benzene dianhydride, p-phenylenebis( Trimellitic acid monoester anhydride), bis(1,3-dioxo-1,3-dihydroisobenzfuran-5-carboxylic acid) 1,4-phenylene, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis(4-(3,4-dicarboxyphenoxy)phenyl)fluorene dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride Anhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzoyloxy)phenyl)hexafluoropropane dianhydride, 1,6-difluoropyromellitic dianhydride, 1-trifluoromethylpyromellitic dianhydride, 1,6-ditrifluoromethylpyromellitic dianhydride, 2,2'-bis(trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,Examples of the dianhydride include, but are not limited to, 2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, and acid dianhydride compounds in which the aromatic ring of these dianhydrides is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

[0072] Examples of the alicyclic acid dianhydride include 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, and 2,3,4,5- Tetrahydrofuran tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic dianhydride, tricyclo[6,3,0,0]octane-2,4,6,8-tetracarboxylic dianhydride 2,6]undecane-3,5,9,11-tetracarboxylic dianhydride, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,1]heptanetetracarboxylic dianhydride, bicyclo[2,2,1]heptane-5-carboxymethyl-2,3,6-tricarboxylic dianhydride, 7-oxabicyclo[2,2,1]heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecahydroanhydride Examples of suitable dianhydrides include, but are not limited to, tetrathane-1,2,8,9-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride, 3,3',4,4'-oxydicyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and "Rikacid" (registered trademark) BT-100 (all trade names, manufactured by New Japan Chemical Co., Ltd.), derivatives thereof, and acid dianhydride compounds in which the alicyclic ring of these dianhydrides is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

[0073] Examples of the aliphatic acid dianhydride include, but are not limited to, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and derivatives thereof.

[0074] Examples of siloxane skeleton-containing acid dianhydrides include, but are not limited to, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 3,3'-((1,1,3,3-tetramethyl-1,3-disiloxanediyl)di-3,1-propanediyl)bis(dihydro-2,5-furandione), and derivatives thereof.

[0075] These aromatic acid dianhydrides, alicyclic acid dianhydrides, aliphatic acid dianhydrides, and siloxane skeleton-containing acid dianhydrides can be used alone or in combination of two or more kinds.

[0076] Rc in the above general formula (15) is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but is preferably a hydrogen atom or a methyl group from the viewpoint of the photosensitive properties of the negative photosensitive resin composition.

[0077] Rd and Re in the general formula (15) are not limited as long as they are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but are preferably a hydrogen atom from the viewpoint of the photosensitive properties of the negative photosensitive resin composition.

[0078] In the general formula (15), m is an integer of 2 to 10, and from the viewpoint of photosensitivity, it is preferably an integer of 2 to 4. More preferably, m is 2.

[0079] Among the compounds having a hydroxyl group at the terminal represented by the above general formula (15), suitable compounds include, for example, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-methacryloyloxyethyl alcohol, and 1-methacryloyloxy-3-propyl alcohol.

[0080] Furthermore, Ra and Rb in the general formula (12) may be a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. A method for introducing a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms into the general formula (12) (i.e., Ra and Rb become linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms) includes a method in which a compound having a terminal hydroxyl group, represented by the general formula (15), and a tetracarboxylic dianhydride are reacted in the presence of a basic catalyst such as pyridine, and a linear, branched, or cyclic alcohol having 1 to 6 carbon atoms is simultaneously added.

[0081] Suitable alcohols that can be used in this case include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, cyclopentanol, and cyclohexanol.

[0082] The reaction of the tetracarboxylic dianhydride represented by the general formula (14) with the compound having a terminal hydroxyl group represented by the general formula (15) can be carried out by stirring, dissolving, and mixing the tetracarboxylic dianhydride represented by the general formula (14) and the compound having a terminal hydroxyl group represented by the general formula (15) in a reaction solvent in the presence of a basic catalyst such as pyridine at a reaction temperature of 20 to 50°C for 4 to 10 hours, thereby causing a half-esterification reaction of the acid dianhydride to proceed, and the desired tetracarboxylic diester compound represented by the general formula (12) can be obtained as a solution dissolved in the reaction solvent.

[0083] The resulting tetracarboxylic acid diester compound may be isolated, or the resulting solution may be used as is in the reaction with a diamine in the next step described below.

[0084] The reaction solvent is preferably one that can dissolve the tetracarboxylic acid diester compound and the polymer having structural units of a polyimide precursor obtained by the subsequent polycondensation reaction of the tetracarboxylic acid diester compound with a diamine. Examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and γ-butyrolactone. Ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons can also be used. Specific examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, and xylene. These solvents may be used alone or in combination as needed.

[0085] Suitable examples of the diamine represented by the general formula (13) include (2-methyl-4-amino)phenyl-4-aminobenzoate, (3-methyl-4-amino)phenyl-4-aminobenzoate, (2-ethyl-4-amino)phenyl-4-aminobenzoate, (3-ethyl-4-amino)phenyl-4-aminobenzoate, (2-propyl-4-amino)phenyl-4-aminobenzoate, (3-propyl-4-amino)phenyl-4-aminobenzoate, and (2-isopropyl-4-amino)phenyl-4-aminobenzoate. , (3-isopropyl-4-amino)phenyl-4-aminobenzoate, (2-butyl-4-amino)phenyl-4-aminobenzoate, (3-butyl-4-amino)phenyl-4-aminobenzoate, (2-isobutyl-4-amino)phenyl-4-aminobenzoate, (3-isobutyl-4-amino)phenyl-4-aminobenzoate, (2-pentyl-4-amino)phenyl-4-aminobenzoate, (3-pentyl-4-amino)phenyl-4-aminobenzoate, (2-hexyl-4-amino)phenyl-4-aminobenzoate aminobenzoate, (3-hexyl-4-amino)phenyl-4-aminobenzoate, (2-methoxy-4-amino)phenyl-4-aminobenzoate, (3-methoxy-4-amino)phenyl-4-aminobenzoate, (2-ethoxy-4-amino)phenyl-4-aminobenzoate, (3-ethoxy-4-amino)phenyl-4-aminobenzoate, (2-propoxy-4-amino)phenyl-4-aminobenzoate, (3-propoxy-4-amino)phenyl-4-aminobenzoate, (2-butoxy-4-amino) Phenyl-4-aminobenzoate, (3-butoxy-4-amino)phenyl-4-aminobenzoate, (2-pentoxy-4-amino)phenyl-4-aminobenzoate, (3-pentoxy-4-amino)phenyl-4-aminobenzoate, (2-phenyl-4-amino)phenyl-4-aminobenzoate, (3-phenyl-4-amino)phenyl-4-aminobenzoate, (2-methylphenyl-4-amino)phenyl-4-aminobenzoate, (3-methylphenyl-4-amino)phenyl-4-aminobenzoate,(2-ethylphenyl-4-amino)phenyl-4-aminobenzoate, (3-ethylphenyl-4-amino)phenyl-4-aminobenzoate, (2-propylphenyl-4-amino)phenyl-4-aminobenzoate, (3-propylphenyl-4-amino)phenyl-4-aminobenzoate, (2-butylphenyl-4-amino)phenyl-4-aminobenzoate, (3-butylphenyl-4-amino)phenyl-4-aminobenzoate, (2-fluorophenyl-4-amino)phenyl-4-aminobenzoate, (3-fluorophenyl-4-amino)phenyl-4-aminobenzoate, (2-chlorophenyl-4-amino)phenyl-4-aminobenzoate, (3-chlorophenyl-4-amino)phenyl-4-aminobenzoate, (2-bromophenyl-4-amino)phenyl-4-aminobenzoate, (3-bromophenyl-4-amino)phenyl-4-aminobenzoate, (2-methoxyphenyl-4-amino)phenyl-4-aminobenzoate, (3-methoxyphenyl-4-amino)phenyl-4-aminobenzoate, ( 2-ethoxyphenyl-4-amino)phenyl-4-aminobenzoate, (3-ethoxyphenyl-4-amino)phenyl-4-aminobenzoate, (2-ethoxyphenyl-4-amino)phenyl-4-aminobenzoate, (2-aminophenyl-4-amino)phenyl-4-aminobenzoate, (3-aminophenyl-4-amino)phenyl-4-aminobenzoate, (2-nitrophenyl-4-amino)phenyl-4-aminobenzoate, (3-nitrophenyl-4-amino)phenyl-4-aminobenzoate, ( 2-cyanophenyl-4-amino)phenyl-4-aminobenzoate, (3-cyanophenyl-4-amino)phenyl-4-aminobenzoate, (2-phenylethyl-4-amino)phenyl-4-aminobenzoate, (3-phenylethyl-4-amino)phenyl-4-aminobenzoate, (2-phenylamino-4-amino)phenyl-4-aminobenzoate, (3-phenylamino-4-amino)phenyl-4-aminobenzoate, (2-(4,4'-biphenyl)-4-amino)phenyl-4-aminobenzoate,(3-(4,4'-biphenyl)-4-amino)phenyl-4-aminobenzoate, (2-naphthyl-4-amino)phenyl-4-aminobenzoate, (3-naphthyl-4-amino)phenyl-4-aminobenzoate, (2-methylphenoxy-4-amino)phenyl-4-aminobenzoate, (3-methylphenoxy-4-amino)phenyl-4-aminobenzoate, (2-ethylphenoxy-4-amino)phenyl-4-aminobenzoate, (3-ethylphenoxy-4-amino)phenyl-4-aminobenzoate, (2-propylphenoxy (2-ethoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (3-ethoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (2-benzyl-4-amino)phenyl-4-aminobenzoate, (3-benzyl-4-amino)phenyl-4-aminobenzoate, (2-methoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (3-methoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (2-ethoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (3-ethoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (2-benzyl-4-amino)phenyl-4-aminobenzoate, (3-benzyl-4-amino)phenyl (2-methylbenzyl-4-amino)phenyl-4-aminobenzoate, (3-methylbenzyl-4-amino)phenyl-4-aminobenzoate, (2-ethylbenzyl-4-amino)phenyl-4-aminobenzoate, (3-ethylbenzyl-4-amino)phenyl-4-aminobenzoate, (2-propylbenzyl-4-amino)phenyl-4-aminobenzoate, (3-propylbenzyl-4-amino)phenyl-4-aminobenzoate, (2-methoxybenzyl-4-amino)phenyl-4- Aminobenzoate, (3-methoxybenzyl-4-amino)phenyl-4-aminobenzoate, (2-ethoxybenzyl-4-amino)phenyl-4-aminobenzoate, (3-ethoxybenzyl-4-amino)phenyl-4-aminobenzoate, (2-aminobenzyl-4-amino)phenyl-4-aminobenzoate, (3-aminobenzyl-4-amino)phenyl-4-aminobenzoate, (2-nitrobenzyl-4-amino)phenyl-4-aminobenzoate, (3-nitrobenzyl-4-amino)phenyl-4-aminobenzoate,(2-cyanobenzyl-4-amino)phenyl-4-aminobenzoate, (3-cyanobenzyl-4-amino)phenyl-4-aminobenzoate, (2-benzyloxy-4-amino)phenyl-4-aminobenzoate, (3-benzyloxy-4-amino)phenyl-4-aminobenzoate, (2-methylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-methylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (2-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-methylbenzenamine, 4-(4-aminophenoxy)-2-methylbenzenamine, 4-(4-aminophenoxy)-3-ethylbenzenamine, 4-(4-aminophenoxy)-2-ethylbenzenamine benzeneamine, 4-(4-aminophenoxy)-3-propylbenzeneamine, 4-(4-aminophenoxy)-2-propylbenzeneamine, 4-(4-aminophenoxy)-3-isopropylbenzeneamine, 4-(4-aminophenoxy)-2-isopropylbenzeneamine, 4-(4-aminophenoxy)-3-butylbenzeneamine, 4-(4-aminophenoxy)-2-butylbenzeneamine, 4-(4-aminophenoxy)-3-isobutylbenzeneamine,

