Negative-type photosensitive resin composition, patterning method, method for forming cured film, interlayer insulative film, surface-protective film, and electronic component

Abstract

To provide: a negative-type photosensitive resin composition that is soluble in an alkaline aqueous solution, that can form a fine pattern to yield high resolution, that yields good mechanical properties such as breakage elongation and tensile strength even by curing at low temperature, and that causes no deterioration of adhesive force before and after a high-temperature high-humidity test; a patterning method; a method for forming a cured film; an interlayer insulative film; a surface-protective film; and an electronic component.SOLUTION: A negative type photosensitive resin composition contains: a polymer (A) having a structural unit represented by specific formula (1) and / or formula (2), and a structural unit represented by specific formula (3) and / or specific formula (4); an optical acid generator (B); a crosslinking agent (C); and a solvent (D).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to 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 growing demand for semiconductor elements to be smaller, thinner, and denser. Accordingly, the interlayer insulating film and surface protective film 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, such as polyimide films. Their insulating properties, mechanical properties, and adhesion to substrates have continued to attract attention, and they are still being actively developed.

[0004] Various approaches have been taken to further improve the required properties. One of these approaches is a photosensitive resin composition using a ring-closed polyimide resin with the aim of lowering the post-curing temperature (Patent Document 1, Patent Document 2). However, it is difficult to achieve both resolution, mechanical properties (elongation and tensile strength), and cured film properties such as adhesion, and there is room for improvement.

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

[0006] Patent Document 4 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-closing the polyamic acid. However, there is no description regarding a photosensitive resin composition, and there is room for improvement in mechanical strength, particularly elongation.

[0007] In addition, in order to improve the mechanical strength of the cured film, it has been proposed to add a (meth)acrylic resin to achieve both lithography properties and cured film physical properties (Patent Document 5, Patent Document 6, Patent Document 7). However, since the purpose is to modify the main resin, there is room for improvement in the mechanical strength of the cured film.

[0008] As described above, in the future, as chips become increasingly dense and highly integrated, 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, such as the mechanical properties and adhesion, of the patterns and protective coatings obtained by heating. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Patent No. 4530284 [Patent Document 2] JP 2006-313237 A [Patent Document 3] JP 2020-152768 A [Patent Document 4] JP 2021-187934 A [Patent Document 5] Patent No. 5884837 [Patent Document 6] JP 2015-129791 A [Patent Document 7] JP 2015-200819 A Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention has been made in view of the above circumstances, and has an object to provide a negative-type photosensitive resin composition that is soluble in an alkaline aqueous solution, is capable of forming a fine pattern with high resolution, has good mechanical properties such as breaking elongation and tensile strength even when cured at low temperature, and does not deteriorate in adhesion before and after a high-temperature, high-humidity test, a pattern forming method, a cured coating forming method, an interlayer insulating film, a surface protective film, and an electronic component. [Means for solving the problem]

[0011] In order to solve the above problems, the present invention provides a negative photosensitive resin composition, comprising: (A) a polymer containing structural units represented by the following general formula (1) and / or (2) and structural units represented by the following general formula (3) and / or (4): [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, and Es is a -O-C(=O)- bond or a -C(=O)-O- bond.) [ka] (In the formula, X2 is a divalent organic group, and R1 to R4 and Es are the same as above.) [ka] (In the formula, X3 is a tetravalent organic group that is the same as or different from X1, s is 0 or 1, Z is a divalent linking group, and when s=0, the two aromatic rings in the formula are directly linked without a linking group.) [ka] (In the formula, X4 is a divalent organic group that is the same as or different from X2, and s and Z are the same as those defined above.) (B) a photoacid generator, (C) a crosslinking agent, (D) a solvent, The present invention provides a negative type photosensitive resin composition comprising:

[0012] In such a negative type photosensitive resin composition, since the general formula (3) or (4) has a phenolic hydroxyl group, it is soluble in an alkaline aqueous solution, and a fine pattern can be formed, thereby enabling high resolution to be obtained. Furthermore, since the general formula (1) or (2) has an ester group, intermolecular interactions are promoted by hydrogen bonds or the like, and also the composition interacts with the substrate, resulting in good mechanical properties and adhesion to the substrate even when cured at a low temperature.

[0013] In the present invention, it is preferable that either one of R1 and R2 in the general formulas (1) and (2) is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom, the other is a hydrogen atom, and R3 and R4 are hydrogen atoms.

[0014] In such a negative type photosensitive resin composition, 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 site bonded to the ester group, and the intermolecular interaction becomes appropriate, so that the mechanical properties become good even when cured at a low temperature.

[0015] In this case, it is preferable that one of R1 and R2 in the general formulae (1) and (2) is an aromatic group having 1 to 10 carbon atoms, and the other is a hydrogen atom.

[0016] Such a negative photosensitive resin composition has better mechanical properties even when cured at a low temperature.

[0017] In the present invention, Z in the general formulas (3) and (4) is preferably at least one bonding group selected from the groups represented by the following formulas (5), (6), (7) and (8). [ka] (In the formula, the dotted lines represent bonds.)

[0018] Such a negative photosensitive resin composition can have high solubility in an alkaline aqueous solution, making it possible to form finer patterns and obtain high resolution.

[0019] In the present invention, the component (C) is preferably 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 the hydroxyl groups of polyhydric phenols are substituted with glycidyl groups, compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols or polyhydric alcohols are substituted with substituents represented by the following formula (C-1), and compounds containing two or more nitrogen atoms having glycidyl groups represented by the following formula (C-2). [ka] (In the formula, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.)

[0020] Such a negative photosensitive resin composition allows finer patterns to be formed, resulting in high resolution, and also provides good mechanical properties and adhesion to substrates even when cured at low temperatures.

[0021] In the present invention, the negative photosensitive resin composition further comprises: (E) a crosslinkable polymer compound containing a structural unit represented by the following general formula (9) and having a group capable of crosslinking with the component (A): [ka] (In the formula, R5 is a hydrogen atom or a methyl group, R6 is a (n+1)-valent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, a benzyl group, or a naphthalenemethyl group, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. n is an integer of 1 to 5. Y1 is -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R7OH)-, respectively. R7 is a divalent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. p1 is 0 or 1.) It is preferable that the composition contains the following:

[0022] Such a negative photosensitive resin composition allows finer patterns to be formed, resulting in high resolution, and also provides good mechanical properties and adhesion to substrates even when cured at low temperatures.

[0023] In this case, the component (E) is preferably a crosslinkable polymer compound that contains a structural unit represented by the following general formula (10) and also contains a structural unit represented by the following general formula (11) having a group that crosslinks with the component (A). [ka] (In the formula, R8 is a hydrogen atom or a methyl group, and Y2 is -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R9OH)-. R9 is a divalent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. p2 is 0 or 1.) [ka] (In the formula, R 10 is a hydrogen atom or a methyl group, R 11is a group containing an oxazoline group, an isocyanate group, a blocked isocyanate group, an oxetanyl group, or an epoxy group, and Y3 is -C(=O)-O-, a phenylene group, or a naphthylene group. p3 is 0 or 1.

[0024] Such a negative photosensitive resin composition maintains sufficient solubility in an aqueous alkaline solution, can provide a pattern with good rectangularity, and has good mechanical properties and adhesion to a substrate even when cured at a low temperature.

[0025] In this case, the component (E) is preferably a crosslinkable polymer compound containing structural units represented by the following general formula (10) and the following general formula (12). [ka] (In the formula, R8, Y2, and p2 are the same as those described above, and R 12 is a hydrogen atom or a methyl group, and Y is -C(=O)-O-, a phenylene group, or a naphthylene group. 13 is a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may contain a hydroxyl group, an ester group, an ether group or an aromatic hydrocarbon; R 14 is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R 13 R may be bonded to form a ring. 15 is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R 16 is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, and R 13 may be bonded to form a ring. m is 0 or 1. p4 is 0 or 1. 0 <a1<1.0、0<a2<1.0、0<a1+a2≦1.0である。)

[0026] Such a negative photosensitive resin composition maintains sufficient solubility in an alkaline aqueous solution when added to the polymer of component (A), and can obtain a pattern with good rectangularity. In addition, since the composition contains a crosslinking group with excellent crosslinking properties, the composition crosslinks with the phenolic hydroxyl group in the structural unit of component (A) represented by the general formula (3) and / or (4), and there is no deterioration in adhesion to the substrate after a reliability test.

[0027] In the present invention, the component (E) is preferably a crosslinkable polymer compound further comprising a structural unit represented by the following general formula (13). [ka] (In the formula, R 17 is a hydrogen atom or a methyl group, R 18 is a single bond or a (l+1)-valent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. Y5 is -C(=O)-O-, -C(=O)-OR 19 -, -C(=O)-NH-, -C(=O)-N(R 19 OH)-, a phenylene group, or a naphthylene group. 19 is a divalent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. 1 is 0 or 1.

[0028] Such a negative photosensitive resin composition allows finer patterns to be formed, resulting in high resolution, and also provides good mechanical properties and adhesion to substrates even when cured at low temperatures.

[0029] In the present invention, the component (E) is preferably a crosslinkable polymer compound further comprising at least one structural unit selected from structural units formed by cyclopolymerization represented by the following general formula (14), the following general formula (15), the following general formula (16), and the following general formula (17): [ka] (In the formula, R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

[0030] Such a negative type photosensitive resin composition has a ring structure in the main chain, and therefore has good mechanical properties such as breaking elongation and tensile strength even when cured at low temperatures, and further has improved heat resistance.

[0031] In the present invention, it is preferable that the composition further contains one or more selected from the group consisting of (F) a basic compound, (G) a thermal acid generator, (H) an antioxidant, and (I) a silane compound.

[0032] By including such a component (F), not only can the dissolution contrast during lithographic patterning be improved, but also the pattern shape can be controlled. Furthermore, such component (G) can promote the crosslinking and curing reaction further, thereby further improving the mechanical strength, chemical resistance, adhesion, etc. of the obtained pattern or coating. Furthermore, such component (H) can suppress deterioration of the physical properties of the cured coating due to oxidation during reliability tests such as high humidity tests and thermal shock tests, making it possible to form a more suitable cured coating. Furthermore, the component (I) can further improve the adhesion of the resulting pattern or coating to the substrate.

[0033] Further, the present invention provides a pattern forming method, comprising the steps of: (1) A step of applying the above-described negative photosensitive resin composition onto a substrate to form a photosensitive film; (2) subsequently exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask after the heat treatment; (3) developing the substrate that has been subjected to the heat treatment after the exposure using an aqueous alkaline developer; The present invention provides a pattern forming method comprising the steps of:

[0034] In such a pattern forming method, by using the above-mentioned negative photosensitive resin composition, which is soluble in an alkaline aqueous solution, it is possible to form a fine pattern and obtain high resolution.

[0035] The present invention further provides a method for forming a cured coating, comprising the step of heating and post-curing the photosensitive coating having a pattern formed thereon, obtained by the above-described method for forming a pattern, at a temperature of 100 to 300°C.

[0036] Such a method for forming a cured coating can form a cured coating (pattern) that has good mechanical properties even when cured at low temperatures.

[0037] The present invention also provides an interlayer insulating film or a surface protective film which is a cured film formed by curing the above-described negative photosensitive resin composition.

[0038] 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 against alkaline stripping solutions and the like, and also has excellent reliability for semiconductor elements using it as a protective coating. Therefore, the cured coating is suitable as a protective coating (interlayer insulating film or surface protective film) for electric / electronic components, semiconductor elements, etc.

[0039] The present invention also provides an electronic component having the above-described interlayer insulating film or surface protective film.

[0040] Such protective coatings (interlayer insulating films or surface protective films) are effective as insulating films for semiconductor elements, including rewiring applications, and insulating films for multilayer printed circuit boards, due to their heat resistance, chemical resistance, and insulating properties, and can be used to make electronic components with excellent reliability. Effect of the Invention

[0041] As described above, the present invention can provide a negative type photosensitive resin composition that is soluble in an alkaline aqueous solution, can form a fine pattern with high rectangularity and can obtain high resolution, and has good mechanical properties and adhesion to a substrate even when cured at a low temperature. [Brief description of the drawings]

[0042] [Figure 1] FIG. 2 is an explanatory diagram showing a method for measuring adhesion. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0043] As described above, there has been a demand for a photosensitive resin composition that is soluble in an alkaline aqueous solution, can form a fine pattern with high rectangularity and can obtain high resolution, and has good mechanical properties and adhesion to a substrate even when cured at a low temperature.

[0044] As a result of intensive research to achieve the above object, the present inventors have found that a pattern obtained by using a negative photosensitive resin composition containing the following components (A) to (D) is a fine rectangular pattern shape, and the obtained cured coating has good mechanical properties and adhesion to a substrate.

[0045] Furthermore, it was found that when the negative-type photosensitive resin composition was used to form a pattern and then heated at a low temperature, the protective coating obtained had excellent mechanical strength and adhesion. That is, it was found that the cured coating having a pattern formed using the negative-type photosensitive resin composition is excellent as a protective coating for electric and electronic components and an insulating protective coating, and the present invention was completed. In this specification, electric and electronic components are also collectively referred to as "electronic components".

[0046] That is, the present invention is a negative photosensitive resin composition, (A) a polymer containing structural units represented by the following general formula (1) and / or (2) and structural units represented by the following general formula (3) and / or (4): [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, and Es is a -O-C(=O)- bond or a -C(=O)-O- bond.) [ka] (In the formula, X2 is a divalent organic group, and R1 to R4 and Es are the same as above.) [ka] (In the formula, X3 is a tetravalent organic group that is the same as or different from X1, s is 0 or 1, Z is a divalent linking group, and when s=0, the two aromatic rings in the formula are directly linked without a linking group.) [ka] (In the formula, X4 is a divalent organic group that is the same as or different from X2, and s and Z are the same as those defined above.) (B) a photoacid generator, (C) a crosslinking agent, (D) a solvent, The negative type photosensitive resin composition comprises:

[0047] The present invention will be described in detail below, but the present invention is not limited thereto.

[0048] [Negative-type photosensitive resin composition] The negative photosensitive resin composition of the present invention contains the following components (A) to (D). Each component will be described in detail below.

[0049] [(A) Polymer] The (A) polymer contained in the negative photosensitive resin composition of the present invention contains structural units represented by the following general formulas (1) and / or (2) (hereinafter also referred to as structural unit (1) or structural unit (2)) and structural units represented by the following general formulas (3) and / or (4) (hereinafter also referred to as structural unit (3) or structural unit (4)). [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, and Es is a -O-C(=O)- bond or a -C(=O)-O- bond.) [ka] (In the formula, X2 is a divalent organic group, and R1 to R4 and Es are the same as above.) [ka] (In the formula, X3 is a tetravalent organic group that is the same as or different from X1, s is 0 or 1, Z is a divalent linking group, and when s=0, the two aromatic rings in the formula are directly linked without a linking group.) [ka] (In the formula, X4 is a divalent organic group that is the same as or different from X2, and s and Z are the same as those defined above.)

[0050] 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. It is preferably a tetravalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a tetravalent aromatic group having 6 to 40 carbon atoms, and may contain a siloxane skeleton. It is more preferably a tetravalent organic group represented by the following formula (18). 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.

[0051] In the above general formula (1), any of R1 to R4 is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom, preferably any one of R1 and R2 is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom, the other is a hydrogen atom, R3 and R4 are hydrogen atoms, more preferably any 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, the other is a hydrogen atom, and R3 and R4 are hydrogen atoms. More preferably, any one of R1 and R2 is a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom, the other is a hydrogen atom, and R3 and R4 are hydrogen atoms.

[0052] Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and a hexyl group. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group. Examples of the aromatic group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a diethylphenyl group, a propylphenyl group, a butylphenyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, a methoxyphenyl group, a dimethoxyphenyl group, an ethoxyphenyl group, a diethoxyphenyl group, an aminophenyl group, a nitrophenyl group, a cyanophenyl group, a phenethyl group, a phenylpropyl group, a phenylamino group, a diphenylamino group, a biphenyl group, and a naphthyl group. Examples of the phenoxy group having 6 to 10 carbon atoms include a methylphenoxy group, an ethylphenoxy group, a propylphenoxy group, a dimethylphenoxy group, a diethylphenoxy group, a methoxyphenoxy group, an ethoxyphenoxy group, and a dimethoxyphenoxy group. Examples of the benzyl group having 7 to 10 carbon atoms include a benzyl group, a methylbenzyl group, an ethylbenzyl group, a propylbenzyl group, a dimethylbenzyl group, a diethylbenzyl group, a methoxybenzyl group, an ethoxybenzyl group, a dimethoxybenzyl group, a diethoxybenzyl group, an aminobenzyl group, a nitrobenzyl group, and a cyanobenzyl group. Examples of the benzyloxy group having 7 to 10 carbon atoms include a benzyloxy group, a methylbenzyloxy group, an ethylbenzyloxy group, a propylbenzyloxy group, a dimethylbenzyloxy group, a diethylbenzyloxy group, a methoxybenzyloxy group, and an ethoxybenzyloxy group.

[0053] Among the above, aromatic groups having 6 to 12 carbon atoms, phenoxy groups having 6 to 10 carbon atoms, benzyl groups having 7 to 10 carbon atoms, and benzyloxy groups having 7 to 10 carbon atoms are preferred, aromatic groups having 6 to 12 carbon atoms are more preferred, and phenyl groups, methylphenyl groups, dimethylphenyl groups, ethylphenyl groups, and diethylphenyl groups are even more preferred. It is believed that such organic groups suppress free rotation of polymer chains due to their bulkiness, thereby suppressing the packing effect between molecules and making the interaction between molecules appropriate, thereby improving the mechanical properties of the cured coating, particularly the breaking elongation.

[0054] X2 in the above general formula (2) is a divalent organic group, and is not limited as long as it is a divalent organic group. It is preferably a divalent organic group having an aliphatic chain length structure with 4 to 40 carbon atoms, a divalent alicyclic aliphatic group with 4 to 40 carbon atoms, or a divalent aromatic group with 6 to 40 carbon atoms. It is more preferably a divalent organic group represented by the following formula (19). The structure of X2 may be one type or a combination of two or more types. [ka] (In the formula, R a3 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, q3 represents an integer of 1 to 30, and the dotted line represents a bond.

[0055] In the above general formula (2), R1 to R4 are the same as those in the above general formula (1).

[0056] X3 in the above general formula (3) 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. It is preferably a tetravalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a tetravalent aromatic group having 6 to 40 carbon atoms, and may contain a siloxane skeleton. It is more preferably a tetravalent organic group represented by the above formula (18). The structure of X3 may be one type or a combination of two or more types.

[0057] In the above general formula (3), s is 0 or 1. When s=0, the two aromatic rings in the above general formula (3) are directly bonded to each other without the divalent bonding group Z therebetween.

[0058] On the other hand, when s=1, the two aromatic rings in the above general formula (3) are bonded via a divalent bonding group Z. There are no limitations on Z as long as it is a divalent group. It is preferably a divalent alicyclic aliphatic group having 4 to 40 carbon atoms or a divalent aromatic group having 6 to 40 carbon atoms, and more preferably a divalent bonding group represented by the following formula (20). The structure of Z may be one type or a combination of two or more types.

[0059] [ka] (In the formula, q4, q5, and q6 represent integers of 1 to 6, and q7 and q8 represent integers of 1 to 10. The dotted lines represent bonds.)

[0060] Particularly preferred divalent linking groups Z are divalent groups represented by the following general formulae (5), (6), (7), and (8). That is, it is preferred that Z in the general formulae (3) and (4) is at least one linking group selected from the groups represented by the following formulae (5), (6), (7), and (8). [ka] (In the formula, the dotted lines represent bonds.)

[0061] Furthermore, the divalent linking group Z is preferably a divalent group represented by the above general formula (5) or (6).

[0062] As the structural unit represented by the above general formula (3), when Z in the above general formula (3) is a group represented by the above formula (5), a structural unit represented by the following general formula (3-1) is preferred, and when Z in the above general formula (3) is a group represented by the above formula (6), a structural unit represented by the following general formula (3-2) is preferred. [ka] (In the formula, X3 is the same as defined above.)

[0063] As in the above general formula (3-1), when the divalent bonding group Z is a hexafluoropropylene group represented by the above formula (5) and is located at the p-position of the phenolic hydroxyl group, the hexafluoropropylene group is an electron-withdrawing group, and therefore the acidity of the phenolic hydroxyl group is increased, and the solubility in an alkaline aqueous developer is improved, which is preferable.

[0064] Similarly, as in the above general formula (3-2), when the divalent bonding group Z is a sulfone group represented by the above formula (6) and is located at the p-position of the phenolic hydroxyl group, the sulfone group is also an electron-withdrawing group, and therefore the acidity of the phenolic hydroxyl group is increased, and the solubility in an alkaline aqueous developer is improved, which is preferable.

[0065] X4 in the above general formula (4) is a divalent organic group, which may be the same as or different from X2 above, and is not limited as long as it is a divalent organic group. Preferably, it is a divalent organic group having an aliphatic chain length structure with 4 to 40 carbon atoms, a divalent alicyclic aliphatic group with 4 to 40 carbon atoms, or a divalent aromatic group with 6 to 40 carbon atoms. More preferably, it is a divalent organic group represented by the above formula (19). Furthermore, the structure of X4 may be one type or a combination of two or more types.

[0066] When X4 in the above general formula (4) is a divalent organic group having an aliphatic chain structure, the mechanical strength, particularly the elongation, of the cured coating of the negative photosensitive resin composition of the present invention is preferably high.

[0067] In the above general formula (4), s and Z are the same as defined above, and Z is preferably the above general formula (5) or (6) from the viewpoint of solubility in an aqueous alkaline developer.

[0068] The (A) polymer contained in the negative photosensitive resin composition of the present invention can further contain, in addition to the structural units represented by the above general formulae (1), (2), (3), and (4), any one or more of the structural units represented by the following general formulae (21) to (24). [ka] (In the formula, X5 is a tetravalent organic group that is the same as or different from X1, and X6 is a divalent organic group.) [ka] (In the formula, X7 is a divalent organic group that is the same as or different from X2, and X8 is a divalent organic group that is the same as or different from X6.) [ka] (In the formula, X9 is a tetravalent organic group that is the same as or different from X1, 10 is a divalent organic group that is the same as or different from X6, and Rb may be the same as or different from each other, and is a hydrogen atom or an organic group having 1 to 10 carbon atoms, which may contain a heteroatom between them, and may have a substituent. [ka] (In the formula, X 11 is a divalent organic group that is the same as or different from X2, 12 is a tetravalent organic group.

[0069] X5 in the above general formula (21) 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. It is preferably a tetravalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a tetravalent aromatic group having 6 to 40 carbon atoms, and may contain a siloxane skeleton. It is more preferably a tetravalent organic group represented by the above formula (18). The structure of X5 may be one type or a combination of two or more types.

[0070] X6 in the above general formula (21) 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 aromatic or aliphatic rings having a substituent, or a divalent aliphatic group without a cyclic structure, or a siloxane group. More preferred X6 includes the structure represented by the following formula (25) or (26). The structure of X6 may be one type or a combination of two or more types. [ka] (In the formula, 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.

[0071] [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.

[0072] A negative photosensitive resin composition containing a polymer containing a structural unit represented by the above general formula (21) is preferable because it can improve the mechanical strength, adhesion to a substrate, and heat resistance of a cured film obtained by pattern formation. In addition, the structural unit (21) is preferable because it does not require a ring-closing reaction in post-curing and can relatively lower the curing reaction temperature.

[0073] X7 in the above general formula (22) is a divalent organic group, which may be the same as or different from X2 above, and is not limited as long as it is a divalent organic group. Preferably, it is a divalent organic group having an aliphatic chain length structure with 4 to 40 carbon atoms, a divalent alicyclic aliphatic group with 4 to 40 carbon atoms, or a divalent aromatic group with 6 to 40 carbon atoms. More preferably, it is a divalent organic group represented by the above formula (19). In addition, the structure of X7 may be one type or a combination of two or more types.

[0074] X8 in the above general formula (22) is a divalent organic group, but may be the same as or different from X6 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 aromatic or aliphatic rings having a substituent, or a divalent aliphatic group without a cyclic structure, or a siloxane group. More preferably, the structure represented by the above formula (25) or (26) can be mentioned. The structure of X8 may be one type or a combination of two or more types.

[0075] A negative photosensitive resin composition containing a polymer having a structural unit represented by the above general formula (22) is preferred because it can improve the mechanical properties, such as elongation, of a cured coating obtained by pattern formation, and the adhesion to a substrate.

[0076] X9 in the above general formula (23) 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. It is preferably a tetravalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a tetravalent aromatic group having 6 to 40 carbon atoms, and may contain a siloxane skeleton. It is more preferably a tetravalent organic group represented by the above formula (18). The structure of X9 may be one type or a combination of two or more types.

[0077] X in the above general formula (23) 10is 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. It is preferably a divalent organic group having 6 to 40 carbon atoms, and is a divalent cyclic organic group containing 1 to 4 aromatic or aliphatic rings having a substituent, or a divalent aliphatic group having no cyclic structure, or a siloxane group. More preferably, it is a structure represented by the above formula (25) or (26). In addition, X 10 The structure may be one type or a combination of two or more types.

[0078] A negative photosensitive resin composition containing a polymer containing a structural unit represented by the above general formula (23) is preferred because it improves the mechanical strength of the cured coating and the adhesion to the substrate.

[0079] X in the above general formula (24) 11 is a divalent organic group, which may be the same as or different from X2 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 having 4 to 40 carbon atoms, a divalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a divalent aromatic group having 6 to 40 carbon atoms. More preferably, it is a divalent organic group represented by the above formula (19). In addition, X 11 The structure may be one type or a combination of two or more types.

[0080] X in the above general formula (24) 12 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 aromatic or aliphatic rings having a substituent, or a tetravalent aliphatic group not having a cyclic structure, or a siloxane group. 12 Examples of the structure include the structure represented by the following formula (27). 12 The structure may be one type or a combination of two or more types. [ka] (In the formula, q 12 , q 13 , and q 14is an integer from 1 to 10, and q 15 is an integer from 1 to 20, and the dotted lines represent bonds.

[0081] A negative photosensitive resin composition containing a polymer containing a structural unit represented by the above general formula (24) is preferable because it can improve the mechanical strength, adhesion to the substrate, and heat resistance of the cured film obtained by pattern formation. In addition, when the structure represented by formula (27) is contained, it is preferable because it is not necessary to carry out a ring-closing reaction in the post-curing, and the curing reaction temperature can be relatively lowered.