[0086] 4-(4-aminophenoxy)-2-isobutylbenzenamine, 4-(4-aminophenoxy)-3-pentylbenzenamine, 4-(4-aminophenoxy)-2-pentylbenzenamine, 4-(4-aminophenoxy)-3-hexylbenzenamine, 4-(4-aminophenoxy)-2-hexylbenzenamine, 4-(4-aminophenoxy)-3-(trifluoromethyl)benzenamine, 4-(4-aminophenoxy)-2-(trifluoromethyl)benzenamine, 4-(4-aminophenoxy)-3-methoxybenzenamine, 4 -(4-aminophenoxy)-2-methoxybenzenamine, 4-(4-aminophenoxy)-3-ethoxybenzenamine, 4-(4-aminophenoxy)-2-ethoxybenzenamine, 4-(4-aminophenoxy)-3-propoxybenzenamine, 4-(4-aminophenoxy)-2-propoxybenzenamine, 4-(4-aminophenoxy)-3-butoxybenzenamine, 4-(4-aminophenoxy)-2-butoxybenzenamine, 4-(4-aminophenoxy)-3-phenylbenzenamine, 4-(4-aminophenoxy)-2 -phenylbenzenamine, 4-(4-aminophenoxy)-3-methylphenylbenzenamine, 4-(4-aminophenoxy)-2-methylphenylbenzenamine, 4-(4-aminophenoxy)-3-ethylphenylbenzenamine, 4-(4-aminophenoxy)-2-ethylphenylbenzenamine, 4-(4-aminophenoxy)-3-propylphenylbenzenamine, 4-(4-aminophenoxy)-2-propylphenylbenzenamine, 4-(4-aminophenoxy)-3-butylphenylbenzenamine, 4-(4-aminophenoxy)-3-propylphenylbenzenamine, 4-(4-aminophenoxy)-2-butylphenylbenzenamine, 4-(4-aminophenoxy)-3-fluorophenylbenzenamine, 4-(4-aminophenoxy)-2-fluorophenylbenzenamine, 4-(4-aminophenoxy)-3-chlorophenylbenzenamine, 4-(4-aminophenoxy)-2-chlorophenylbenzenamine, 4-(4-aminophenoxy)-3-bromophenylbenzenamine, 4-(4-aminophenoxy)-2-bromophenylbenzenamine, 4-(4-aminophenoxy)-3-methoxyphenylbenzenamine,4-(4-aminophenoxy)-2-methoxyphenylbenzenamine, 4-(4-aminophenoxy)-3-ethoxyphenylbenzenamine, 4-(4-aminophenoxy)-2-ethoxyphenylbenzenamine, 4-(4-aminophenoxy)-3-(phenylethyl)phenylbenzenamine, 4-(4-aminophenoxy)-2-(phenylethyl)phenylbenzenamine, 4-(4-aminophenoxy)-3-naphthylphenylbenzenamine, 4-(4-aminophenoxy)-2-naphthylphenylbenzenamine, 4-(4-amino phenoxy)-3-benzylphenylbenzenamine, 4-(4-aminophenoxy)-2-benzylphenylbenzenamine, 4-((4-aminophenyl)thio)-3-methylbenzenamine, 4-((4-aminophenyl)thio)-2-methylbenzenamine, 4-((4-aminophenyl)thio)-3-ethylbenzenamine, 4-((4-aminophenyl)thio)-2-ethylbenzenamine, 4-((4-aminophenyl)thio)-3-propylbenzenamine, 4-((4-aminophenyl)thio)-2-propylbenzenamine, 4-(( 4-aminophenyl)thio)-3-isopropylbenzenamine, 4-((4-aminophenyl)thio)-2-isopropylbenzenamine, 4-((4-aminophenyl)thio)-3-butylbenzenamine, 4-((4-aminophenyl)thio)-2-butylbenzenamine, 4-((4-aminophenyl)thio)-3-isobutylbenzenamine, 4-((4-aminophenyl)thio)-2-isobutylbenzenamine, 4-((4-aminophenyl)thio)-3-(trifluoromethyl)benzenamine, 4-((4-aminophenyl)thio)- 2-(trifluoromethyl)benzenamine, 4-((4-aminophenyl)thio)-3-methoxybenzenamine, 4-((4-aminophenyl)thio)-2-methoxybenzenamine, 4-((4-aminophenyl)thio)-3-ethoxybenzenamine, 4-((4-aminophenyl)thio)-2-ethoxybenzenamine, 4-((4-aminophenyl)thio)-3-propoxybenzenamine, 4-((4-aminophenyl)thio)-2-propoxybenzenamine, 4-((4-aminophenyl)thio)-3-isopropoxybenzenamine,4-((4-aminophenyl)thio)-2-isopropoxybenzenamine, 4-((4-aminophenyl)thio)-3-butoxybenzenamine, 4-((4-aminophenyl)thio)-2-butoxybenzenamine, 4-((4-aminophenyl)thio)-3-phenylbenzenamine, 4-((4-aminophenyl)thio)-2-phenylbenzenamine, 4-((4-aminophenyl)thio)-3-naphthylbenzenamine, 4-((4-aminophenyl)thio)-2-naphthylbenzenamine, 4-((4-aminophenyl)thio )-3-methoxyphenylbenzenamine, 4-((4-aminophenyl)thio)-2-methoxyphenylbenzenamine, 4-((4-aminophenyl)methyl)-3-methylbenzenamine, 4-((4-aminophenyl)methyl)-2-methylbenzenamine, 4-((4-aminophenyl)methyl)-3-ethylbenzenamine, 4-((4-aminophenyl)methyl)-2-ethylbenzenamine, 4-((4-aminophenyl)methyl)-3-propylbenzenamine, 4-((4-aminophenyl)methyl)-2-propylbenzenamine benzophenoneamine, 4-((4-aminophenyl)methyl)-3-isopropylbenzophenoneamine, 4-((4-aminophenyl)methyl)-2-isopropylbenzophenoneamine, 4-((4-aminophenyl)methyl)-3-butylbenzophenoneamine, 4-((4-aminophenyl)methyl)-2-butylbenzophenoneamine, 4-((4-aminophenyl)methyl)-3-isobutylbenzophenoneamine, 4-((4-aminophenyl)methyl)-2-isobutylbenzophenoneamine, 4-((4-aminophenyl)methyl)-3-(trifluoromethyl)benzophenone amine, 4-((4-aminophenyl)methyl)-2-(trifluoromethyl)benzenamine, 4-((4-aminophenyl)methyl)-3-methoxybenzenamine, 4-((4-aminophenyl)methyl)-2-methoxybenzenamine, 4-((4-aminophenyl)methyl)-3-ethoxybenzenamine, 4-((4-aminophenyl)methyl)-2-ethoxybenzenamine, 4-((4-aminophenyl)methyl)-3-propoxybenzenamine, 4-((4-aminophenyl)methyl)-2-propoxybenzenamine,4-((4-aminophenyl)methyl)-3-isopropoxybenzenamine, 4-((4-aminophenyl)methyl)-2-isopropoxybenzenamine, 4-((4-aminophenyl)methyl)-3-butoxybenzenamine, 4-((4-aminophenyl)methyl)-2-butoxybenzenamine, 4-((4-aminophenyl)methyl)-3-phenylbenzenamine, 4-((4-aminophenyl)methyl)-2-phenylbenzenamine, 4-((4-aminophenyl)methyl)-3-naphthylbenzenamine, 4-((4-aminophenyl)methyl)-2-naphthylbenzenamine, 4-((4-aminophenyl)methyl)-3-methoxyphenylbenzenamine, 4-((4-aminophenyl)methyl)-2-methoxyphenylbenzenamine, (4-amino-2-methylphenyl Examples of suitable phenyl phenyl (4-aminophenyl)methanone include, but are not limited to, (4-amino-2-ethylphenyl)(4-aminophenyl)methanone, (4-amino-2-propylphenyl)(4-aminophenyl)methanone, (4-amino-2-isopropylphenyl)(4-aminophenyl)methanone, (4-amino-2-butylphenyl)(4-aminophenyl)methanone, (4-amino-2-(trifluoromethyl)phenyl)(4-aminophenyl)methanone, 4-amino-2-methoxyphenyl)(4-aminophenyl)methanone, 4-amino-2-ethoxyphenyl)(4-aminophenyl)methanone, (4-amino-2-(phenyl)phenyl)(4-aminophenyl)methanone, and (4-amino-2-(methoxyphenyl)phenyl)(4-aminophenyl)methanone.