[0082] The suitable molecular weight of the polymer (A) is preferably 5,000 to 100,000, more preferably 7,000 to 50,000. If the molecular weight is 5,000 or more, the negative type photosensitive resin composition of the present invention containing the polymer (A) can be easily formed into a film of a desired thickness on a substrate, and if the molecular weight is 100,000 or less, the viscosity of the negative type photosensitive resin composition does not become significantly high, and there is no risk of it being impossible to form a film. In the present invention, the weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0083] [(A) Method for Producing Polymer] The polymer (A) contains structural units represented by the following general formulae (1) and / or (2) and structural units represented by the following general formulae (3) and / or (4). [ka] (In the formula, X1, R1 to R4, and Es are the same as defined above.) [ka] (In the formula, X2, R1 to R4, and Es are the same as defined above.) [ka] (In the formula, X3, Z, and s are the same as defined above.) [ka] (In the formula, X4, Z, and s are the same as defined above.)

[0084] A polymer containing a structural unit represented by the above general formula (1) can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (28) with a diamine represented by the following general formula (29). First, a tetracarboxylic dianhydride represented by the following general formula (28) is reacted with a diamine represented by the following general formula (29) to synthesize an amide acid, and then the resulting mixture is heated and dehydrated to form an imide ring, thereby obtaining a polymer containing the structural unit (1).

[0085] The structural unit (1) can be produced by dissolving a diamine in a solvent having a high boiling point and high polarity, such as γ-butyrolactone or N-methyl-2-pyrrolidone, adding an acid anhydride, and reacting the resulting mixture at 0 to 80° C., preferably 10 to 50° C., to form an amide acid. Thereafter, a non-polar solvent, such as xylene, is added, and the mixture is heated to 100 to 200° C., preferably 130 to 180° C., to carry out an imidization reaction while removing water from the reaction system. [ka] (In the formula, X1 is the same as defined above.) [ka] (In the formula, R1 to R4 and Es are the same as above.)

[0086] Suitable examples of the tetracarboxylic acid dianhydride represented by the above general formula (28) include aromatic acid dianhydrides, alicyclic acid dianhydrides, aliphatic acid dianhydrides, and siloxane skeleton-containing acid dianhydrides.

[0087] 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, benzoic acid dianhydride, and the like. 3,3',4,4'-dihydrobenzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1,4-(3,4-dicarboxyphenoxy)benzene dianhydride, p-phenylene bis( Trimellitic 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 rings of these dianhydrides are substituted with alkyl groups, alkoxy groups, halogen atoms, or the like.

[0088] Examples of the alicyclic acid dianhydride include 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 1,2,4,5-cyclopentane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cycloheptane tetracarboxylic dianhydride, 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 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]heptane tetracarboxylic dianhydride, bicyclo[2,2,1]heptane-5-carboxymethyl-2,3,6-tricarboxylic dianhydride, 7-oxabicyclo[2,2,1]heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecahydroanhydride Examples of the dianhydride 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.) and their derivatives, as well as 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] Suitable examples of the diamine represented by the above general formula (29) 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)phenyl-4-aminobenzoate, (2-methylphenoxy-4-amino)phenyl-4-aminobenzoate, (2 ...methylphenoxy-4-amino)phenyl-4-aminobenzoate, (2-ethylphenoxy-4-amino)phenyl-4-aminobenzoate, (2-propylphenoxy)phenyl-4-aminobenzoate, (2-methylphenoxy-4-amino)phenyl-4-aminobenzoate, (2-methylphenoxy-4-amino)phenyl-4-aminobenzoate, (2-methylphenoxy-4-amino)phenyl-4-aminobenzoate, (2-methylphenoxy-4-amino)phenyl-4 (2-methoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (3-methoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (2-ethoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (3-ethoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (2-benzyl-4-amino)phenyl-4-aminobenzoate, (3-benzyl-4-amino)phenyl-4-aminobenzoate (2-methylbenzyl-4-amino)phenyl-4-aminobenzoate, (3-methylbenzyl-4-amino)phenyl-4-aminobenzoate, (2-ethylbenzyl-4-amino)phenyl-4-aminobenzoate, (3-ethylbenzyl-4-amino)phenyl-4-aminobenzoate, (2-propylbenzyl-4-amino)phenyl-4-aminobenzoate, (3-propylbenzyl-4-amino)phenyl-4-aminobenzoate, (2-methoxybenzyl-4-amino)phenyl-4- Aminobenzoate, (3-methoxybenzyl-4-amino)phenyl-4-aminobenzoate, (2-ethoxybenzyl-4-amino)phenyl-4-aminobenzoate, (3-ethoxybenzyl-4-amino)phenyl-4-aminobenzoate, (2-aminobenzyl-4-amino)phenyl-4-aminobenzoate, (3-aminobenzyl-4-amino)phenyl-4-aminobenzoate, (2-nitrobenzyl-4-amino)phenyl-4-aminobenzoate, (3-nitrobenzyl-4-amino)phenyl-4-aminobenzoate,(2-cyanobenzyl-4-amino)phenyl-4-aminobenzoate, (3-cyanobenzyl-4-amino)phenyl-4-aminobenzoate, (2-benzyloxy-4-amino)phenyl-4-aminobenzoate, (3-benzyloxy-4-amino)phenyl-4-aminobenzoate, (2-methylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-methylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (2-ethylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-ethylbenzyloxy-4-amino) Examples of the benzoic acid esters include, but are not limited to, 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, and (3-ethoxybenzyloxy-4-amino)phenyl-4-aminobenzoate.

[0093] On the other hand, a polymer containing a structural unit represented by the above general formula (2) can be obtained by reacting a dicarboxylic acid compound represented by the following general formula (30) with a diamine represented by the above general formula (29). [ka] (In the formula, X2 is the same as defined above.)

[0094] Here, the polymer containing the structural unit (2) can be obtained, for example, by reacting the dicarboxylic acid compound represented by the general formula (30) with the diamine represented by the general formula (29) in the presence of a dehydration condensation agent. That is, the dicarboxylic acid compound represented by the general formula (30) is used in the reaction in a state dissolved in a reaction solvent, and a known dehydration condensation agent (e.g., dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc.) is added and mixed into this reaction solution under ice cooling to convert the dicarboxylic acid compound represented by the general formula (30) into an acid anhydride, and then the diamine represented by the general formula (29) dissolved or dispersed in a separate solvent is dropped into this to polycondense, thereby obtaining a polymer containing the structural unit (2).

[0095] In addition, as another method for obtaining a polymer containing the structural unit (2) by reacting a dicarboxylic acid compound represented by the general formula (30) with a diamine represented by the general formula (29) (diamine compound), a synthesis method can be mentioned in which the dicarboxylic acid compound represented by the general formula (30) is converted into an acid chloride using a chlorinating agent such as thionyl chloride or dichlorooxalic acid, and then reacted with the diamine represented by the general formula (29).

[0096] In the reaction of converting the dicarboxylic acid compound into an acid chloride using a chlorinating agent, a basic compound such as pyridine, N,N-dimethyl-4-aminopyridine, or triethylamine may be used.

[0097] Next, the acid chloride of the dicarboxylic acid compound thus obtained is reacted with the diamine represented by the above general formula (29) in the presence of a basic catalyst to obtain a polymer containing the target structural unit (2). Examples of the basic catalyst include pyridine, N,N-dimethyl-4-aminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[4.3.0]non-5-ene. These basic catalysts may be used alone or in combination of two or more kinds.

[0098] Among the methods for producing the polymer (A), the solvent used in the method using an acid chloride is preferably one that dissolves well the above dicarboxylic acid compound and its acid chloride, and further the polymer obtained by polycondensation reaction with a diamine.Specific examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, etc.In addition to polar solvents, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. 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 kinds.

[0099] Suitable examples of X2 in the dicarboxylic acid compound represented by the above general formula (30) include the same as those mentioned above.

[0100] Examples of the dicarboxylic acid compound represented by the above general formula (30) 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 pimeline. Examples of the acid include 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, eicosanediacid, heneicosanediacid, docosanediacid, tricosanediacid, tetracosanediacid, pentacosanediacid, hexacosanediacid, heptacosanediacid, octacosanediacid, nonacosanediacid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, and diglycolic acid.

[0101] 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-phenylenediethane acid, bis(2,4-diphenyl ether dicarboxylic acid, bis(2,4-diphenyl ether dicarboxylic acid), ... Examples of the carboxyphenyl group include, but are not limited to, (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.

[0102] On the other hand, a polymer containing the structural unit (3) can be obtained by carrying out the same reaction procedure as that for the structural unit (1). That is, the polymer can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (31) with a diamine represented by the following general formula (32). First, an amide acid is synthesized by reacting a tetracarboxylic dianhydride represented by the following general formula (31) with a diamine represented by the following general formula (32), and then an imide ring is formed by thermal dehydration to obtain a polymer containing the structural unit (3). [ka] (In the formula, X3 is the same as defined above.) [ka] (In the formula, s and Z are the same as above.)

[0103] As suitable examples of the tetracarboxylic dianhydride represented by the above general formula (31), the examples given for the tetracarboxylic dianhydride represented by the above general formula (28) can be mentioned.

[0104] On the other hand, s in the above general formula (32) represents 0 or 1, and when s=0, the two aromatic rings in the above general formula (32) are directly bonded without the divalent bonding group Z therebetween.

[0105] Furthermore, when s in the above general formula (32) is s=1, Z in the above general formula (32) is not limited as long as it is a divalent group. As described above, it is preferably a divalent alicyclic aliphatic group having 4 to 40 carbon atoms or a divalent aromatic group having 6 to 40 carbon atoms, and more preferably a divalent linking group represented by the above formula (20). Furthermore, the structure of Z may be one type or a combination of two or more types.

[0106] Further, suitable examples of the diamine represented by the above general formula (32) are the compounds represented by the following formulae (33), (34), (35) and (36). [ka]

[0107] Furthermore, particularly preferred examples of the diamine represented by the above general formula (32) are the compounds represented by the above formulas (33) and (34).

[0108] The polymer obtained by reacting the diamine represented by the above formula (33) with the tetracarboxylic dianhydride represented by the above general formula (31) is a polymer containing the structural unit represented by the above general formula (3-1), which is a preferred structural unit.

[0109] On the other hand, the polymer obtained by reacting the diamine represented by the above formula (34) with the tetracarboxylic dianhydride represented by the above general formula (31) is a polymer containing the structural unit represented by the above general formula (3-2), which is a preferred structural unit.

[0110] On the other hand, a polymer containing the structural unit (4) can be obtained by carrying out the same reaction procedure as that for the structural unit (2), that is, by reacting a dicarboxylic acid compound represented by the following general formula (37) in the presence of a dehydration condensation agent or by converting the compound into an acid chloride using a chlorinating agent, and then reacting the compound with a diamine represented by the above general formula (32). [ka] (In the formula, X4 is the same as defined above.)

[0111] As suitable examples of the dicarboxylic acid compound represented by the above general formula (37), the examples given for the dicarboxylic acid compound represented by the above general formula (30) can be mentioned.

[0112] As described above, the (A) polymer contained in the negative type photosensitive resin composition of the present invention can further contain a structural unit represented by the following general formula (21), in addition to the structural units represented by the above general formulas (1), (2), (3), and (4). [ka] (In the formula, X5 and X6 are the same as above.)

[0113] A polymer containing the structural unit represented by the above general formula (21) can be obtained by carrying out the same reaction procedure as that for the structural unit (1). That is, a tetracarboxylic dianhydride represented by the following general formula (38) is reacted with a diamine represented by the following general formula (39) to synthesize an amide acid, and then a heat dehydration step is carried out to form an imide ring, thereby obtaining a polymer containing the structural unit represented by the above general formula (21). [ka] (In the formula, X5 is the same as defined above.) [ka] (In the formula, X6 is the same as defined above.)

[0114] As suitable examples of the tetracarboxylic dianhydride represented by the above general formula (38), the examples given for the tetracarboxylic dianhydride represented by the above general formula (28) can be mentioned.

[0115] Examples of the diamine represented by the general formula (39) include aromatic diamines, alicyclic diamines, aliphatic diamines, and polyether diamines.

[0116] Preferred aromatic diamines include, for example, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 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-phenyl Nylenediamine, 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, or diamine compounds in which the aromatic rings of these are substituted with alkyl groups, alkoxy groups, halogen atoms, or the like, but are not limited thereto.

[0117] Examples of the alicyclic diamine 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 alkyl group 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 alkyl groups is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

[0118] Examples of aliphatic diamines include alkylene diamines such as ethylene diamine, 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; and 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.

[0119] 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.

[0120] These aromatic diamines, alicyclic diamines, aliphatic diamines, and polyether diamines may be used alone or in combination of two or more kinds.

[0121] Siloxane diamines can also be suitably used.

[0122] As described above, the (A) polymer contained in the negative photosensitive resin composition of the present invention can further contain a structural unit represented by the following general formula (22), in addition to the structural units represented by the above general formulas (1), (2), (3), and (4). [ka] (In the formula, X7 and X8 are the same as above.)

[0123] A polymer containing the structural unit represented by the above general formula (22) can be obtained by carrying out the same reaction procedure as that for the structural unit (2) above. That is, the dicarboxylic acid compound represented by the following general formula (40) is reacted in the presence of a dehydration condensation agent or converted into an acid chloride using a chlorinating agent, and then reacted with a diamine represented by the following general formula (41). [ka] (In the formula, X7 is the same as defined above.) [ka] (In the formula, X8 is the same as defined above.)

[0124] As suitable examples of the dicarboxylic acid compound represented by the above general formula (40), the examples given for the dicarboxylic acid compound represented by the above general formula (30) can be mentioned.

[0125] As suitable examples of the diamine represented by the above general formula (41), there can be mentioned the examples given for the diamine represented by the above general formula (39).

[0126] As described above, the (A) polymer contained in the negative photosensitive resin composition of the present invention can further contain a structural unit represented by the following general formula (23), in addition to the structural units represented by the above general formulas (1), (2), (3), and (4). [ka] (In the formula, X9, 10 , and R b is the same as above.)

[0127] The polymer containing the structural unit represented by the above general formula (23) can be obtained by carrying out the same reaction procedure as that for the structural unit (2) above. That is, the polymer can be obtained by reacting a tetracarboxylic acid diester compound represented by the following general formula (42) in the presence of a dehydrating condensation agent or by converting the compound into an acid chloride using a chlorinating agent, and then reacting the compound with a diamine represented by the following general formula (43). [ka] (In the formula, R b and X9 are the same as above.) [ka] (In the formula, X 10 is the same as above.)

[0128] As a method for producing the tetracarboxylic acid diester compound represented by the above general formula (42), a tetracarboxylic acid dianhydride represented by the following general formula (44) is reacted with a compound having a terminal hydroxyl group represented by the following general formula (45) in the presence of a basic catalyst such as pyridine to give R b Here, the tetracarboxylic dianhydride represented by the following general formula (44) is the source of X9 in the above general formula (23) (for example, the tetravalent organic group represented by the above formula (18)). [ka] (In the formula, X9 is the same as defined above.) [ka] (In the formula, R b is the same as above.)

[0129] As suitable examples of the tetracarboxylic dianhydride represented by the above general formula (44), the examples given for the tetracarboxylic dianhydride represented by the above general formula (28) can be mentioned.

[0130] The reaction between the tetracarboxylic dianhydride represented by the general formula (44) and the compound having a hydroxyl group at its terminal represented by the general formula (45) can be carried out by stirring, dissolving and mixing the tetracarboxylic dianhydride represented by the general formula (44) and the compound having a hydroxyl group at its terminal represented by the general formula (45) 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, whereby a half-esterification reaction of the acid dianhydride proceeds, and the desired tetracarboxylic diester compound represented by the general formula (42) can be obtained as a solution dissolved in the reaction solvent.

[0131] The resulting tetracarboxylic acid diester compound may be isolated, or the resulting solution may be used as it is in the reaction with a diamine in the next step described above.

[0132] The reaction solvent is preferably one that dissolves well the tetracarboxylic acid diester compound and the polymer having the structural unit of the polyimide precursor obtained by the subsequent polycondensation reaction of the tetracarboxylic acid diester compound and diamines, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, γ-butyrolactone, etc. Ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. can also be used, and specific examples thereof 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, xylene, etc. These may be used alone or in combination as needed.

[0133] As suitable examples of the diamine represented by the above general formula (43), the examples given for the diamine represented by the above general formula (39) can be mentioned.

[0134] As described above, the polymer (A) contained in the negative photosensitive resin composition of the present invention can further contain a structural unit represented by the following general formula (24), in addition to the structural units represented by the general formulas (1), (2), (3), and (4). [ka] (In the formula, X 11 and X 12 is the same as above.)

[0135] The polymer containing the structural unit represented by the above general formula (24) can be obtained by reacting a dicarboxylic acid compound represented by the following general formula (46) 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 (47) to synthesize a hydroxyamide (polyoxazole precursor), which is then subjected to a heating dehydration step to form an oxazole ring. [ka] (In the formula, X 11 is the same as above.) [ka] (In the formula, X 12 is the same as above.)

[0136] As suitable examples of the dicarboxylic acid compound represented by the above general formula (46), the examples given for the dicarboxylic acid compound represented by the above general formula (30) can be mentioned.

[0137] Examples of the dihydroxydiamine compound represented by the above general formula (47) 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.

[0138] (Polymer molecular weight and introduction of end-capping agent) The suitable molecular weight of the polymer is preferably 5,000 to 100,000, more preferably 7,000 to 50,000. When the molecular weight is 5,000 or more, it becomes easy to form the negative type photosensitive resin composition of the present invention using the polymer into a film of a desired thickness on a substrate, and when the molecular weight is 100,000 or less, the viscosity of the negative type photosensitive resin composition does not become extremely high, and there is no risk of it being impossible to form a film.

[0139] The above polymer may be capped at both ends with a terminal capping agent in order to control the molecular weight in the polycondensation reaction and to suppress the change in molecular weight of the obtained polymer over time, i.e., gelation. Examples of terminal capping agents that react with acid dianhydrides include monoamines and monohydric alcohols. Examples of terminal capping agents that react with diamine compounds include acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds, dicarbonates, vinyl ethers, etc. In addition, various organic groups can be introduced as terminal groups by reacting with a terminal capping agent.

[0140] Examples of monoamines used as a blocking agent for the acid anhydride group terminal include aniline, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 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.

[0141] On the other hand, examples of monohydric alcohols used as a blocking agent for the acid anhydride group terminals 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 the glycerol 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.

[0142] Examples of acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds that can be used as the amino end 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 the monoacid chloride compounds include monoacid chloride compounds in which only the monocarboxy groups 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 are converted to acid chlorides, and monoactive ester compounds obtained by reacting the monoacid chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide.

[0143] Examples of the dicarbonate compound used as a blocking agent for the amino group terminal include di-tert-butyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.

[0144] Examples of vinyl ether compounds used as a blocking agent for the amino group terminal 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.

[0145] Other compounds used as a sealing agent for amino group terminals 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.

[0146] The introduction ratio of the blocking agent for the acid anhydride group terminal is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, and further 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 blocking agent for the amino group terminal is preferably in the range of 0.1 to 100 mol%, particularly preferably 5 to 90 mol%, based on the diamine component. A plurality of different terminal blocking agents may be reacted to introduce a plurality of different terminal groups.

[0147] [(B) Photoacid generator] The photoacid generator (B) contained in the negative photosensitive resin composition of the present invention is not particularly limited, but may be one that generates an acid by irradiation with light having a wavelength of 190 to 500 nm, and the acid serves as a curing catalyst. For example, onium salts, diazomethane derivatives, glyoxime derivatives, oxime sulfonate derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonic acid ester derivatives, imide-yl-sulfonate derivatives, iminosulfonate derivatives, triazine derivatives, etc. As described in detail below, these may be used alone or in combination of two or more kinds.

[0148] The onium salt includes, for example, a compound represented by the following general formula (48). (R 26 ) j M + K - (48) (In the formula, R 26 represents a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, which may have a substituent; M + is an iodonium ion or a sulfonium ion, and K - is a non-nucleophilic counterion, and j is 2 or 3.

[0149] Above R 26In the above, examples of the linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a 2-oxocyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group; an alkoxyphenyl group such as an o-, m-, or p-methoxyphenyl group, an ethoxyphenyl group, or an m- or p-tert-butoxyphenyl group; and an alkylphenyl group such as a 2-, 3-, or 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, or a dimethylphenyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a phenethyl group, and the like.

[0150] K - Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkylsulfonates such as triflate, 1,1,1-trifluoroethanesulfonate and nonafluorobutanesulfonate; arylsulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate and 1,2,3,4,5-pentafluorobenzenesulfonate; and alkylsulfonates such as mesylate and butanesulfonate.

[0151] The diazomethane derivative includes a compound represented by the following general formula (49). [ka] (In the formula, R 27 may be the same or different and represent a linear, branched, or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

[0152] Above R 27In the above formula, examples of the linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the linear, branched, or cyclic halogenated alkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group; an alkoxyphenyl group such as an o-, m-, or p-methoxyphenyl group, an ethoxyphenyl group, or an m- or p-tert-butoxyphenyl group; and an alkylphenyl group such as a 2-, 3-, or 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, or a dimethylphenyl group. Examples of halogenated aryl groups having 6 to 12 carbon atoms include a fluorophenyl group, a chlorophenyl group, a 1,2,3,4,5-pentafluorophenyl group, etc. Examples of aralkyl groups having 7 to 12 carbon atoms include a benzyl group, a phenethyl group, etc.

[0153] Specific examples of such photoacid generators include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, )phenylsulfonium, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate and other onium salts;Bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane diazomethane derivatives such as 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-amylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-amylsulfonyl)diazomethane, 1-tert-amylsulfonyl-1-(tert-butylsulfonyl)diazomethane, and 1-tert-amylsulfonyl-1-(tert-butylsulfonyl)diazomethane;Bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis -o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime glyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, bis-o-(camphorsulfonyl)-α-dimethylglyoxime, etc. oxime derivatives; oxime sulfonate derivatives such as α-(benzenesulfonium oxyimino)-4-methylphenylacetonitrile; β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane; disulfone derivatives such as diphenyl disulfone and dicyclohexyl disulfone; nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate;Sulfonic acid ester derivatives such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3-tris(p-toluenesulfonyloxy)benzene; phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene 2,3-dicarboximido-yl-triflate, 5-norbornene 2,3-dicarboximido-yl-tosylate, 5-norbornene 2,3-dicarboximido-yl-n-butylsulfonate, n-trifluoromethy iminosulfonate derivatives such as (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile, 2-methyl-2[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane, etc. Among these, iminosulfonate derivatives, iminosulfonate derivatives, oxime sulfonate derivatives, etc. are preferably used. The above photoacid generators can be used alone or in combination of two or more kinds.

[0154] From the viewpoints of the light absorption of the photoacid generator itself and the photocurability in a thick film, the amount of the photoacid generator (B) in the negative type photosensitive resin composition of the present invention is preferably 0.05 to 20 parts by mass, and particularly preferably 0.2 to 5 parts by mass, per 100 parts by mass of the component (A).

[0155] [(C) Crosslinking agent] The (C) crosslinking agent contained in the negative photosensitive resin composition of the present invention may be any compound having a group crosslinking with the (A) component. The (C) component is preferably one or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule, a compound in which the hydrogen atom of the hydroxyl group of a polyhydric phenol is replaced with a glycidyl group, a compound in which the hydrogen atom of the hydroxyl group of a polyhydric phenol or the hydroxyl group of a polyhydric alcohol is replaced with a substituent represented by the following formula (C-1), and a compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2). [ka] (In the formula, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.)

[0156] 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.

[0157] The above-mentioned 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 (50). The above-mentioned alcohol is preferably a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms.

[0158] [ka] (In the formula, R 28may be the same or different and are a methylol group, an alkoxymethyl group containing an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, provided that at least one of them is a methylol group or the above alkoxymethyl group.

[0159] Above R 28 Examples of the alkyl group include alkoxymethyl groups including alkoxy groups having 1 to 4 carbon atoms, such as a methylol group, a methoxymethyl group, and an ethoxymethyl group, and a hydrogen atom.

[0160] Specific examples of modified melamine represented by the above general formula (50) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethylol melamine, etc. Next, the modified melamine represented by the above general formula (50) or its multimer (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.

[0161] The above-mentioned urea condensate modified with formaldehyde or formaldehyde-alcohol can be prepared, for example, according to a known method, by modifying a urea condensate having a desired molecular weight with formaldehyde by methylolation, or by further modifying the urea condensate by alkoxylation with an alcohol.

[0162] Specific examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, and propoxymethylated urea condensate.

[0163] The modified melamine condensates and modified urea condensates may be used alone or in combination of two or more.

[0164] 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 (C-3) to (C-7). [ka] (In the formula, Me is a methyl group.)

[0165] The phenol compounds having two or more methylol groups or alkoxymethylol groups on average per molecule can be used either individually or in combination of two or more.

[0166] On the other hand, examples of compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are replaced 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 replaced with glycidyl groups include the compounds represented by the following formulas (C-8) to (C-14). [ka] (In the formula, t is 2≦t≦3.)

[0167] 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 alone or in combination as a crosslinking agent.

[0168] Examples of compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols or polyhydric alcohols are substituted with the substituents represented by the following formula (C-1) include compounds containing two or more of the above-mentioned substituents and represented by the following general formula (C-15). [ka] (In the formula, the dotted lines represent bonds.) [ka] (In the formula, 1≦u≦3.)

[0169] One or a combination of two or more compounds in which the hydrogen atoms of the hydroxyl groups of a polyhydric phenol or the hydroxyl groups of a polyhydric alcohol are substituted with the substituents represented by the above formula (C-1) can be used as a crosslinking agent.

[0170] On the other hand, examples of the compound having two or more nitrogen atoms having a glycidyl group, as shown in the following formula (C-2), include those shown in the following general formula (C-16). [ka] (In the formula, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.) [ka] (In the formula, U represents a linear, branched, or cyclic alkylene group having 2 to 12 carbon atoms, or a divalent aromatic group having 6 to 12 carbon atoms.)

[0171] Examples of the compound represented by the above general formula (C-16) include compounds represented by the following formulae (C-17) to (C-20). [ka]

[0172] On the other hand, as the compound containing two or more nitrogen atoms having a glycidyl group represented by the above formula (C-2), a compound represented by the following formula (C-21) can also be suitably used. [ka]

[0173] These compounds having two or more nitrogen atoms with a glycidyl group, as represented by the above formula (C-2), can be used as a crosslinking agent either individually or in combination of two or more.

[0174] As described above, the (C) component of the negative photosensitive resin composition of the present invention is a component that can form a negative pattern by crosslinking the crosslinking group of the (C) component with the polymer of the (A) component using the acid generated from the (B) component as a catalyst, and also causes a crosslinking reaction during post-curing after pattern formation, thereby further increasing the strength of the cured product. From the viewpoints of photocurability and heat resistance, the weight-average molecular weight of such a (C) component is preferably 150 to 10,000, and particularly preferably 200 to 3,000.