[0087] Here, a polymer having a polyimide precursor containing a structural unit represented by the general formula (1) can be obtained, for example, by reacting a tetracarboxylic acid diester compound represented by the general formula (12) with a diamine represented by the general formula (13) in the presence of a dehydrating condensation agent. That is, the tetracarboxylic acid diester compound represented by the general formula (12) is used in the reaction in a state of being dissolved in the reaction solvent, and a known dehydration condensation agent (e.g., dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc.) is added to and mixed with this reaction solution under ice cooling to convert the tetracarboxylic acid diester compound represented by the general formula (12) into a polyanhydride, and then a diamine represented by the general formula (13) dissolved or dispersed in a separate solvent is added dropwise to the polyanhydride to carry out polycondensation, thereby obtaining a polymer having a polyimide precursor containing a structural unit represented by the general formula (1).

[0088] Another method for obtaining a polymer having a polyimide precursor containing a structural unit represented by the general formula (1) by reacting a tetracarboxylic acid diester compound represented by the general formula (12) with a diamine compound represented by the general formula (13) includes converting the tetracarboxylic acid diester compound represented by the general formula (12) into an acid chloride using a chlorinating agent such as thionyl chloride or dichlorooxalic acid, and reacting the acid chloride with the diamine represented by the general formula (13).

[0089] In the reaction of converting the above-mentioned tetracarboxylic acid diester compound into an acid chloride using a chlorinating agent, a basic compound such as pyridine, 4-dimethylaminopyridine, or triethylamine may be used.

[0090] The acid chloride of the resulting tetracarboxylic acid diester compound is then reacted with the diamine represented by the general formula (13) in the presence of a basic catalyst to obtain a polymer having a polyimide precursor containing the structural unit represented by the general formula (1). Examples of the basic catalyst include pyridine, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[4.3.0]non-5-ene.

[0091] Among the methods for producing a polymer having a polyimide precursor of the present invention, the method using an acid chloride is preferably one that can dissolve the above-mentioned tetracarboxylic acid diester compound, its acid chloride, and the polyimide precursor polymer obtained by polycondensation with a diamine. Solvents similar to those described above can be used. Specific examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, and γ-butyrolactone. In addition to polar solvents, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons can also be used. Examples of the organic solvent include acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, etc. These organic solvents may be used alone or in combination of two or more.

[0092] As described above, the polymer of the present invention may further contain a structural unit represented by the following general formula (4) in addition to the structural unit represented by the above general formula (1). [ka] (In the formula, X2, X3, Ra, and Rb are the same as above.)

[0093] A polymer containing the structural unit represented by the general formula (4) can be obtained by the same reaction procedure as that for the structural unit (1), namely, by reacting a tetracarboxylic acid diester compound represented by the following general formula (16) in the presence of a dehydration condensation agent or by converting it into an acid chloride using a chlorinating agent, and then reacting it with a diamine represented by the following general formula (17). [ka] (In the formula, X 2、 Ra and Rb are the same as above.) [ka] (wherein X3 is the same as defined above.)

[0094] The tetracarboxylic acid diester compound represented by the general formula (16) can be produced by the same reaction procedure as that of the general formula (12). That is, one example is a method of introducing Ra and Rb by reacting a tetracarboxylic acid dianhydride represented by the following general formula (18) with a compound having a terminal hydroxyl group represented by the general formula (15) or a linear, branched, or cyclic alcohol having 1 to 6 carbon atoms in the presence of a basic catalyst such as pyridine. Here, the tetracarboxylic acid dianhydride represented by the following general formula (18) is the source of X2 in the general formula (4) (for example, the tetravalent organic group represented by the formula (3)). [ka] (wherein X2 is the same as defined above).

[0095] As the tetracarboxylic dianhydride represented by the above general formula (18), the examples given for the tetracarboxylic dianhydride represented by the above general formula (14) can be mentioned as suitable examples.

[0096] Examples of the diamine represented by the general formula (17) include aromatic diamines, alicyclic diamines, aliphatic diamines, and polyether diamines.

[0097] Preferred examples of aromatic diamines include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzidine, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2'3,3'-tetramethylbenzidine, 2,2'-dichlorobenzidine, 3,3'-dichlorobenzidine, 2,2'3,3'-tetrachlorobenzidine, m-phenoxybenzidine, 2,2'-bis(trifluoromethyl) ...bis(trifluoromethyl)benzidine, 2,2'-bis(trifluoromethyl)benzidine, 2,2'-bis(trifluoromethyl)benzidine, 2,2'-bis(trifluoromethyl)benzidine, 2,2'-bis(trifluoromethyl)benzidine, 2,2'-bis(trifluoromethyl)benzidine, 2, Examples of the diamine compound include, but are not limited to, phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)fluorene, 2,2'-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminobenzanilide, and diamine compounds in which the aromatic ring of these compounds is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

[0098] Examples of alicyclic diamines include cyclobutanediamine, isophoronediamine, bicyclo[2,2,1]heptanebismethylamine, tricyclo[3,3,1,1] 3,7]Decane-1,3-diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-diaminocyclohexane, trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5 '-tetramethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexylmethane, 3,5-diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, 3,3'-dimethyl-4,4'-diaminodicyclohexyl ether, 3,3'-diethyl-4,4'-diaminodicyclohexyl ether, 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexyl ether, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexyl ether, 3,5-diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexyl ether, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(3-methyl-4-aminocyclohexyl)propane, 2,2-bis(3-ethyl-4-aminocyclohexyl)propane Examples of the alicyclic amine compounds include, but are not limited to, 2,2-bis(3,5-dimethyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-diethyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexyl)propane, and diamine compounds in which the alicyclic ring of these amine compounds is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

[0099] Examples of aliphatic diamines include alkylenediamines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane; siloxane diamines such as bis(aminomethyl)ether, bis(2-aminoethyl)ether, and 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, and α,ω-bis(3-aminopropyl)polydimethylsiloxane; but are not limited to these.

[0100] Examples of polyether diamines include, but are not limited to, 1,2-bis(aminoethoxy)ethane, HK-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-230, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009, RT-1000, HE-1000, and HT-1700 (all trade names, manufactured by HUNTSMAN Co., Ltd.). These may be used alone or in combination.

[0101] These aromatic diamines, alicyclic diamines, aliphatic diamines, and polyether diamines can be used alone or in combination of two or more.

[0102] Siloxane diamines can also be suitably used.

[0103] As described above, the polymer of the present invention can further contain a structural unit represented by the following general formula (5) in addition to the structural unit represented by the above general formula (1). [ka] (In the formula, X4 and X5 are the same as above.)

[0104] A polymer containing the structural unit represented by the general formula (5) can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (19) with a diamine represented by the following general formula (20): First, a tetracarboxylic dianhydride represented by the following general formula (19) is reacted with a diamine represented by the following general formula (20) to synthesize an amide acid, and then the amide acid is imidized by chemical imidization or thermal dehydration to obtain a polymer containing the structural unit (5).

[0105] The structural unit (5) can be produced by dissolving a diamine represented by the following general formula (20) in a solvent having a high boiling point and high polarity, such as γ-butyrolactone or N-methyl-2-pyrrolidone, adding a tetracarboxylic dianhydride represented by the following general formula (19), and reacting the resulting mixture at 0 to 80°C, preferably 10 to 50°C, to form an amide acid. In the case of chemical imidization, for example, acetic anhydride and pyridine are added to the resulting mixture, or in the case of imidization by thermal dehydration, a nonpolar solvent such as xylene is added, and the mixture is heated to 100 to 200°C, preferably 130 to 180°C, to carry out the imidization reaction while removing water from the reaction system. [ka] (In the formula, X4 is the same as above.) [ka] (In the formula, X5 is the same as above.)

[0106] As the tetracarboxylic dianhydride represented by the above general formula (19), the examples given for the tetracarboxylic dianhydride represented by the above general formula (14) can be mentioned as suitable examples.

[0107] As the diamine represented by the above general formula (20), the examples of the diamine represented by the above general formula (17) can be mentioned as suitable examples.

[0108] As described above, the polymer of the present invention can further contain a structural unit represented by the following general formula (6) in addition to the structural unit represented by the above general formula (1). [ka] (In the formula, X6 and X7 are the same as above.)

[0109] A polymer containing the structural unit represented by the general formula (6) can be obtained by the same reaction procedure as that for the structural unit (1), namely, by reacting a dicarboxylic acid compound represented by the following general formula (21) in the presence of a dehydration condensation agent or by converting it into an acid chloride using a chlorinating agent, and then reacting the resulting compound with a diamine represented by the general formula (22). [ka] (wherein X6 is the same as above). [ka] (wherein X7 is the same as defined above.)

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

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

[0112] As the diamine represented by the above general formula (22), the examples given for the diamine represented by the above general formula (17) can be mentioned as suitable examples.

[0113] As described above, the polymer of the present invention may further contain a structural unit represented by the following general formula (7) in addition to the structural unit represented by the above general formula (1). [ka] (In the formula, X8 and X9 are the same as above.)

[0114] The polymer containing the structural unit represented by the general formula (7) can be obtained by reacting a dicarboxylic acid compound represented by the following general formula (23) in the presence of a dehydrating condensation agent or by converting it into an acid chloride using a chlorinating agent, and then reacting it with a dihydroxydiamine compound represented by the following general formula (24) to synthesize a hydroxyamide (polyoxazole precursor), which is then subjected to a thermal dehydration step to form an oxazole ring. [ka] (wherein X8 is the same as defined above.) [ka] (In the formula, X9 is the same as above.)

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

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

[0117] (Polymer molecular weight and introduction of end-capping agent) The polymer preferably has a molecular weight of 5,000 to 100,000, more preferably 7,000 to 50,000. If the molecular weight is 5,000 or more, the negative-type photosensitive resin composition of the present invention using the polymer can be formed into a film of a desired thickness on a substrate without any problems. If the molecular weight is 100,000 or less, the viscosity of the negative-type photosensitive resin composition becomes appropriate, and there is no problem in forming a film.