[0175] The amount of the component (C) blended in the negative photosensitive resin composition of the present invention is preferably 0.5 to 50 parts by mass, and particularly preferably 1 to 30 parts by mass, per 100 parts by mass of the component (A).

[0176] [(D) Solvent] The solvent for component (D) in the present invention is not limited as long as it dissolves components (A), (B), and (C). Examples of the solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-amyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol-mono-tert-butyl ether acetate, and γ-butyrolactone. One or more of these may be used. Particularly, ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, or a mixed solvent thereof is preferred.

[0177] The blend amount of component (D) 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).

[0178] [(E) Crosslinkable polymer compound] The negative photosensitive resin composition of the present invention may contain (E) a crosslinkable polymer compound. That is, the negative photosensitive resin composition may further contain: (E) a crosslinkable polymer compound containing a structural unit represented by the following general formula (9) and having a group capable of crosslinking with the component (A): [ka] (In the formula, R5 is a hydrogen atom or a methyl group, R6 is a (n+1)-valent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, a benzyl group, or a naphthalenemethyl group, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. n is an integer of 1 to 5. Y1 is -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R7OH)-, respectively. R7 is a divalent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. p1 is 0 or 1.) It is preferable that the composition contains the following:

[0179] In addition, in the structure represented by the above general formula (9), specific examples that can be preferably used are given below. [ka] (In the formula, R5 is as defined above.)

[0180] [ka] (In the formula, R5 is as defined above.)

[0181] [ka] (In the formula, R5 is as defined above.)

[0182] The (E) crosslinkable polymer compound contained in the negative photosensitive resin composition of the present invention is more preferably a crosslinkable polymer compound that contains a structural unit represented by the following general formula (10) and a structural unit represented by the following general formula (11) having a group that crosslinks with the (A) component, in order to improve the crosslink density while maintaining alkali solubility. [ka] (In the formula, R8 is a hydrogen atom or a methyl group, and Y2 is -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R9OH)-. R9 is a divalent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. p2 is 0 or 1.) [ka] (In the formula, R 10 is a hydrogen atom or a methyl group, R 11 is a group containing an oxazoline group, an isocyanate group, a blocked isocyanate group, an oxetanyl group, or an epoxy group, and Y3 is -C(=O)-O-, a phenylene group, or a naphthylene group. p3 is 0 or 1.

[0183] The blocked isocyanate group is an organic group in which an isocyanate group (-N=C=O) is blocked with an appropriate protecting group. The blocked isocyanate group can be formed by reacting the isocyanate group with a blocking agent.

[0184] When reacting with the hydroxyl or carboxyl groups in the component (A), the blocking agent is eliminated, and the hydroxyl or carboxyl groups react with the isocyanate groups to form a crosslinked structure. The blocking agent is an active hydrogen-containing compound capable of reacting with isocyanate, such as alcohol, phenol, polycyclic phenol, amide, imide, imine, thiol, oxime, lactam, active hydrogen-containing heterocycle, and active methylene-containing compound.

[0185] Suitable blocked isocyanate groups are described in paragraphs

[0015] to

[0025] of Japanese Patent No. 6601628, and the compounds thereof can be used.

[0186] On the other hand, when the structure represented by the general formula (10) has a carbonyl group or an amide group, which is an electron-withdrawing group, at the p-position of the phenolic hydroxyl group, the acidity of the phenolic hydroxyl group is increased, and the solubility in an alkaline aqueous developer is improved. Specific examples that can be preferably used include the following. However, the present invention is not limited to these.

[0187] [ka] (In the formula, R8 is as defined above.)

[0188] [ka] (In the formula, R8 is as defined above.)

[0189] The above general formula (10) is effective as a unit that promotes crosslinking in addition to improving alkali solubility, and by using it in combination with a crosslinkable group, it becomes possible to further improve the curability.

[0190] The crosslinkable polymer compound (E) contained in the negative photosensitive resin composition of the present invention preferably further contains a structural unit having an epoxy group or an oxetanyl group represented by the following general formula (12) in order to improve the crosslink density. [ka]

[0191] In the general formula (12), R 12 is R 12 is a hydrogen atom or a methyl group, and Y is -C(=O)-O-, a phenylene group, or a naphthylene group. 13 is a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may contain a hydroxyl group, an ester group, an ether group or an aromatic hydrocarbon; R 14 is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R 13R may be bonded to form a ring. 15 is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R 16 is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, and R 13 may be bonded to form a ring. m is 0 or 1. p4 is 0 or 1.

[0192] Examples of the unit of the above general formula (12) are as follows: [ka] (In the formula, R 12 is as above.)

[0193] [ka] (In the formula, R 12 is as above.)

[0194] [ka] (In the formula, R 12 is as above.)

[0195] In addition, some of the monomers for obtaining repeating units having an epoxy group or an oxetanyl group are disclosed in Japanese Patent Application Laid-Open Nos. 2003-055362, 2005-008847, and 2005-018012.

[0196] The structural unit represented by the above general formula (10) has excellent solvent solubility and alkali solubility, but is not crosslinkable, and is therefore preferably copolymerized with the structural unit represented by the above general formula (12) having crosslinkability. The polymer consisting of only epoxy groups and oxetanyl groups represented by the above general formula (12) having crosslinkability has excellent crosslinkability, but is not soluble in alkali, and is therefore preferably copolymerized with the structural unit represented by the above general formula (10).

[0197] Therefore, when the repeating units are copolymerized in this manner, the component (E) is preferably a crosslinkable polymer compound containing structural units represented by the following general formula (10) and the following general formula (12). [ka] (In the formula, R8~~R 16 , Y2, Y4, m, p2, and p4 are the same as above, and 0 <a1<1.0、0<a2<1.0、0<a1+a2≦1.0である。)

[0198] The (E) crosslinkable polymer compound contained in the negative photosensitive resin composition of the present invention is more preferably a crosslinkable polymer compound further containing a structural unit represented by the following general formula (13), from the viewpoints of further improving the crosslinking reactivity during lithopatterning and improving the dissolution contrast of the unexposed / exposed areas in an alkali developer. [ka] (In the formula, R 17 is a hydrogen atom or a methyl group, R 18 is a single bond or a (l+1)-valent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. Y5 is -C(=O)-O-, -C(=O)-OR 19 -, -C(=O)-NH-, -C(=O)-N(R 19 OH)-, a phenylene group, or a naphthylene group. 19 is a divalent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. 1 is 0 or 1.

[0199] Examples of the unit of the above general formula (13) include those which do not contain an aromatic hydrocarbon group among the examples of the unit of the above general formula (9).

[0200] From the viewpoint of improving adhesion to a substrate and heat resistance, the (E) crosslinkable polymer compound contained in the negative photosensitive resin composition of the present invention is more preferably a crosslinkable polymer compound further containing at least one structural unit selected from structural units formed by cyclopolymerization and represented by the following general formula (14), the following general formula (15), the following general formula (16), and the following general formula (17). [ka] (In the formula, R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

[0201] In particular, structural units obtained by cyclopolymerization of monomer units represented by the following general formulae (51) and (52) are preferred. These monomers may be used alone or in combination of two or more kinds.

[0202] [ka] (In the formula, R 23 , R 24 , and R 25 is as stated above.)

[0203] In particular, specific examples of commercially available products include the ACRYCURE RD series and the ACRYCURE RE series (product names, manufactured by Nippon Shokubai Co., Ltd.).

[0204] In particular, from the viewpoints of polymerizability and stability, the above monomer unit (51), which becomes a structural unit of the above general formula (16) upon cyclopolymerization, is more preferred.

[0205] Here, in order to achieve compatibility among mechanical properties, alkali solubility, and crosslinkability, it is preferable that the component (E) is a crosslinkable polymer compound containing structural units represented by the following general formula (10), the following general formula (12), the following general formula (13), and the following general formula (16).

Chemical formula

[0206] Here, 0 < a1 < 1.0, 0 < a2 < 1.0, 0 < a3 < 1.0, 0 < a4 < 1.0, and 0 < a1 + a2 + a3 + a4 ≤ 1.0. In general formulas (10), (12), (13), and (16), R8, R 12 ~R 18 、R 23 、Y2, Y4, Y5, m, p2, p4, and l are the same as described above.

[0207] From the viewpoints of improving the adhesion to the substrate, the flexibility of the cured film, and further improving the mechanical properties and heat shock resistance, the crosslinkable polymer compound (E) contained in the negative photosensitive resin composition of the present invention can further contain a structural unit represented by the following general formula (53).

[0208]

Chemical formula

[0209] Here, in the above general formula (53), R 28 is a hydrogen atom or a methyl group, and R 29 is a monovalent organic group having a primary, secondary, or tertiary amino group, an alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alicyclic group having 6 to 10 carbon atoms. Y6 is -C(=O)-O- or -C(=O)-NH-.

[0210] Specific examples of monomers from which the repeating unit represented by the above general formula (53) is derived include the following: aminoethyl(meth)acrylate, N-methylaminoethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N-ethylaminoethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, aminopropyl(meth)acrylate, N-methylaminopropyl(meth)acrylate, N,N-dimethylaminopropyl(meth)acrylate, N-ethylaminopropyl(meth)acrylate, N,N-diethylaminopropyl(meth)acrylate, aminoethyl(meth)acrylamide, N-methylaminoethyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N-ethylaminoethyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylate. Examples of the ethylaminoethyl (meth)acrylamide include ethylaminoethyl (meth)acrylamide, aminopropyl (meth)acrylamide, N-methylaminopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N-ethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, piperidin-4-yl (meth)acrylate, 1-methylpiperidin-4-yl (meth)acrylate, 2,2,6,6-tetramethylpiperidin-4-yl (meth)acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth)acrylate, (piperidin-4-yl)methyl (meth)acrylate, and 2-(piperidin-4-yl)ethyl (meth)acrylate.

[0211] Further, specific examples of the (meth)acrylic acid alkyl ester include (meth)acrylic acid butyl ester, (meth)acrylic acid pentyl ester, (meth)acrylic acid hexyl ester, (meth)acrylic acid heptyl ester, (meth)acrylic acid octyl ester, (meth)acrylic acid nonyl ester, (meth)acrylic acid decyl ester, (meth)acrylic acid undecyl ester, (meth)acrylic acid dodecyl ester, (meth)acrylic acid tridecyl ester, (meth)acrylic acid tetradecyl ester, (meth)acrylic acid pentadecyl ester, (meth)acrylic acid hexadecyl ester, (meth)acrylic acid heptadecyl ester, (meth)acrylic acid octadecyl ester, (meth)acrylic acid nonadecyl ester, (meth)acrylic acid eicosyl ester, and the like.

[0212] Furthermore, for the purpose of improving the mechanical strength of the cured coating, olefins having aromatic groups, such as styrenes, vinylnaphthalenes, vinylanthracenes, vinylcarbazoles, acenaphthylenes, and indenes, and alicyclic olefins, such as norbornenes and norbornadienes, may be copolymerized.

[0213] The crosslinkable polymer compound (E) contained in the negative photosensitive resin composition of the present invention preferably has a weight average molecular weight of 1,000 to 500,000, particularly 2,000 to 30,000, as measured by gel permeation chromatography (GPC) in terms of polystyrene. If the weight average molecular weight is 1,000 or more, the glass transition temperature is high, and the pattern does not deform during thermal crosslinking after development of the negative photosensitive resin composition, and if it is 500,000 or less, pinhole defects do not occur during application. It is also possible to blend two or more polymers having different composition ratios, molecular weight distributions, or molecular weights.

[0214] In addition, the amount of the crosslinkable polymer compound (E) added is preferably 10 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the polymer (A). When the amount added is 10 parts by mass or more, the toughness of the cured film with the polymer (A) as described above is high, and when the amount added is 100 parts by mass or less, the tensile strength of the cured film does not decrease, so the amount of the crosslinkable polymer compound (E) added is preferably within the above range. The amount of the crosslinkable polymer compound (E) added is more preferably 10 parts by mass or more and 70 parts by mass or less, and even more preferably 30 parts by mass or more and 50 parts by mass or less. By setting it within this range, a good balance between lithography patterning performance and cured film properties is achieved.

[0215] The negative type photosensitive resin composition of the present invention may contain, in addition to the essential components (A), (B), (C), and (D) and preferably the component (E), one or more selected from the group consisting of a basic compound (F), a thermal acid generator (G), an antioxidant (H), and a silane compound (I). Components (F), (G), (H), and (I) will be described in detail below.

[0216] [(F) Basic compounds] The basic compound of the component (F) is preferably a compound capable of suppressing the diffusion rate of the acid generated by the photoacid generator (B) when it diffuses into the photosensitive resin composition. By incorporating such a basic compound (F), the diffusion rate of the acid in the photosensitive resin composition is suppressed, and the resolution is improved, the change in sensitivity after exposure is suppressed, and the dependency on the substrate and environment is reduced, and the exposure margin and pattern profile can be improved.

[0217] Examples of the (F) basic compound include ammonia, primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, and imide derivatives.

[0218] Specific examples of primary aliphatic amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, and tetraethylenepentamine. Specific examples of secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, and diethylamine. Examples of the tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyltetraethylenepentamine, and the like.

[0219] Examples of mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine.