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

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

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

[0121] Examples of acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds that can be used as the amino group terminal capping agents include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-Hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene Phthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid Monocarboxylic acids such as 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid, and 8-ethynyl-2-naphthoic acid, and monoacid chloride compounds in which the carboxy group of these acids is converted into an acid chloride, as well as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,Examples of such compounds include monoacid chloride compounds in which only the monocarboxy group of dicarboxylic acids such as 3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, and 2,7-dicarboxynaphthalene is converted to an acid chloride, and monoactive ester compounds obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide.

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

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

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

[0125] The introduction ratio of the acid anhydride terminal-capping agent is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, and even more preferably 5 to 20 mol%, based on the total amount of the tetracarboxylic dianhydride component and the dicarboxylic acid component. The introduction ratio of the amino terminal-capping agent is preferably in the range of 0.1 to 100 mol%, particularly preferably 5 to 90 mol%, based on the diamine component. Multiple different terminal groups may be introduced by reacting multiple terminal-capping agents.

[0126] [Negative-type photosensitive resin composition] Next, a photosensitive resin composition using a polymer having a polyimide precursor of the present invention as a base resin will be described. In the present invention, a negative photosensitive resin composition can be obtained by using the above-mentioned polymer having a polyimide precursor of the present invention as a base resin. Hereinafter, a photosensitive resin composition using a polymer having a polyimide precursor of the present invention as a base resin will be described, specifically, a negative photosensitive resin composition that can form a negative pattern and can be developed with an organic solvent, but is not limited thereto.

[0127] The negative photosensitive resin composition of the present invention comprises: (A) a polymer having a polyimide precursor containing a structural unit represented by the general formula (1), (B) a photoradical initiator, and (E) solvent, The negative photosensitive resin composition comprises:

[0128] The component (A) in the negative-type photosensitive resin composition of the present invention is a polymer having a polyimide precursor containing a structural unit represented by the above general formula (1) (i.e., a polymer containing the structural unit (1)). Because this polymer has a polymerizable unsaturated bond group in the molecule, a negative-type photosensitive resin composition can be obtained by combining this polymer with a photoradical initiator.

[0129] The component (B) in the negative-type photosensitive resin composition of the present invention is a photoradical initiator. The photoradical initiator can be selected from any of the compounds conventionally used as photopolymerization initiators for UV curing. Examples of photoradical initiators include benzophenone derivatives such as benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzil derivatives such as benzil, benzil dimethyl ketal, and benzyl β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; and 1-phenyl-1 Preferred examples of the photoradical initiator include, but are not limited to, oximes such as 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-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride; and aromatic biimidazoles. These may be used alone or in combination. Among the above photoradical initiators, oximes are more preferred, particularly in terms of photosensitivity.

[0130] The blending amount of component (B) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polymer having the polyimide precursor of the present invention (component (A)), and from the viewpoint of photosensitivity characteristics, more preferably 2 to 15 parts by mass. By blending 0.1 part by mass or more of component (B) relative to 100 parts by mass of component (A), the resulting negative-type photosensitive resin composition has excellent photosensitivity, while by blending 20 parts by mass or less, the resulting negative-type photosensitive resin composition has excellent thick-film curing properties.

[0131] Next, component (E) in the negative photosensitive resin composition of the present invention is a solvent. There are no limitations on the solvent for component (E), so long as it dissolves components (A) and (B). Examples of solvents include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-amyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and propylene glycol monomethyl ether. Examples of suitable solvents include esters such as tert-butyl acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone; and amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, and N,N-dimethylformamide. One or more of these solvents may be used. Particularly preferred are ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, N-methyl-2-pyrrolidone, and mixed solvents thereof.

[0132] The blend amount of component (E) is preferably 50 to 2,000 parts by mass, and particularly preferably 100 to 1,000 parts by mass, per 100 parts by mass of the combined blend amounts of components (A) and (B).

[0133] The negative photosensitive resin composition of the present invention further comprises, as component (C), (C) a crosslinking agent having two or more photopolymerizable unsaturated bond groups in one molecule may include:

[0134] Inclusion of a crosslinking agent having two or more photopolymerizable unsaturated bonds in one molecule in this manner can promote crosslinking by photopolymerization of component (A) in the exposed areas, thereby improving the contrast between the exposed and unexposed areas.

[0135] The component (C) of the negative photosensitive resin composition of the present invention is a crosslinking agent having two or more photopolymerizable unsaturated bond groups in one molecule. The crosslinking agent having two or more photopolymerizable unsaturated bond groups in one molecule is preferably a (meth)acrylic compound, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate (each having 2 to 20 ethylene glycol units), polyethylene glycol dimethacrylate (each having 2 to 20 ethylene glycol units), poly(1,2-propylene glycol) diacrylate, poly(1,2-propylene glycol) dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolpropane tetraacrylate, tetraethylene glycol di ... diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, glycerol diacrylate, glycerol dimethacrylate, methylenebisacrylamide, N-methylolacrylamide, ethylene glycol diglycidyl ether-methacrylic acid adduct, glycerol diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-methacrylic acid adduct, N,N'-bis(2-methacryloyloxyethyl)urea, and the like are preferred, but are not limited to these.

[0136] The component (C) is preferably blended in an amount of 1 to 100 parts by mass, more preferably 3 to 50 parts by mass, per 100 parts by mass of the component (A). When the amount is in the range of 1 to 100 parts by mass, the desired effect can be sufficiently obtained without adversely affecting the developability. As the copolymerizable monomer, one type of compound may be used, or several types may be mixed and used.

[0137] The negative-type photosensitive resin composition of the present invention may further contain, as a thermal crosslinking agent (D) component, one or more crosslinking agents selected from the group consisting of amino condensates modified with formaldehyde or formaldehyde-alcohol, phenol compounds having an average of two or more methylol groups or alkoxymethylol groups per molecule, compounds in which the hydrogen atoms of hydroxyl groups of polyhydric phenols are substituted with glycidyl groups, compounds in which the hydrogen atoms of hydroxyl groups of polyhydric phenols or hydroxyl groups of polyhydric alcohols are substituted with substituents represented by the following formula (D-1), and compounds containing two or more nitrogen atoms and having glycidyl groups represented by the following formula (D-2). [ka] (In the formula, the dotted line represents a bond, Rf represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.)

[0138] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include a melamine condensate modified with formaldehyde or formaldehyde-alcohol, and a urea condensate modified with formaldehyde or formaldehyde-alcohol.

[0139] The melamine condensate modified with formaldehyde or formaldehyde-alcohol can be prepared, for example, by first modifying a melamine monomer with formalin by methylolation according to a known method, or by further modifying the melamine monomer by alkoxylation with an alcohol to obtain a modified melamine represented by the following general formula (25): The alcohol is preferably a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms.

[0140] [ka] (In the formula, R5 may be the same or different and is a methylol group, an alkoxymethyl group including an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, provided that at least one R5 is a methylol group or the above alkoxymethyl group.) Examples of R5 include alkoxymethyl groups such as a methylol group, a methoxymethyl group, and an ethoxymethyl group, and a hydrogen atom.

[0141] Specific examples of modified melamine represented by the general formula (25) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethylol melamine, etc. Next, the modified melamine represented by the general formula (25) or a multimer thereof (for example, an oligomer such as a dimer or trimer) is subjected to addition condensation polymerization with formaldehyde according to a conventional method until a desired molecular weight is reached, thereby obtaining a melamine condensate modified with formaldehyde or formaldehyde-alcohol.

[0142] The above-mentioned urea condensate modified with formaldehyde or formaldehyde-alcohol can be prepared, for example, by methylolating a urea condensate having a desired molecular weight with formaldehyde to modify it, or by further alkoxylating it with an alcohol to modify it, according to a known method. Specific examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, and propoxymethylated urea condensate. The modified melamine condensates and modified urea condensates may be used alone or in combination of two or more.

[0143] Next, examples of phenol compounds having an average of two or more methylol groups or alkoxymethylol groups per molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and compounds represented by the following formulas (D-3) to (D-8). [ka]

[0144] The above crosslinking agents can be used alone or in combination of two or more.

[0145] On the other hand, examples of compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are substituted with glycidyl groups include compounds obtained by reacting the hydroxyl groups of bisphenol A, tris(4-hydroxyphenyl)methane, and 1,1,1-tris(4-hydroxyphenyl)ethane with epichlorohydrin in the presence of a base. Suitable examples of compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are substituted with glycidyl groups include the compounds represented by the following formulas (D-9) to (D-15). [ka] (wherein t is 2≦t≦3.)

[0146] Furthermore, preferred examples of compounds other than those represented by the above formulas (D-9) to (D-15) include Epicron 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron EXA-4710, Epicron HP-4770, Epicron EXA-859CRP, Epicron EXA-4880, Examples of suitable inks include Epicron EXA-4850, Epicron EXA-4816, and Epicron EXA-4822 (all trade names, manufactured by Dainippon Ink and Chemicals, Inc.), Rikaresin BPO-20E and Rikaresin BEO-60E (all trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4000S, and EP-4000L (all trade names, manufactured by Adeka Corporation), and jER828EL and YX7105 (all trade names, manufactured by Mitsubishi Chemical Corporation).

[0147] One or two of these compounds in which the hydroxyl groups of polyhydric phenols are substituted with glycidoxy groups (compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are substituted with glycidyl groups) can be used as the crosslinking agent.

[0148] Examples of compounds in which the hydrogen atoms of the hydroxyl groups of a polyhydric phenol are substituted with substituents represented by the following formula (D-1) include compounds containing two or more of the substituents and represented by the following formula (D-16). [ka] (In the formula, dotted lines indicate bonds.) [ka] (wherein 1≦u≦3.)

[0149] Furthermore, preferred examples of compounds other than those represented by the above formulas (D-9) to (D-15) include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, and the Aronoxetane series manufactured by Toagosei Co., Ltd.

[0150] On the other hand, examples of the compound containing two or more nitrogen atoms having a glycidyl group, represented by the following formula (D-2), include those represented by the following formula (D-17). [ka] (In the formula, the dotted line represents a bond, Rf represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.) [ka] (In the formula, W represents a linear, branched, or cyclic alkylene group having 2 to 12 carbon atoms, or a divalent aromatic group. Note that W here applies only to the above formula.)

[0151] Examples of the compound represented by the above formula (D-17) include compounds represented by the following formulae (D-18) to (D-21). [ka]

[0152] On the other hand, as the compound containing two or more nitrogen atoms having a glycidyl group represented by the above formula (D-2), compounds represented by the following formulas (D-22) and (D-23) can be suitably used. [ka]

[0153] One or two of these compounds containing two or more nitrogen atoms having a glycidyl group, as represented by the above formula (D-2), can be used as the crosslinking agent.

[0154] The epoxy group has a large ring distortion and is highly reactive, but the oxetane is highly basic and does not bond with acids. The reactivity of cationic polymerization is improved by combining an oxetanyl group with an epoxy group. Significant improvements have been reported.

[0155] Component (D) is a component that undergoes a crosslinking reaction during post-curing after pattern formation of the negative-type photosensitive resin composition of the present invention, thereby further increasing the strength of the cured product. From the viewpoints of photocurability and heat resistance, the weight-average molecular weight of such component (D) is preferably 150 to 10,000, and particularly preferably 200 to 3,000.

[0156] The amount of component (D) blended in the negative photosensitive resin composition of the present invention is preferably 0.5 to 100 parts by mass, and particularly preferably 1 to 80 parts by mass, per 100 parts by mass of component (A).

[0157] Furthermore, the negative-type photosensitive resin composition of the present invention may further contain, in addition to the components (A), (B), (C), (D), and (E), one or more selected from the group consisting of (F) a protected amine compound, (G) a thermal acid generator, (H) an antioxidant, and (I) a silane compound.

[0158] The negative-type photosensitive resin composition of the present invention can further contain a protected amine compound (F) in addition to the above components (A), (B), (C), (D), and (E). The protected amine compound (F) can be any nitrogen-containing organic compound in which a group that can be deprotected by heat or acid is bonded to a nitrogen atom. In particular, there are no particular limitations on the protected amine compound as long as it has a carbamate structure represented by the following general formula (26) or (27): [ka] where R 1 , R 2 , R 3 and R 4 each independently represents hydrogen, an optionally substituted alkyl group of 1 to 8 carbon atoms, an optionally substituted cycloalkyl group of 3 to 8 carbon atoms, an optionally substituted alkoxyl group of 1 to 8 carbon atoms, an optionally substituted alkenyl group of 2 to 8 carbon atoms, an optionally substituted alkynyl group of 2 to 8 carbon atoms, an optionally substituted aryl group, or an optionally substituted heterocyclic group; R 5 and R 6 each independently represents hydrogen, an alkyl group of 1 to 8 carbon atoms which may have a substituent, a cycloalkyl group of 3 to 8 carbon atoms which may have a substituent, an alkoxyl group of 1 to 8 carbon atoms which may have a substituent, an alkenyl group of 2 to 8 carbon atoms which may have a substituent, an alkynyl group of 2 to 8 carbon atoms which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a monocyclic ring which is bonded to each other and may have a substituent, or a polycyclic ring which is bonded to each other and may have a substituent (provided that the total number of carbon atoms in the formula is 10 or less). Also, R 7represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 12 carbon atoms which may have a substituent, an alkynyl group having 2 to 12 carbon atoms which may have a substituent, an aryl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, an aralkyl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, or a heterocyclic group which may have a substituent. (However, R 7 The total number of carbon atoms constituting the group is 12 or less.) Any substituent may be used as the substituent that the above group may have, as long as it does not go against the spirit of the present invention.

[0159] [ka]

[0160] Specific examples of the above formulas (26) and (27) include the following: N-(isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(isopropoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(isopropoxycarbonyl)diisopropylamine, N-(isopropoxycarbonyl)pyrrolidine, N-(isopropoxycarbonyl)-2,5-dimethylpyrrolidine, N-(isopropoxycarbonyl)-azetidine, N-(1-ethylpropoxycarbonyl)-2,6-dimethylpiperidine, N-(1-ethyl ...-2,5-dimethylpyrrolidine, N-(isopropoxycarbonyl)-azetidine, N-(1-ethylpropoxycarbonyl)-2,5-dimethylpyrrolidine, N-(1-ethylpropoxycarbonyl)-azetidine, N-(1-ethylpropoxycarbonyl)-2,5-dimethylpyrrolidine, N-(1-ethylpropoxycarbonyl)-azetidine, N-(1-ethylpropoxycarbonyl)-2,5-dimethylpyrrolidine, N-(1-ethylpropoxycarbonyl)-azetidine, N-(1-ethylpropoxycarbonyl)-azetidine, N-(1-ethylpropoxycarbonyl)-azetidine, N-(1-ethylpropoxycarbonyl)-azetidine, N-(1-ethylpropoxycarbonyl)-azetidine, N-(1-ethylpropoxycarbonyl)-azetidine, N tetramethylpiperidine, N-(1-ethylpropoxycarbonyl)diisopropylamine, N-(1-ethylpropoxycarbonyl)pyrrolidine, N-(1-ethylpropoxycarbonyl)-2,5-dimethylpyrrolidine, N-(1-ethylpropoxycarbonyl)-azetidine, N-(1-propylbutoxycarbonyl)-2,6-dimethylpiperidine, N-(1-propylbutoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(1-propylbutoxycarbonyl)diisopropylamine, N-(1-propylbutoxycarbonyl)- N-(cyclopentoxycarbonyl)pyrrolidine, N-(1-propylbutoxycarbonyl)-2,5-dimethylpyrrolidine, N-(1-propylbutoxycarbonyl)-azetidine, N-(cyclopentoxycarbonyl)-2,6-dimethylpiperidine, N-(cyclopentoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(cyclopentoxycarbonyl)diisopropylamine, N-(cyclopentoxycarbonyl)pyrrolidine, N-(cyclopentoxycarbonyl)-2,5-dimethylpyrrolidine, N-(cyclopentoxycarbonyl) N-(cyclohexylcarbonyl)azetidine, N-(cyclohexylcarbonyl)-2,6-dimethylpiperidine, N-(cyclohexylcarbonyl)-2,2,6,6-tetramethylpiperidine, N-(cyclohexylcarbonyl)diisopropylamine, N-(cyclohexylcarbonyl)pyrrolidine, N-(cyclohexylcarbonyl)-2,5-dimethylpyrrolidine, N-(cyclohexylcarbonyl)azetidine, N-(tert-butoxycarbonyl)-2,6-dimethylpiperidine, N-(tert-butoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(tert-butoxycarbonyl)diisopropylamine, N-(tert-butoxycarbonyl)pyrrolidine, N-(tert-butoxycarbonyl)-2,5-dimethylpyrrolidine, N-(tert-butoxycarbonyl)-azetidine, N-(benzyloxycarbonyl)-2,6-dimethylpiperidine, N-(benzyloxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(benzyloxycarbonyl)diisopropylamine, N-(benzyloxycarbonyl)pyrrolidine, N-(benzyloxycarbonyl)-2,5-dimethylpyrrolidine, N-(benzyloxycarbonyl)-azetidine, 1,4-bis(N,N'-diisopropylaminocarbonyloxy)cyclohexane, and the imidazole compounds described in Japanese Patent No. 5609815.

[0161] It is particularly preferred that the protected amine compound according to this embodiment is one that is 100% decomposed at 200°C or less. This makes it possible to more efficiently generate a base compound and promote the imidization of the polyimide precursor or the crosslinking reaction between the thermal crosslinking agent and the resin. The boiling point of the base and other decomposition products obtained by heating the protected amine compound at 1 atmosphere (0.1 GPa) is preferably 200°C or less. This is because setting the boiling point at 200°C or less allows the decomposition products to be volatilized from the coating film in a low-temperature process. There is no particular restriction on the lower limit of the boiling point of the decomposition products at 1 atmosphere, but from the viewpoint of ease of synthesis of the protected amine compound, it is preferred to use a protected amine compound that is -150°C or higher.

[0162] If an amine compound is directly added to the photosensitive resin composition of the present invention, the crosslinking agent (D) and the amine compound may react at room temperature, causing the viscosity of the composition to increase over time and resulting in a deterioration in storage stability. On the other hand, if the basicity of the amine compound is protected by a protecting group, the amine compound will not react with component (D) at room temperature, just as it does when not heated, thereby improving the storage stability of the photosensitive resin composition over time. Furthermore, since a base is generated only upon heating, it can act as a catalyst for the imide ring-closing reaction and the reaction between the polymer (A) and the crosslinking agent (D), effectively promoting the crosslinking reaction.

[0163] The amount of the protected amine compound is preferably 0 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the polymer of component (A). If the amount exceeds 10 parts by mass, the solubility of the composition decreases, and the lithographic patterning properties deteriorate.

[0164] The negative-type photosensitive resin composition of the present invention may further contain (G) a thermal acid generator in addition to the above-mentioned components (A), (B), (C), (D), and (E). The component (G), a compound that generates an acid when heated, may be added for the purpose of thermally promoting imide ring closure and promoting the crosslinking reaction between components (A) and (D) in the step of heating and post-curing at a temperature of 100 to 300°C after the pattern formation.

[0165] In particular, component (G) is preferably one that does not promote film curing until a pattern is formed by development and does not inhibit pattern formation. To achieve this, component (G) is preferably one that does not generate acid at the temperatures used in the processes of removing the solvent and drying after coating the photosensitive resin composition, but generates acid only upon heat treatment after pattern formation, thereby promoting the curing of the pattern or coating of the negative-type photosensitive resin composition. Specifically, component (G) is preferably a compound that decomposes and generates acid upon heat treatment at 100°C to 300°C, preferably 150°C to 300°C. By including such component (G), the pattern or coating of the negative-type photosensitive resin composition can be transformed into a pattern or coating with a more advanced crosslinking and curing reaction during the heating and post-curing process at a temperature of 100°C to 300°C after pattern formation. Component (G) further promotes the crosslinking and curing reaction, thereby further improving the mechanical strength, chemical resistance, adhesion, etc. of the resulting pattern or coating.