[0220] Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (e.g., aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, etc.), diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (e.g., oxazole, isoxazole, etc.), thiazole derivatives (e.g., thiazole, isothiazole, etc.), imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives Examples of the conductors include quinoline derivatives (e.g., quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, and uridine derivatives.

[0221] Further, examples of nitrogen-containing compounds having a carboxy group include aminobenzoic acid, indole carboxylic acid, amino acid derivatives (e.g., nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.), and the like.

[0222] Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridine sulfonic acid and pyridinium p-toluenesulfonate.

[0223] Examples of nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)morpholine, and 2-(2-hydroxyethyl)morpholine. Examples of the 1-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidineethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyjurolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N-(2-hydroxyethyl)phthalimide, and N-(2-hydroxyethyl)isonicotinamide.

[0224] Examples of the amide derivatives include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, and benzamide.

[0225] Examples of the imide derivative include phthalimide, succinimide, and maleimide.

[0226] The basic compound (F) can be used alone or in combination of two or more, and the amount of the basic compound is preferably 0 to 2 parts by mass, more preferably 0.01 to 2 parts by mass, and particularly preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer (A). If the amount is 2 parts by mass or less, the sensitivity does not decrease.

[0227] [(G) Thermal acid generator] The negative type photosensitive resin composition of the present invention may further contain a thermal acid generator (G). The thermal acid generator (G) can be added for the purpose of thermally promoting the crosslinking reaction of the components (A), (C), and (E) in the process of heating and post-curing at a temperature of 100 to 300° C. after pattern formation, which will be described later.

[0228] In particular, the (G) component is preferably one that does not promote the curing of the film until a pattern is formed by development and does not inhibit pattern formation. To achieve this, the (G) component is preferably one that does not generate acid at the temperature of the process of removing the solvent and drying after coating the photosensitive resin composition, but generates acid only by heat treatment after pattern formation to promote the curing of the pattern or coating of the negative photosensitive resin composition. Specifically, it is preferable that the (G) component is a compound that decomposes and generates acid by heat treatment at 100°C to 300°C, preferably 150°C to 300°C. By containing such a (G) component, the pattern or coating of the negative photosensitive resin composition can be changed to a pattern or coating in which the crosslinking and curing reaction has progressed further in the process of heating and post-curing at a temperature of 100 to 300°C applied after pattern formation. The (G) component further advances the crosslinking and curing reaction, making it possible to further improve the mechanical strength, chemical resistance, adhesion, etc. of the obtained pattern or coating.

[0229] As suitable (G) thermal acid generators, the compounds described in paragraphs

[0061] to

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

[0230] The amount of the thermal acid generator (G) 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 5 parts by mass or less, relative to 100 parts by mass of the component (A) in the negative photosensitive resin composition of the present invention. When the amount is 0.1 parts by mass or more, the crosslinking reaction is promoted. When the amount is 30 parts by mass or less, the alkali developability of the composition is not deteriorated, and development residue is not generated.

[0231] [(H) Antioxidants] The negative photosensitive resin composition of the present invention may further contain an antioxidant (H). By containing the antioxidant (H), the oxidation deterioration of the aliphatic group and the phenolic hydroxyl group of the component (A) is suppressed. In addition, due to the rust-preventing effect on the metal material, it is possible to suppress metal oxidation caused by external moisture, photoacid generators, thermal acid generators, etc., and the resulting decrease in adhesion and peeling.

[0232] Specific examples of the (H) antioxidant that can be used here include hindered phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. However, the antioxidants are not limited to these. These (H) antioxidants can be used alone or in combination of two or more.

[0233] 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), Adeka STAB Examples of the hindered phenol-based antioxidant include AO-20 (manufactured by ADEKA Corporation, product name), ADK STAB AO-30 (manufactured by ADEKA Corporation, product name), ADK STAB AO-40 (manufactured by ADEKA Corporation, product name), ADK STAB AO-50 (manufactured by ADEKA Corporation, product name), ADK STAB AO-60 (manufactured by ADEKA Corporation, product name), ADK STAB AO-80 (manufactured by ADEKA Corporation, product name), ADK STAB AO-330 (manufactured by ADEKA Corporation, product name), and the hindered phenol-based antioxidants described in WO 2017 / 188153.

[0234] 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-diisodecyl phosphite, tetradecylpoly(oxyethylene)-bis(ethylphenyl) phosphite, phenyl-dicyclohexyl phosphite, phenyl-diisooctyl phosphite, phenyl-di(tridecyl) phosphite, diphenyl-cyclohexyl phosphite, diphenyl-isooctyl phosphite, diphenyl-2-ethylhexyl phosphite, diphenyl-isodecyl phosphite, diphenyl-cyclohexyl phenyl phosphite, diphenyl-(tridecyl)thiophosphite, and the like.

[0235] Further specific examples of the (H) antioxidant include sulfur-based antioxidants such as ADK STAB AO-412S (manufactured by ADEKA CORPORATION, product name), AO-503S (manufactured by ADEKA CORPORATION, product name), and Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd., product name).

[0236] The sulfur-based antioxidant and the phosphorus-based antioxidant are expected to have the effect of decomposing peroxides.

[0237] The content of the (H) antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the polymer (A). When the content is 0.1 part by mass or more, adhesion to metal materials is improved and peeling is suppressed. When the content is 10 parts by mass or less, the alkali developability of the composition and the toughness of the cured coating are not deteriorated.

[0238] [(I) Silane compound] The negative photosensitive resin composition of the present invention may further contain (I) a silane compound. By containing the silane compound as component (I), not only can the adhesion to metal materials be improved, but also peeling of the cured coating can be suppressed during reliability tests such as thermal shock tests and high temperature and high humidity tests.

[0239] The silane compound (I) that can be used here is not particularly limited, but is preferably one having an alkoxysilyl group. In addition, preferred specific examples are shown below. γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, bis(2-hydroxyethyl)-3-aminopropyl-triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyl ... Examples of the silane compounds include aminopropyl triethoxysilane, triethoxysilyl propyl ethyl carbamate, 3-(triethoxysilyl)propyl succinic anhydride, phenyl triethoxysilane, phenyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, 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 Publication No. 2017-044964. However, the examples are not limited to these. Furthermore, these (I) silane compounds can be used alone or in combination of two or more.

[0240] The content of the silane compound (I) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 3 to 6 parts by mass, based on 100 parts by mass of the polymer (A). When the content is 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, and when the content is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed. When the content is 10 parts by mass or less, the alkali developability of the composition is not deteriorated, and development residue is not generated.

[0241] [Other ingredients] The negative photosensitive resin composition of the present invention may further contain components other than the components (A), (B), (C), (D), (E), (F), (G), (H) and (I). Examples of the other components include a surfactant (J) and a dissolution inhibitor (K). The compounds exemplified below can be suitably used. However, they are not limited thereto.

[0242] [(J) Surfactants] The (J) surfactant is preferably a nonionic surfactant, such as a fluorine-based surfactant, specifically, perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, fluorine-containing organosiloxane compound, or non-fluorine-containing organosiloxane compound.

[0243] As these (J) surfactants, commercially available products can be used, 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.), and the like. 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 preferable.

[0244] 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 the coatability onto the substrate without impairing the patterning performance or the properties of the cured coating.

[0245] [(K) Dissolution inhibitor] Examples of the (K) dissolution inhibitor include a compound having a weight-average molecular weight of 100 to 1,000, preferably 150 to 800, and having two or more phenolic hydroxyl groups in the molecule, in which the hydrogen atoms of the phenolic hydroxyl groups are substituted with acid labile groups in an average ratio of 0 to 100 mol % as a whole, and a compound having a carboxy group in the molecule, in which the hydrogen atoms of the carboxy groups are substituted with acid labile groups in an average ratio of 50 to 100 mol % as a whole.

[0246] The substitution rate of hydrogen atoms of phenolic hydroxyl groups with acid labile groups is, on average, 0 mol % or more, preferably 30 mol % or more, with an upper limit of 100 mol %, more preferably 80 mol % of all phenolic hydroxyl groups. The substitution rate of hydrogen atoms of carboxyl groups with acid labile groups is, on average, 50 mol % or more, preferably 70 mol % or more, with an upper limit of 100 mol % of all carboxyl groups.

[0247] In this case, the compound having two or more phenolic hydroxyl groups or the compound having a carboxy group is preferably one represented by the following formulae (K1) to (K14).

[0248] [ka]

[0249] However, in the above formula, R 201 , R 202 R represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms. 203 R represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms. 204 Ha-(CH2) i1 -(i1=2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom, or a sulfur atom. 205 R represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom, or a sulfur atom. 206 R represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a phenyl group or naphthyl group each substituted with a hydroxyl group. 208 represents a hydrogen atom or a hydroxyl group. v1 is an integer of 0 to 2, and v2 is 0 or 1. w1 and h1 are 0 or 1. t1, u1, t2, u2, t3, and u3 are numbers that satisfy t1+u1=8, t2+u2=5, and t3+u3=4, respectively, and each phenyl skeleton has at least one hydroxyl group. aa is a number that makes the molecular weight of the compound of formula (K8) or (K9) 100 to 1,000.

[0250] The amount of the dissolution inhibitor (K) to be blended is more than 0 and not more than 50 parts by mass, preferably 5 to 50 parts by mass, and more preferably 5 to 20 parts by mass, per 100 parts by mass of the polymer (A), and they can be used alone or in combination of two or more. The blending of component (K) improves the resolution, and by keeping the blending amount at 50 parts by mass or less, no film loss of the pattern occurs, and no decrease in resolution occurs.

[0251] (Pattern formation method) The present invention provides a pattern forming method, comprising the steps of: (1) A step of applying the above-described negative photosensitive resin composition onto a substrate to form a photosensitive film; (2) subsequently exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask after the heat treatment; (3) developing the substrate that has been subjected to the heat treatment after the exposure using an aqueous alkaline developer; The present invention provides a pattern forming method comprising the steps of: Hereinafter, a pattern forming method using the negative photosensitive resin composition of the present invention will be described.

[0252] In the negative photosensitive resin composition of the present invention, a pattern can be formed by employing a known lithography technique. For example, the negative photosensitive resin composition is applied by spin coating to a substrate having a pattern formed thereon, such as a silicon wafer, a SiO2 substrate, a SiN substrate, or copper wiring, and 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.

[0253] In the spin coating method, the photosensitive resin composition is applied onto a silicon substrate by dispensing about 5 mL of the photosensitive resin composition onto the substrate and then rotating the substrate. At this time, the thickness of the photosensitive film on the substrate can be easily adjusted by adjusting the rotation speed.

[0254] Next, a photomask for forming a desired pattern is placed over the photosensitive film, and high-energy rays such as i-rays and g-rays having a wavelength 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 The light is irradiated and exposed to light so that the intensity of the light is approximately 100 nm.

[0255] Next, post-exposure bake (PEB) is performed on a hot plate at 60 to 150° C. for 1 to 10 minutes, preferably at 80 to 120° C. for 1 to 5 minutes.

[0256] In the negative photosensitive resin composition of the present invention, alkaline development is possible using an aqueous alkaline developer.

[0257] On the other hand, a suitable alkaline aqueous developer that can be used for alkaline development is a 2.38% aqueous solution of tetramethylhydroxyammonium (TMAH). Development can be carried out by a normal method such as a spray method or a paddle method, or by immersion in the developer. Thereafter, washing, rinsing, drying, etc. can be carried out as necessary to obtain a photosensitive film having a desired pattern.

[0258] (Hardened film formation method) The present invention also provides a method for forming a cured coating, comprising the step of heating and post-curing the patterned photosensitive coating obtained by the pattern formation method described above at a temperature of 100 to 300°C.

[0259] That is, the photosensitive material film patterned by the above-mentioned pattern forming method can be heated and post-cured using an oven or a 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 film. If the post-curing temperature is 100 to 300°C, the crosslink density of the photosensitive resin composition film can be increased and residual volatile components can be removed, which is preferable from the viewpoints of adhesion to the substrate, heat resistance and strength, and further electrical properties. The post-curing time can be 10 minutes to 10 hours.

[0260] The above-mentioned formed patterns are used for the purpose of forming 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, such as Cu, of the wiring or circuit they cover, metal electrodes present on the substrate, or insulating substrates, such as SiN, present on the wiring or circuit they cover, and can significantly improve resolution performance to enable the formation of even finer patterns while retaining the mechanical strength suitable for a protective coating.

[0261] (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 the like, and also has excellent reliability for semiconductor elements using it as a protective coating, particularly in preventing cracks during temperature cycle tests. Thus, it is suitable for use as a protective coating (interlayer insulating film or surface protective film) for electrical / electronic components, semiconductor elements, etc.

[0262] That is, the present invention provides an interlayer insulating film or a surface protective film which is a cured film obtained by curing the above-mentioned negative photosensitive resin composition.

[0263] 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.

[0264] (Electronic Components) Furthermore, the present invention provides an electronic component having the above-mentioned interlayer insulating film or the above-mentioned surface protective film. Such an electronic component has excellent reliability because it has a protective coating (interlayer insulating film or surface protective film) that has heat resistance, chemical resistance, and insulating properties. EXAMPLES

[0265] The present invention will be specifically described below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. The weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0266] I. Polymer (resin) synthesis The chemical structures and names of the compounds used in the synthesis examples are shown below. [ka]

[0267] DA-1: 4-aminophenyl-4-amino-2-methylbenzoate DA-2: (2-phenyl-4-aminophenyl)-4-aminobenzoate 6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane BPS: Bis(3-amino-4-hydroxyphenyl)sulfone BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane BAHF: 9,9-bis(3-amino-4-hydroxyphenyl)fluorene 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 X-1: Tetracarboxylic acid diester compound synthesized in Synthesis Example 14 below

[0268] In addition to the above, D-400 and RT-1000 (both diamines manufactured by HUNTSMAN Co., Ltd.) were used.