[0166] The compound that generates an acid when exposed to suitable heat is not particularly limited, but for example, the compounds described in paragraphs

[0061] to

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

[0167] The amount of the compound that generates an acid upon heating is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, per 100 parts by mass of the polymer of component (A) in the negative-type photosensitive resin composition of the present invention.

[0168] The negative-type photosensitive resin composition of the present invention may further contain (H) an antioxidant in addition to the above-described components (A), (B), (C), (D), and (E). The inclusion of the antioxidant (H) can suppress unnecessary crosslinking between components (A) themselves or between components (A) and (C) during patterning, thereby improving contrast. Furthermore, its rust-preventing effect on metal materials can suppress metal oxidation caused by external moisture, photoacid generators, thermal acid generators, etc., as well as the resulting loss of adhesion and peeling.

[0169] Specific examples of the (H) antioxidant that can be used include, but are not limited to, hindered phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. These (H) antioxidants can be used alone or in combination of two or more.

[0170] Among the specific examples of the antioxidant (H), further examples of hindered phenol-based antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan Ltd., Irganox 1010 (trade name)), thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan Ltd., Irganox 1035 (trade name)), octadecyl [3- (3,5-di-tert-butyl-4-hydroxyphenyl)propionate (BASF Japan Ltd., Irganox 1076 (trade name)), octyl 1-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate (BASF Japan Ltd., Irganox 1135 (trade name)), 4,6-bis(octylthiomethyl-o-cresol) (BASF Japan Ltd., Irganox 1520L), Sumilizer GA80 (Sumitomo Chemical Co., Ltd., trade name), ADK STAB Examples of the antioxidant include AO-20 (manufactured by ADEKA Corporation, trade name), ADK STAB AO-30 (manufactured by ADEKA Corporation, trade name), ADK STAB AO-40 (manufactured by ADEKA Corporation, trade name), ADK STAB AO-50 (manufactured by ADEKA Corporation, trade name), ADK STAB AO-60 (manufactured by ADEKA Corporation, trade name), ADK STAB AO-80 (manufactured by ADEKA Corporation, trade name), ADK STAB AO-330 (manufactured by ADEKA Corporation, trade name), and the hindered phenol-based antioxidants described in WO 2017 / 188153.

[0171] Among the specific examples of the antioxidant (H), further examples of phosphorus-based antioxidants include triphenyl phosphite, tris(methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tris(nonylphenyl) phosphite, tris(octylphenyl) phosphite, tris[decylpoly(oxyethylene) phosphite, tris(cyclohexylphenyl) phosphite, tricyclohexyl phosphite, tri(decyl)thiophosphite, triisodecylthiophosphite, phenyl-bis(2 -ethylhexyl)phosphite, phenyl-diisodecylphosphite, tetradecylpoly(oxyethylene)-bis(ethylphenyl)phosphat, phenyl-dicyclohexylphosphite, phenyl-diisooctylphosphite, phenyl-di(tridecyl)phosphite, diphenyl-cyclohexylphosphite, diphenyl-isooctylphosphite, diphenyl-2-ethylhexylphosphite, diphenyl-isodecylphosphite, diphenyl-cyclohexylphenylphosphite, diphenyl-(tridecyl)thiophosphite, and the like.

[0172] Further specific examples of the antioxidant (H) include sulfur-based antioxidants such as ADK STAB AO-412S (trade name, manufactured by ADEKA CORPORATION), AO-503S (trade name, manufactured by ADEKA CORPORATION), and Sumilizer TP-D (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

[0173] The sulfur-based antioxidant and the phosphorus-based antioxidant are expected to have the effect of decomposing peroxides.

[0174] The content of the (H) antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the polymer (A). A content of 0.1 part by mass or more improves adhesion to metal materials and inhibits peeling. A content of 10 parts by mass or less prevents deterioration of the developability of the composition and the toughness of the cured coating.

[0175] The negative-type photosensitive resin composition of the present invention may further contain (I) a silane compound in addition to the above-mentioned components (A), (B), (C), (D), and (E). The inclusion of the silane compound as component (I) not only improves adhesion to metal materials but also suppresses peeling of the cured coating during reliability tests such as thermal shock tests and high-temperature, high-humidity tests.

[0176] The silane compound (I) that can be used here is not particularly limited, but is preferably one having an alkoxysilyl group. Specific examples of suitable compounds are shown below: γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ ... Examples of suitable silane compounds include aminopropyltriethoxysilane, triethoxysilylpropylethyl carbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, amide group-containing silane compounds described in Japanese Patent No. 6414060, thiourea group-containing silane compounds described in International Publication No. 2016 / 140024 and Japanese Patent No. 5987984, and thiol group-containing silane compounds described in Japanese Patent Laid-Open No. 2017-044964. However, these silane compounds (I) may be used alone or in combination of two or more.

[0177] The content of the (I) silane compound is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, and even more preferably 3 to 6 parts by weight, per 100 parts by weight of the polymer of component (A). An amount of 0.1 part by weight or more can provide sufficient adhesion to the substrate, while an amount of 20 parts by weight or less can further suppress problems such as an increase in viscosity during storage at room temperature. A content of 10 parts by weight or less prevents the developability of the composition from deteriorating and prevents development residues.

[0178] The negative photosensitive resin composition of the present invention may further contain (J) a surfactant. (J) The surfactant is preferably a nonionic surfactant, such as a fluorine-containing surfactant, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkyl amine oxide, fluorine-containing organosiloxane compound, or non-fluorine-containing organosiloxane compound.

[0179] These (J) surfactants may be commercially available, and examples thereof include Fluorad FC-4430 (trade name, manufactured by Sumitomo 3M Limited), PF-6320 (trade name, manufactured by OMNOVA), PF-636 (trade name, manufactured by OMNOVA), Surflon S-141 and S-145 (all of which are trade names, manufactured by Asahi Glass Co., Ltd.), Unidyne DS-401, DS-4031, and DS-451 (all of which are trade names, manufactured by Daikin Industries, Ltd.), Megafac F-8151 (trade name, manufactured by DIC Corporation), X-70-093, and KP-341 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, Fluorad FC-4430 (trade name, manufactured by Sumitomo 3M Limited), PF-6320 (trade name, manufactured by OMNOVA), PF-636 (trade name, manufactured by OMNOVA), and KP-341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) are preferred.

[0180] The amount of surfactant (J) added is preferably 0.01 to 0.05 parts by mass per 100 parts by mass of the polymer (A), which has the advantage of improving substrate coatability without impairing patterning performance or the properties of the cured coating.

[0181] The negative-type photosensitive resin composition of the present invention may further contain (K) a sensitizer. Examples of (K) sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminophenylvinylene)benzothi ... (4'-diethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl- Examples include 5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, and 2-(p-dimethylaminobenzoyl)styrene. These can be used alone or in combination of, for example, 2 to 5 types.

[0182] The amount of the sensitizer (K) added is preferably 0.05 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the polymer of the component (A).

[0183] (Pattern formation method) Next, a pattern forming method using the negative photosensitive resin composition of the present invention will be described.

[0184] A pattern of the negative photosensitive resin composition of the present invention can be formed by employing a known lithography technique. For example, the negative photosensitive resin composition is applied by spin coating to a silicon wafer, SiO2 substrate, SiN substrate, or a substrate on which a pattern of copper wiring or the like has been formed, and the composition is prebaked at 80 to 130°C for about 50 to 600 seconds to form a photosensitive coating having a thickness of 1 to 50 μm, preferably 1 to 30 μm, and more preferably 5 to 20 μm.

[0185] In the spin coating method, approximately 5 mL of the negative photosensitive resin composition is dispensed onto a silicon substrate, and then the substrate is rotated to coat the negative photosensitive resin composition onto the substrate. The thickness of the photosensitive film on the substrate can be easily adjusted by adjusting the rotation speed. The remaining solvent can then be removed by pre-baking.

[0186] Next, a mask for forming a desired pattern is placed over the photosensitive film, and high-energy rays such as i-rays and g-rays with wavelengths of 190 to 500 nm or electron beams are irradiated at an exposure dose of 1 to 5,000 mJ / cm. 2 Approximately, preferably 100 to 2,000 mJ / cm 2 Expose to a level that is approximately

[0187] Any of the negative photosensitive resin compositions of the present invention can be developed with an organic solvent.

[0188] Suitable organic solvents that can be used in organic solvent development include the solvents described above used when preparing the negative photosensitive resin composition of the present invention. For example, ketones such as cyclohexanone and cyclopentanone, and glycols such as propylene glycol monomethyl ether are preferred. Development can be carried out by a conventional method such as a spray method or a puddle method, or by immersion in a developer. Thereafter, washing, rinsing, drying, etc. can be carried out as necessary to obtain a resist film having a desired pattern.

[0189] (Hardened film formation method) Furthermore, the patterned coating obtained by the above-described pattern formation method can be post-cured using an oven or hot plate at a temperature of 100 to 300°C, preferably 150 to 300°C, and more preferably 180 to 250°C, to form a cured coating. A post-curing temperature of 100 to 300°C increases the crosslink density of the photosensitive resin composition coating and removes remaining volatile components, which is preferable from the viewpoints of adhesion to the substrate, heat resistance, strength, and electrical properties. The post-curing time can be 10 minutes to 10 hours.

[0190] The patterns formed as described above are used as protective coatings to cover wiring, circuits, substrates, etc., and these formed patterns and protective coatings have excellent insulating properties and exhibit excellent adhesion to the metal layers of the wiring or circuit, such as Cu, that they cover, metal electrodes that exist on the substrate, or insulating substrates, such as SiN, that exist on the wiring or circuit that they cover. They also have mechanical strength suitable for a protective coating, while significantly improving resolution performance to enable the formation of even finer patterns.

[0191] (hardened film) The cured coating thus obtained has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance to alkaline stripping solutions, and also has excellent reliability for semiconductor elements using it as a protective coating, particularly in preventing cracking during temperature cycle tests. Therefore, it is suitable for use as a protective coating (interlayer insulating film or surface protective film) for electrical and electronic components, semiconductor elements, etc.

[0192] That is, the present invention provides an interlayer insulating film or a surface protective film comprising a cured film obtained by curing the above-mentioned negative photosensitive resin composition.

[0193] The protective coating is effective for applications such as insulating films for semiconductor elements including rewiring, insulating films for multilayer printed circuit boards, solder masks, and coverlay films due to its heat resistance, chemical resistance, and insulating properties.

[0194] Furthermore, the present invention provides an electronic component having the above interlayer insulating film or the above surface protective film. Such electronic components have excellent reliability because they have a protective coating (interlayer insulating film or surface protective film) that is heat-resistant, chemical-resistant, and insulating. [Example]

[0195] The present invention will be specifically explained below by showing synthesis examples, comparative synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

[0196] I. Polymer Synthesis The chemical structures and names of the compounds used in the synthesis examples are shown below. [ka]

[0197] DA-1 4-aminophenyl-4-amino-2-methylbenzoate DA-2 (2-phenyl-4-aminophenyl)-4-aminobenzoate DA-3 4-(4-aminophenoxy)-3-methylbenzenamine DA-4 2-phenyl-4,4'-diaminodiphenyl ether DA-5 4-(4-aminophenoxy)-3-(trifluoromethyl)benzenamine DA-6 4-((4-aminophenyl)thio)-3-phenylbenzenamine DA-7 (4-amino-2-(phenyl)phenyl)(4-aminophenyl)methanone DA-8 4-((4-aminophenyl)methyl)-3-phenylbenzenamine ODA 4,4'-diaminodiphenyl ether APB 1,3-bis(3-aminophenoxy)benzene s-ODPA 3,3',4,4'-oxydiphthalic dianhydride s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride DC-1 Sebacic acid dichloride PAP 4-aminophenol 6FAP 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0198] [Synthesis Example 1] Synthesis of tetracarboxylic acid diester compound (X-1) In a 3 L flask equipped with a stirrer and thermometer, 100 g (322 mmol) of 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA), 65.2 g (644 mmol) of triethylamine, 39.3 g (322 mmol) of N,N-dimethyl-4-aminopyridine, and 400 g of γ-butyrolactone were added and stirred at room temperature. 83.8 g (644 mmol) of hydroxyethyl methacrylate (HEMA) was added dropwise, followed by stirring at room temperature for 24 hours. The reaction was then quenched by adding 370 g of 10% aqueous hydrochloric acid solution dropwise under ice cooling. 800 g of 4-methyl-2-pentanone was added to the reaction mixture, and the organic layer was separated and washed six times with 600 g of water. The solvent in the resulting organic layer was evaporated to yield 180 g of tetracarboxylic acid diester compound (X-1) with the following structure. [ka]

[0199] [Synthesis Example 2] Synthesis of tetracarboxylic acid diester compound (X-2) In Synthesis Example 1, 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA) was replaced with 94.8 g (322 mmol) of 3,3',4,4'-bisphthalic dianhydride (s-BPDA), and the rest of the procedure was the same as above, to obtain 172 g of a tetracarboxylic acid diester compound (X-2) having the following structure. [ka]

[0200] [Synthesis Example 3] Synthesis of polyimide precursor (A-1) A 1-L flask equipped with a stirrer and thermometer was charged with 44.0 g (77.1 mmol) of (X-1) and 176 g of N-methyl-2-pyrrolidone, and the mixture was stirred and dissolved at room temperature. Next, 18.8 g (158.1 mmol) of thionyl chloride was added dropwise under ice cooling, maintaining the reaction solution temperature below 10°C. After the addition, the mixture was stirred for 2 hours under ice cooling. Subsequently, a solution of 17.4 g (71.7 mmol) of (DA-1) and 25.0 g (316.2 mmol) of pyridine in 70 g of N-methyl-2-pyrrolidone was added dropwise under ice cooling, maintaining the reaction solution temperature below 10°C. After the addition, the mixture was returned to room temperature, and the reaction solution was added dropwise to 3 L of stirring water. The precipitate was filtered, washed appropriately, and then dried under reduced pressure at 40°C for 48 hours to obtain polyimide precursor (A-1). The molecular weight of this polymer was measured by GPC and found to be 25,000 in terms of polystyrene.

[0201] [Synthesis Example 17] Synthesis of polyimide precursor (A-15) A 1-L flask equipped with a stirrer and thermometer was charged with 44.0 g (77.1 mmol) of (X-1) and 176 g of N-methyl-2-pyrrolidone, and the mixture was stirred and dissolved at room temperature. Next, 18.8 g (158.1 mmol) of thionyl chloride was added dropwise under ice cooling, maintaining the reaction solution temperature below 10°C. After the addition, the mixture was stirred for 2 hours under ice cooling. Next, 4.6 g (19.3 mmol) of (DC-1) was added, followed by a solution of 2.9 g (9.6 mmol) of (DA-2), 16.4 g (81.9 mmol) of (ODA), 1.0 g (9.6 mmol) of (PAP), and 15.3 g (192.8 mmol) of pyridine dissolved in 135 g of N-methyl-2-pyrrolidone, which was added dropwise under ice cooling, maintaining the reaction solution temperature below 10°C. After the dropwise addition was completed, the mixture was returned to room temperature, and the reaction solution was added dropwise to 3 L of water under stirring. The precipitate was filtered, washed appropriately with water, and then dried under reduced pressure at 40°C for 48 hours to obtain polyimide precursor (A-15). The molecular weight of this polymer was measured by GPC and found to be 32,000 in terms of polystyrene.

[0202] [Synthesis Example 18] Synthesis of polyimide resin (A-16) A 1-L flask equipped with a stirrer and thermometer was charged with 31.0 g (100.0 mmol) of (s-ODPA) and 279 g of N-methyl-2-pyrrolidone, and the mixture was stirred at room temperature to dissolve. Next, a solution of 15.2 g (50.0 mmol) of (DA-2), 9.0 g (45.0 mmol) of (ODA), and 1.1 g (10.0 mmol) of (PAP) dissolved in 228 g of N-methyl-2-pyrrolidone was added dropwise at room temperature. After the addition, the mixture was stirred at room temperature for 1 hour. 30 g of xylene was then added to the reaction mixture, and the mixture was heated to 180 °C under reflux for 3 hours, while removing the water generated. After cooling to room temperature, the reaction mixture was added dropwise to 2 L of stirred ultrapure water. The precipitate was filtered, washed appropriately, and then dried under reduced pressure at 40 °C for 48 hours to obtain polyimide resin (A-16). The molecular weight of this polymer was measured by GPC and found to be 34,000 in terms of polystyrene.

[0203] [Synthesis Example 19] Synthesis of polyamide resin (A-17) In a 1 L flask equipped with a stirrer and thermometer, 15.2 g (50.0 mmol) of (DA-2), 9.0 g (45.0 mmol) of (ODA), 1.1 g (10.0 mmol) of (PAP), and 228 g of N-methyl-2-pyrrolidone were added and stirred at room temperature to dissolve. Next, 15.8 g (200.0 mmol) of pyridine was added, and 23.9 g (100.0 mmol) of (DC-1) was added dropwise to maintain the temperature below 20°C. After the addition, the reaction solution was added dropwise to 2 L of ultrapure water with stirring. The precipitate was filtered, washed appropriately, and dried under reduced pressure at 40°C for 48 hours to obtain polyamide resin (A-17). The molecular weight of this polymer was measured by GPC to find a weight-average molecular weight of 38,000 in terms of polystyrene.

[0204] Synthesis Examples 4 to 16, 20, and Comparative Synthesis Examples 1 and 2: Synthesis of Polyimide Precursors (A-2) to (A-14), and (A-18) to (A-20) Using the tetracarboxylic acid diester compound, diamine compound, monoamine compound, tetracarboxylic acid dianhydride, and dicarboxylic acid dichloride compounds with weights shown in Table 1 below, (A-2) to (A-14) and (A-18) to (A-20) were obtained according to the same formulation as in Synthesis Example 3. The molecular weight of each polymer was measured by GPC at 40°C using DMF as the eluent, and the weight average molecular weight in terms of polystyrene is shown in Table 1 below. [Table 1]

[0205] II. Preparation of Photosensitive Resin Composition Using the polymers synthesized in Synthesis Examples 3 to 20 and Comparative Synthesis Examples 1 and 2 as base resins, resin compositions were prepared at 35 mass % resin equivalent, with the formulations and blending amounts shown in Table 2. After stirring, mixing, and dissolution, the mixture was microfiltered through a 1.0 μm Teflon (registered trademark) filter to obtain a photosensitive resin composition. In the table, the solvent GBL stands for γ-butyrolactone.

[0206] [Table 2]

[0207] Photosensitive resin compositions 1 to 21 shown in Table 2 relate to the above-mentioned negative photosensitive resin compositions of the present invention. Comparative photosensitive resin compositions 1 and 2 are the negative photosensitive resin compositions of the present invention described above, except that the polymers synthesized in Comparative Synthesis Examples 1 and 2 were used as the base resin instead of the polymer of the present invention.

[0208] In Table 2, the details of the photoradical generator (B-1), crosslinker (C-1), thermal crosslinker (D-1), (D-2), protected amine compound (F-1), thermal acid generator (G-1), antioxidant (H-1), silane compound (I-1), surfactant (J-1), and sensitizer (K-1) are as follows: Parts by weight have the same meaning as parts by mass.

[0209] Photoradical initiator (B-1): N-1919 manufactured by ADEKA Corporation

[0210] Crosslinker (C-1): Tetraethylene glycol dimethacrylate

[0211] Thermal crosslinking agent (D-1) [ka]

[0212] Thermal crosslinking agent (D-2) Epoxy resin: ADEKA Corporation EP4000L

[0213] Protected amine compound (F-1) [ka]

[0214] Thermal Acid Generator (G-1) [ka]

[0215] Antioxidant (H-1) Hindered phenolic antioxidant: Sumilizer GA-80 manufactured by Sumitomo Chemical Co., Ltd.