[0269] [Synthesis Example 1] Synthesis of polyimide resin (A-1) In a 1L flask equipped with a stirrer and a thermometer, 2.5g (9.6mmol) of DA-1, 30.0g (81.9mmol) of 6FAP, 1.0g (9.6mmol) of PAP, and 134g of N-methyl-2-pyrrolidone were added and dissolved by stirring at room temperature. Next, a solution of 29.9g of s-ODPA (96.4mmol) dissolved in 269g of N-methyl-2-pyrrolidone was added dropwise at room temperature, and after the dropwise addition, the mixture was stirred at room temperature for 1 hour. Then, 20g of xylene was added to the reaction solution, and the mixture was heated to reflux at 170°C for 3 hours while removing the water generated outside the system. After cooling to room temperature, the reaction solution was dropped into 2L of ultrapure water under stirring, and the precipitate was filtered off, washed appropriately, and then dried under reduced pressure at 40°C for 48 hours to obtain polyimide resin (A-1). The molecular weight of this polymer was measured by GPC and found to be 34,000 in terms of polystyrene.

[0270] [Synthesis Example 7] Synthesis of polyamide-imide resin (A-7) In a 1L flask equipped with a stirrer and a thermometer, 2.5g (9.6mmol) of DA-1, 30.0g (81.9mmol) of 6FAP, 1.0g (9.6mmol) of PAP, and 134g of N-methyl-2-pyrrolidone were added and stirred at room temperature to dissolve. Next, a solution of 23.9g of s-ODPA (77.1mmol) dissolved in 215g of N-methyl-2-pyrrolidone was added dropwise at room temperature, and after the dropwise addition, the mixture was stirred at room temperature for 1 hour. Then, 20g of xylene was added to the reaction solution, and the mixture was heated to reflux for 3 hours while removing the water generated at 170°C from the system. After cooling to room temperature, 3.1g (38.6mmol) of pyridine was added, and 4.6g of DC-1 (19.3mmol) was added dropwise to keep the temperature below 20°C. After the dropwise addition, the reaction solution was dropped into 2 L of ultrapure water under stirring, and the precipitate was filtered off, appropriately washed with water, and then dried under reduced pressure at 40° C. for 48 hours to obtain polyamideimide resin (A-7). The molecular weight of this polymer was measured by GPC and found to be 33,000 in terms of polystyrene.

[0271] [Synthesis Example 13] Synthesis of polyamide resin (A-13) In a 1L flask equipped with a stirrer and a thermometer, 2.9g (9.6mmol) of DA-2, 30.0g (81.9mmol) of 6FAP, 1.0g (9.6mmol) of PAP, and 136g of N-methyl-2-pyrrolidone were added and stirred at room temperature to dissolve. Next, 15.3g (192.8mmol) of pyridine was added, and 23.1g of DC-1 (96.4mmol) was added dropwise to keep the temperature below 20°C. After the dropwise addition, the reaction solution was dropped into 2L of ultrapure water under stirring, and the precipitate was filtered off, washed appropriately, and dried under reduced pressure at 40°C for 48 hours to obtain polyamide resin (A-13). The molecular weight of this polymer was measured by GPC, and the weight average molecular weight was 38,000 in terms of polystyrene.

[0272] [Synthesis Example 14] Synthesis of tetracarboxylic acid diester compound (X-1) In a 3L flask equipped with a stirrer and a thermometer, 100g (322mmol) of s-ODPA, 65.2g (644mmol) of triethylamine, 39.3g (322mmol) of N,N-dimethyl-4-aminopyridine, and 400g of γ-butyrolactone were added, and 83.8g (644mmol) of hydroxyethyl methacrylate (HEMA) was added dropwise while stirring at room temperature, and the mixture was stirred at room temperature for 24 hours. After that, 370g of 10% aqueous hydrochloric acid was added dropwise under ice cooling to stop the reaction. 800g of 4-methyl-2-pentanone was added to the reaction solution, and the organic layer was separated and washed six times with 600g of water. The solvent of the obtained organic layer was distilled off to obtain 180g of tetracarboxylic acid diester compound (X-1).

[0273] [Synthesis Example 15] Synthesis of polyimide resin (A-15) In a 1L flask equipped with a stirrer and a thermometer, 44.0g (77.1mmol) of X-1 and 176g of N-methyl-2-pyrrolidone were added and dissolved by stirring at room temperature. Next, 18.8g (158.1mmol) of thionyl chloride was added dropwise under ice cooling so that the reaction solution temperature was kept below 10°C, and after the dropwise addition, the mixture was stirred for 2 hours under ice cooling. Next, 4.6g of DC-1 (19.3mmol) was added, and then 2.9g of DA-2 (9.6mmol), 30.0g of 6FAP (81.9mmol), 1.0g of PAP (9.6mmol), and a solution of 15.3g (192.8mmol) of pyridine dissolved in 136g of N-methyl-2-pyrrolidone were added dropwise under ice cooling so that the reaction solution temperature was kept below 10°C. After the dropwise addition, the mixture was cooled to room temperature, and the reaction solution was dropped into 3 L of water under stirring, and the precipitate was filtered off, appropriately washed with water, and then dried under reduced pressure at 40° C. for 48 hours to obtain polyimide resin (A-15). The molecular weight of this polymer was measured by GPC and found to be 35,000 in terms of polystyrene.

[0274] [Synthesis Examples 2] to [Synthesis Examples 6], [Synthesis Examples 8] to [Synthesis Examples 12], and [Comparative Synthesis Examples 1 and 2] Synthesis of polyimide resins or polyamideimide resins (A-2) to (A-6), (A-8) to (A-12), (A-16), and (A-17) The diamine compounds, monoamine compounds, tetracarboxylic dianhydrides, and dicarboxylic dichlorides shown in the weights in Table 1 below were used to obtain resins (A-2) to (A-6), (A-8) to (A-12), (A-16), and (A-17) using the same formulation as in Synthesis Example 1 for polyimide resins and the same formulation as in Synthesis Example 7 for polyamideimide resins. The molecular weights of the respective polymers were measured by GPC, and the weight average molecular weights calculated in terms of polystyrene are shown in Table 1 below.

[0275] [Table 1]

[0276] II. Synthesis of crosslinkable polymer compound (E) As a crosslinkable polymer compound (polymer additive), each monomer was combined and copolymerized in tetrahydrofuran solvent, crystallized in hexane, and dried to obtain the polymer compounds (polymers E1 to E8) with the compositions shown below. The composition of the obtained polymer compounds was confirmed by 1H-NMR, and the molecular weight was confirmed by gel permeation chromatography.

[0277] [Synthesis Example 16] Polymer E1 Molecular weight (Mw)=11,600 [ka]

[0278] [Synthesis Example 17] Polymer E2 Molecular weight (Mw)=11,800 [ka]

[0279] [Synthesis Example 18] Polymer E3 Molecular weight (Mw)=11,300 [ka]

[0280] [Synthesis Example 19] Polymer E4 Molecular weight (Mw)=12,300 [ka]

[0281] [Synthesis Example 20] Polymer E5 Molecular weight (Mw)=11,400 [ka]

[0282] [Synthesis Example 21] Polymer E6 Molecular weight (Mw)=12,000 [ka]

[0283] [Synthesis Example 22] Polymer E7 Molecular weight (Mw)=11,500 [ka]

[0284] [Synthesis Example 23] Polymer E8 Molecular weight (Mw)=12,000 [ka]

[0285] III. Preparation of Photosensitive Resin Composition The resins synthesized in the above Synthesis Examples 1 to 15 and Comparative Synthesis Examples 1 and 2, and the crosslinkable polymer compounds (E1) to (E8) synthesized in Synthesis Examples 16 to 23 were used as base resins to prepare resin compositions of 20 mass% in resin equivalent with the composition and blending amounts shown in Table 2. After stirring, mixing, and dissolving, the mixture was precision filtered through a 0.5 μm Teflon (registered trademark) filter to obtain a photosensitive resin composition. In Table 2, the solvent PGMEA stands for propylene glycol monomethyl ether acetate, and GBL stands for gamma-butyrolactone.

[0286] [Table 2]

[0287] In Table 2, the details of the oxime sulfonate compound photoacid generator (PAG-1), crosslinking agents (CL-1), (CL-2), (CL-3), basic compound (F-1), thermal acid generators (G-1), (G-2), antioxidant (H-1), silane compound (I-1), dissolution inhibitor (K-1), and surfactant (J-1) are as follows: Parts by weight means the same as parts by mass.

[0288] Photoacid generator (PAG-1) [ka]

[0289] Crosslinker (CL-1) [ka]

[0290] Crosslinker (CL-2) [ka]

[0291] Crosslinker (CL-3) Epoxy resin: ADEKA Corporation EP4000L

[0292] Basic compound (F-1) [ka]

[0293] Thermal acid generator (G-1) [ka]

[0294] Thermal acid generator (G-2) [ka]

[0295] Antioxidant (H-1) Hindered phenol-based antioxidant: Sumilizer GA-80 manufactured by Sumitomo Chemical Co., Ltd.

[0296] Silane Compounds (I-1) Aminosilane coupling agent: KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.

[0297] Dissolution inhibitor (K-1) [ka]

[0298] Surfactant (J-1) Fluorosurfactant: OMNOVA PF-6320

[0299] IV. Pattern Formation The above-mentioned photosensitive resin compositions 1 to 23 and comparative photosensitive resin compositions 1 to 3 were dispensed in an amount of 5 mL onto a silicon substrate treated with hexamethylsilazane, and then the substrate was rotated, i.e., by a spin coating method, so that the film thickness would be 2 μm after heating for post-curing performed after pattern formation. That is, after considering in advance that the film thickness would decrease after the post-curing process, the rotation speed during application was adjusted so that the finished film thickness after post-curing would be 2 μm. Next, the substrate was prebaked on a hot plate at 100°C for 2 minutes. Next, i-line exposure was performed using a Veeco i-line stepper AP300E. After exposure, the substrate was post-exposure baked (PEB) at 110°C for 2 minutes, and then cooled. A mask for negative patterns was used for pattern formation. The mask had a pattern capable of forming a 2 μm line and space pattern (hereinafter referred to as LS pattern) with a 1:1 vertical / horizontal arrangement, and was capable of forming an LS pattern in 1 μm increments from 10 μm to 2 μm.

[0300] Thereafter, paddle development was carried out for 1 minute using a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer until the coating film in the unexposed areas was dissolved, and then rinsing was carried out with ultrapure water.

[0301] The patterned substrate was then post-cured in an oven at 180° C. for 2 hours with a nitrogen purge.

[0302] Next, each substrate was cut out so that the shape of the obtained LS pattern could be observed, and the LS pattern shape was observed using a scanning electron microscope (SEM). The shape of the 2 μm LS line pattern after post-curing was evaluated. In addition to these results, the sensitivity and number of developments required to form a 2 μm pattern are shown in Table 3.

[0303] The shape of the LS pattern was evaluated according to the following criteria, and the evaluation results are shown in Table 3. The cross section of the smallest LS pattern was observed, and the widths of the top and bottom of the cross section of the pattern were compared. Patterns with a difference of 0 μm or more and 0.2 μm or less were rated A, those with a difference of more than 0.2 μm and 0.5 μm or less were rated B, those with a difference of more than 0.5 μm and 1.0 μm or less were rated C, and those with a difference of more than 1.0 μm were rated D.

[0304] V. Breaking elongation and tensile strength The above-mentioned photosensitive resin compositions 1 to 23 and comparative photosensitive resin compositions 1 to 3 were spin-coated on an aluminum substrate so that the final film thickness after curing was 10 μm. Then, the coating was pre-baked on a hot plate at 100° C. for 4 minutes to obtain a photosensitive resin film.

[0305] Then, using a Quintel contact aligner UL-7000, a broadband wavelength of 500 mJ / cm 2The entire substrate was exposed to contact light with an exposure dose of 100 nm. After exposure, PEB treatment was performed at 110°C for 4 minutes, and then cooled. Then, the substrate was cured in an oven at 190°C for 2 hours while purging with nitrogen, to obtain a photosensitive resin cured film. Next, the wafer with the cured film was cut into strips with a width of 10 mm and a length of 60 mm, and the cured film was peeled off from the substrate by immersing it in 20% by mass hydrochloric acid. The breaking elongation and tensile strength of the obtained cured film were measured using an autograph AGX-1KN manufactured by Shimadzu Corporation. The measurement was performed 10 times for each sample, and the average values ​​are shown in Table 3.

[0306] [Table 3]

[0307] VI. Adhesion Using the same procedure as the above pattern formation, the above photosensitive resin compositions 1 to 23 and comparative photosensitive resin compositions 1 and 2 were exposed to i-line to form a 1 cm square pattern on a SiN substrate so that the final film thickness after curing was 5 μm, and a pattern was obtained in a lattice shape over the entire surface of the substrate. The exposure dose was the exposure dose at which the minimum pattern determined by the above LS pattern evaluation could be formed. In addition, pre-baking was performed at 100°C for 4 minutes, and PEB was performed at 110°C for 4 minutes. In addition, development was performed by paddle development for 1 minute until the coating film in the unexposed area was dissolved, and was performed a specified number of times.