[0216] Silane Compound (I-1) Aminosilane coupling agent: KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.

[0217] Surfactant (J-1) Silicone surfactant: KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

[0218] Sensitizer (K-1) N-Phenyldiethanolamine

[0219] III. Pattern Formation 5 mL of each of the above photosensitive resin compositions 1 to 21 and comparative photosensitive resin compositions 1 and 2 was dispensed onto a silicon substrate, and then the substrate was rotated, i.e., by spin coating, so that the film thickness would be 5 μm after heating for post-curing, which is performed after pattern formation. That is, considering in advance that the film thickness would decrease after the post-curing step, the rotation speed during application was adjusted so that the finished film thickness after post-curing would be 5 μm. Next, the film was prebaked on a hot plate at 100°C for 2 minutes. Then, i-line exposure and pattern formation were performed using a Nikon i-line stepper NSR-2205i11. In pattern formation, a mask for a positive pattern or a negative pattern was used as appropriate, depending on the photosensitive resin composition used. The mask had a pattern capable of forming 20 μm holes in a 1:1 vertical / horizontal arrangement, with 10 μm intervals from 50 μm to 20 μm, 5 μm from 20 μm to 10 μm, and 1 μm from 10 μm to 1 μm.

[0220] In the development process, cyclopentanone was used as the developer. For organic solvent development, spray development with each organic solvent was performed once for 1 minute, followed by rinsing with isopropyl alcohol.

[0221] The resulting pattern on the substrate was then post-cured in an oven at 250° C. for 2 hours while purging with nitrogen.

[0222] Next, each substrate was cut out so that the shape of the resulting hole pattern could be observed, and the hole pattern shape was observed using a scanning electron microscope (SEM). The diameter of the smallest opening hole at a film thickness of 5 μm after post-curing was determined, and the pattern shape was evaluated. These results, along with the sensitivity at which the smallest pattern could be formed, are shown in Table 3.

[0223] The hole pattern shape was evaluated according to the following criteria, and the evaluation results are shown in Table 3. Good: Holes that are rectangular or tapered (the dimensions of the top of the hole are larger than the dimensions of the bottom) Poor: Reverse tapered shape (the dimensions of the top of the hole are smaller than the dimensions of the bottom), overhang shape (the top of the hole protrudes), significant film loss, or residue at the bottom of the hole

[0224] IV. Breaking elongation, breaking strength The above-mentioned photosensitive resin compositions 1 to 21 and comparative photosensitive resin compositions 1 and 2 were spin-coated onto an aluminum substrate so that the final film thickness after curing would be 10 μm. Next, the coating was pre-baked on a hot plate at 100°C for 4 minutes, and then irradiated with 1000 mJ / cm 2 The entire surface was exposed to broadband light at an exposure dose of 1000 to obtain a resin film.

[0225] The wafer was then cured in an oven at 250°C for 2 hours while purging with nitrogen, yielding a cured resin film. The wafer with the cured film was then cut into strips measuring 10 mm wide and 60 mm long, and the cured film was peeled off from the substrate by immersing in 20% by weight hydrochloric acid. The resulting cured film was measured for breaking elongation and breaking strength using an autograph AGX-1KN manufactured by Shimadzu Corporation. Ten measurements were performed per sample, and the average values ​​are shown in Table 3.

[0226] Table 3 shows the patterning results and the breaking elongation and breaking strength of the cured films obtained using the negative photosensitive resin compositions (photosensitive resin compositions 1 to 21, comparative photosensitive resin compositions 1 and 2).

[0227] [Table 3]

[0228] As shown in Table 3, the negative-type photosensitive resin composition of the present invention, which uses as component (A) a polymer in which at least one of R1 to R4 represented by general formula (1) is a monovalent organic group having 1 to 15 carbon atoms, which may contain a heteroatom, exhibits a good pattern shape in cyclopentanone development, and the minimum hole dimension is 5 μm or less for a finished film thickness of 5 μm, demonstrating that an aspect ratio of 1 or more can be achieved.

[0229] Furthermore, even when the negative photosensitive composition of the present invention was cured at a low temperature of 250° C. or less, a cured film having good mechanical properties was obtained.

[0230] On the other hand, the cured films obtained using comparative photosensitive resin compositions 1 and 2, which use as component (A) a polymer represented by general formula (1) in which R1 to R4 are all hydrogen atoms, have pattern shapes and minimum hole dimensions equivalent to those of the composition of the present invention, but are inferior in mechanical properties to the cured films obtained from the composition of the present invention in both breaking elongation and breaking strength.

[0231] The present specification includes the following aspects. [1]: A polymer having a polyimide precursor, characterized in that it contains a structural unit represented by the following general formula (1): [ka] (In the formula, X1 is a tetravalent organic group; R1 to R4 may be different or the same and are a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom or a hydrogen atom, at least one of which is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom; L is a divalent linking group; Ra and Rb are each independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group represented by the following general formula (2), and at least one of Ra and Rb is an organic group represented by the following general formula (2).) [ka] (In the formula, the dotted line represents a bond, Rc is a hydrogen atom or an organic group having 1 to 3 carbon atoms, Rd and Re are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10.) [2]: The polymer according to [1], wherein one of R1 and R2 in the general formula (1) is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom, and the other is a hydrogen atom, and R3 and R4 are hydrogen atoms. [3]: The polymer according to [1] or [2], wherein one of R1 and R2 in the general formula (1) is an aromatic group having 6 to 12 carbon atoms, and the other is a hydrogen atom. [4]: The polymer according to any one of [1] to [3], wherein L in the general formula (1) is at least one organic group selected from the group consisting of an oxygen atom, a sulfur atom, an ester group, a carbonyl group, a linear alkylene group having 1 to 15 carbon atoms, and a branched alkylene group having 3 to 15 carbon atoms. [5]: The polymer according to any one of [1] to [4], wherein L in the general formula (1) is at least one organic group selected from the group consisting of an oxygen atom and an ester group. [6]: A negative photosensitive resin composition, (A) the polymer according to any one of [1] to [5] above; (B) a photoradical initiator, and (E) solvent, A negative photosensitive resin composition comprising: [7]: The negative-type photosensitive resin composition according to [6], further comprising a crosslinking agent having two or more photopolymerizable unsaturated bond groups in one molecule as component (C). [8]: The negative photosensitive resin composition according to any one of [6] or [7], characterized in that (D) the thermal crosslinking agent comprises one or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or a formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol or a polyhydric alcohol is substituted with a substituent represented by the following formula (D-1), and a compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (D-2): [ka] (In the formula, the dotted line represents a bond, Rf represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.) [9]: The negative photosensitive resin composition according to any one of [6] to [8], further comprising one or more of (F) a protected amine compound, (G) a thermal acid generator, (H) an antioxidant, and (I) a silane compound.

[10] : A pattern forming method, comprising: (1) A step of applying the negative photosensitive resin composition according to any one of [6] to [9] onto a substrate to form a photosensitive film; (2) heating the photosensitive coating; (3) exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask; and (4) developing using an organic solvent developer; A pattern forming method comprising the steps of:

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

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

[12] : An interlayer insulating film comprising a cured film obtained by curing the negative photosensitive resin composition according to any one of [6] to [9].

[13] : A surface protection film comprising a cured coating formed by curing the negative photosensitive resin composition according to any one of [6] to [9].

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

[12] .

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

[13] .

[0232] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. A polymer having a polyimide precursor, characterized in that it contains a structural unit represented by the following general formula (1): 【Chemistry 1】 (In the formula, X １ is a tetravalent organic group, and R １ ~R ４ may be different or the same and are a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom or a hydrogen atom, at least one of which is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom; L is a divalent linking group; Ra and Rb are each independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group represented by the following general formula (2), and at least one of Ra and Rb is an organic group represented by the following general formula (2): 【Chemistry 2】 (In the formula, the dotted line represents a bond, Rc is a hydrogen atom or an organic group having 1 to 3 carbon atoms, Rd and Re are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10.)

2. The R in the general formula (1) １ and R ２ one of the R is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom, and the other is a hydrogen atom; ３ and R ４ The polymer according to claim 1, wherein is a hydrogen atom.

3. The R in the general formula (1) １ and R ２ and the other is a hydrogen atom.

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

5. 5. The polymer according to claim 4, wherein L in the general formula (1) is at least one organic group selected from the group consisting of an oxygen atom and an ester group.

6. A negative photosensitive resin composition, (A) the polymer according to any one of claims 1 to 5; (B) a photoradical initiator, and (E) a solvent, A negative photosensitive resin composition comprising:

7. 7. The negative photosensitive resin composition according to claim 6, further comprising a crosslinking agent having two or more photopolymerizable unsaturated bond groups in one molecule as a component (C).

8. 7. The negative photosensitive resin composition according to claim 6, wherein the thermal crosslinking agent (D) is one or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or a formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol or a hydroxyl group of a polyhydric alcohol is substituted with a substituent represented by the following formula (D-1), and a compound containing two or more nitrogen atoms and having a glycidyl group represented by the following formula (D-2): 【Transformation 3】 (In the formula, the dotted lines represent bonds, Rf represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.)

9. 7. The negative photosensitive resin composition according to claim 6, further comprising one or more of (F) a protected amine compound, (G) a thermal acid generator, (H) an antioxidant, and (I) a silane compound.

10. A pattern formation method, comprising: (1) A step of applying the negative photosensitive resin composition according to claim 6 onto a substrate to form a photosensitive film; (2) heating the photosensitive coating; (3) exposing the photosensitive coating to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask; and (4) developing the resist using an organic solvent developer; A pattern forming method comprising the steps of:

11. A method for forming a cured film, comprising the step of heating and post-curing the patterned film obtained by the method for forming a pattern according to claim 10 at a temperature of 100 to 300°C.

12. An interlayer insulating film comprising a cured film obtained by curing the negative photosensitive resin composition according to claim 6.

13. A surface protection film comprising a cured coating formed by curing the negative photosensitive resin composition according to claim 6.

14. An electronic component comprising the interlayer insulating film according to claim 12.

15. An electronic component comprising the surface protection film according to claim 13.

Images