[0308] After that, nitrogen was purged at 190°C for 2 hours to post-cure the patterned substrate. Next, the cured substrate was cut into individual pieces along the 1 cm square pattern to obtain chips with a cured coating. Aluminum pins with epoxy resin were set on the obtained chips, and the chips were heated at 150°C for 1 hour to bond the aluminum pins to the chips, creating measurement samples. After cooling, the adhesion was measured using a ROMULUS made by Quad Group by the method shown in Figure 1 (hereinafter referred to as the Stud-pull method). The measurement speed was 20 N / sec as a measurement condition. Figure 1 is an explanatory diagram showing the adhesion measurement method. In Figure 1, 1 is the SiN substrate (substrate), 2 is the cured coating, 3 is the aluminum pin with adhesive, 4 is the support, 5 is the grip, and 6 is the tensile direction. The obtained value is the average value of 10 points, and the higher the value, the higher the adhesion of the cured coating to the SiN substrate. In addition, the peel interface of the cured coating / adhesive has a higher adhesion than the substrate / cured coating. The adhesion was evaluated by comparing the obtained values ​​and the peeled interface.

[0309] Furthermore, as a high temperature and high humidity test (PCT test), the obtained chips were left in a pressure cooker at 120°C and 100% RH for 168 hours under saturated 2 atmospheres pressure. The adhesion strength after the test was evaluated by the stud-pull method, and the results before the test are shown in Table 4 as the adhesion strength to the substrate.

[0310] [Table 4]

[0311] As shown in Tables 3 and 4, it was found that in Examples 1 to 23, which used the negative-type photosensitive composition of the present invention, a cured coating film having good mechanical properties and high-temperature and high-humidity resistance was obtained even when cured at a low temperature of 200°C or less.

[0312] In contrast, Comparative Examples 1 to 3, in which a polymer not containing the structural units represented by general formula (1) and / or (2) was used in the composition, showed poor breaking elongation when cured at a low temperature of 200° C. or less.

[0313] As a result of the above, the compositions of Examples 1 to 23 exhibited good rectangularity and excellent resolution capable of resolving fine patterns of 2 μm, and exhibited sufficient properties as photosensitive materials. In addition, the cured films thereof exhibited good adhesion to substrates and good resistance to high temperatures and high humidity, and were found to be useful as protective films for circuits and electronic components.

[0314] The present specification includes the following aspects. [1]: A negative photosensitive resin composition, (A) a polymer containing structural units represented by the following general formula (1) and / or (2) and structural units represented by the following general formula (3) and / or (4): [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, and Es is a -O-C(=O)- bond or a -C(=O)-O- bond.) [ka] (In the formula, X2 is a divalent organic group, and R1 to R4 and Es are the same as above.) [ka] (In the formula, X3 is a tetravalent organic group that is the same as or different from X1, s is 0 or 1, Z is a divalent linking group, and when s=0, the two aromatic rings in the formula are directly linked without a linking group.) [ka] (In the formula, X4 is a divalent organic group that is the same as or different from X2, and s and Z are the same as those defined above.) (B) a photoacid generator, (C) a crosslinking agent, (D) a solvent, A negative type photosensitive resin composition comprising: [2]: The negative type photosensitive resin composition according to the above [1], wherein one of R1 and R2 in the general formulas (1) and (2) 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 negative type photosensitive resin composition according to [2], wherein one of R1 and R2 in the general formulas (1) and (2) is an aromatic group having 1 to 10 carbon atoms, and the other is a hydrogen atom. [4]: The negative type photosensitive resin composition according to any one of [1] to [3] above, wherein Z in the general formulae (3) and (4) is at least one bonding group selected from the groups represented by the following formulae (5), (6), (7) and (8): [ka] (In the formula, the dotted lines represent bonds.) [5]: The negative photosensitive resin composition according to any one of [1] to [4] above, characterized in that the component (C) 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 (C-1), and a compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2). [ka] (In the formula, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.) [6]: The negative photosensitive resin composition further comprises: (E) a crosslinkable polymer compound containing a structural unit represented by the following general formula (9) and having a group capable of crosslinking with the component (A): [ka] (In the formula, R5 is a hydrogen atom or a methyl group, R6 is a (n+1)-valent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, a benzyl group, or a naphthalenemethyl group, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. n is an integer of 1 to 5. Y1 is -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R7OH)-, respectively. R7 is a divalent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. p1 is 0 or 1.) The negative type photosensitive resin composition according to any one of [1] to [5] above, comprising: [7]: The negative type photosensitive resin composition according to the above [6], wherein the component (E) is a crosslinkable polymer compound containing a structural unit represented by the following general formula (10) and a structural unit represented by the following general formula (11) having a group capable of crosslinking with the component (A): [ka] (In the formula, R8 is a hydrogen atom or a methyl group, and Y2 is -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R9OH)-. R9 is a divalent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. p2 is 0 or 1.) [ka] (In the formula, R 10 is a hydrogen atom or a methyl group, R 11 is a group containing an oxazoline group, an isocyanate group, a blocked isocyanate group, an oxetanyl group, or an epoxy group, and Y3 is -C(=O)-O-, a phenylene group, or a naphthylene group. p3 is 0 or 1. [8]: The negative type photosensitive resin composition according to the above [7], wherein the component (E) is a crosslinkable polymeric compound containing structural units represented by the following general formula (10) and the following general formula (12): [ka] (In the formula, R8, Y2, and p2 are the same as those described above, and R 12 is a hydrogen atom or a methyl group, and Y is -C(=O)-O-, a phenylene group, or a naphthylene group. 13 is a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may contain a hydroxyl group, an ester group, an ether group or an aromatic hydrocarbon; R 14 is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R 13 R may be bonded to form a ring. 15 is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R 16 is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, and R 13 may be bonded to form a ring. m is 0 or 1. p4 is 0 or 1. 0 <a1<1.0、0<a2<1.0、0<a1+a2≦1.0である。) [9]: The negative photosensitive resin composition according to any one of [6] to [8] above, wherein the component (E) is a crosslinkable polymeric compound further comprising a structural unit represented by the following general formula (13): [ka] (In the formula, R 17 is a hydrogen atom or a methyl group, R 18 is a single bond or a (l+1)-valent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. Y5 is -C(=O)-O-, -C(=O)-OR 19 -, -C(=O)-NH-, -C(=O)-N(R 19 OH)-, a phenylene group, or a naphthylene group.19 is a divalent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. 1 is 0 or 1.

[10] : The negative photosensitive resin composition according to any one of [6] to [9] above, wherein the component (E) is a crosslinkable polymeric compound further comprising a structural unit represented by the following general formula (13): [ka] (In the formula, R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

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

[10] above, further comprising one or more selected from the group consisting of (F) a basic compound, (G) a thermal acid generator, (H) an antioxidant, and (I) a silane compound.

[12] : A pattern forming method comprising the steps of: (1) A step of applying any one of the negative photosensitive resin compositions described above in [1] to

[11] onto a substrate to form a photosensitive film; (2) subsequently exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask after the heat treatment; (3) developing the substrate that has been subjected to the heat treatment after the exposure using an aqueous alkaline developer; A pattern forming method comprising the steps of:

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

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

[14] : An interlayer insulating film, comprising a cured coating formed by curing the negative photosensitive resin composition according to any one of [1] to

[11] above.

[15] : A surface protective film, comprising a cured coating formed by curing the negative photosensitive resin composition according to any one of [1] to

[11] above.

[16] : An electronic component, comprising the interlayer insulating film according to

[14] above or the surface protective film according to

[15] above.

[0315] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention. [Explanation of symbols]

[0316] 1...SiN substrate (substrate), 2...hardened coating, 3...aluminum pin with adhesive, 4...support base, 5...grasp, 6...tensile direction.

Claims

1. A negative photosensitive resin composition comprising: (A) a polymer containing structural units represented by the following general formula (1) and / or (2) and structural units represented by the following general formula (3) and / or (4), 【Chemistry 1】 (In the formula, X １ is a tetravalent organic group, R １ ~R ４ may be different or the same, are a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom or a hydrogen atom, at least one of them is a monovalent organic group having 1 to 15 carbon atoms which may contain a heteroatom, and Es is a -O-C(=O)- bond or a -C(=O)-O- bond. 【Chemistry 2】 (In the formula, X ２ is a divalent organic group, R １ ~R ４ and Es are the same as above.) 【Chemistry 3】 (In the formula, X ３ is the above X １ is a tetravalent organic group that may be the same or different from the above, s is 0 or 1, Z is a divalent linking group, and when s=0, the two aromatic rings in the formula are directly linked without a linking group. 【Chemistry 4】 (In the formula, X ４ is the above X ２ is a divalent organic group that may be the same or different from the above, and s and Z are the same as those defined above. (B) a photoacid generator, (C) a crosslinking agent, (D) a solvent, A negative type photosensitive resin composition comprising:

2. The R in the general formulas (1) and (2) １ and R ２ one of 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 2. The negative photosensitive resin composition according to claim 1, wherein is a hydrogen atom.

3. The R in the general formulas (1) and (2) １ and R ２ 3. The negative type photosensitive resin composition according to claim 2, wherein either one of the above is an aromatic group having 1 to 10 carbon atoms, and the other is a hydrogen atom.

4. The negative type photosensitive resin composition according to claim 1, wherein Z in the general formulas (3) and (4) is at least one bonding group selected from the groups represented by the following formulas (5), (6), (7) and (8): 【Chemistry 5】 (In the formula, the dotted lines represent bonds.)

5. The negative type photosensitive resin composition according to claim 1, wherein the component (C) 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 (C-1), and a compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2). 【Chemistry 6】 (In the formula, the dotted line represents a bond, Rc is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v is 1 or 2.)

6. The negative photosensitive resin composition further comprises: (E) a crosslinkable polymer compound containing a structural unit represented by the following general formula (9) and having a group capable of crosslinking with the component (A): 【Chemistry 7】 (In the formula, R ５ is a hydrogen atom or a methyl group, R ６ is a (n+1)-valent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, a benzyl group, or a naphthalenemethyl group, in which a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. n is an integer of 1 to 5. Y １ are respectively -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R ７ OH)-. ７ is a divalent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. １ is 0 or 1.) The negative type photosensitive resin composition according to claim 1, comprising:

7. The negative type photosensitive resin composition according to claim 6, wherein the component (E) is a crosslinkable polymer compound containing a structural unit represented by the following general formula (10) and containing a structural unit represented by the following general formula (11) having a group capable of crosslinking with the component (A): 【Chemistry 8】 (In the formula, R ８ is a hydrogen atom or a methyl group, Y ２ are respectively -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R ９ OH)-. ９ is a divalent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. ２ is 0 or 1.) 【Chemistry 9】 (In the formula, R １０ is a hydrogen atom or a methyl group, R １１ is a group containing an oxazoline group, an isocyanate group, a blocked isocyanate group, an oxetanyl group, or an epoxy group; Y ３ is -C(=O)-O-, a phenylene group, or a naphthylene group. ３ is 0 or 1.)

8. The negative photosensitive resin composition according to claim 7, wherein the component (E) is a crosslinkable polymer compound containing structural units represented by the following general formulas (10) and (12): 【Chemistry 10】 (In the formula, R ８ , Y ２ , p ２ is the same as above, R １２ is a hydrogen atom or a methyl group, Y ４ R is —C(═O)—O—, a phenylene group, or a naphthylene group. １３ is a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may contain a hydroxyl group, an ester group, an ether group or an aromatic hydrocarbon; R １４ is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R １３ may be bonded to form a ring. １５ is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R １６ is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms; R １３ may be bonded to form a ring. m is 0 or 1. ４ is 0 or 1. 0<a1<1.0, 0<a2<1.0, 0<a1+a2≦1.0.)

9. 7. The negative photosensitive resin composition according to claim 6, wherein the component (E) is a crosslinkable polymer compound further comprising a structural unit represented by the following general formula (13): 【Chemistry 11】 (In the formula, R １７ is a hydrogen atom or a methyl group, R １８ Y is a single bond or a (l+1)-valent linear, branched or cyclic saturated aliphatic hydrocarbon group having 1 to 13 carbon atoms, and a carbon atom of the saturated aliphatic hydrocarbon group may be replaced with an oxygen atom. ５ are respectively -C(=O)-O- and -C(=O)-O-R １９ -, -C(=O)-NH-, -C(=O)-N(R １９ OH)-, a phenylene group, or a naphthylene group. １９ is a divalent linear, branched, or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, in which a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom; and l is 0 or 1.

10. The negative photosensitive resin composition according to claim 6, wherein the component (E) is a crosslinkable polymer compound further comprising at least one structural unit selected from structural units formed by cyclopolymerization represented by the following general formula (14), the following general formula (15), the following general formula (16), and the following general formula (17): 【Chemistry 12】 (In the formula, R ２０ , R ２１ , R ２２ , R ２３ , R ２４ , and R ２５ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

11. 2. The negative type photosensitive resin composition according to claim 1, further comprising at least one selected from the group consisting of (F) a basic compound, (G) a thermal acid generator, (H) an antioxidant, and (I) a silane compound.

12. A pattern formation method comprising the steps of: (1) A step of applying the negative photosensitive resin composition according to any one of claims 1 to 11 onto a substrate to form a photosensitive film; (2) after the heat treatment, exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask; (3) developing the substrate that has been subjected to the heat treatment after the exposure using an aqueous alkaline developer; A pattern forming method comprising the steps of:

13. A method for forming a cured film, comprising a step of heating and post-curing the patterned photosensitive film obtained by the pattern formation method according to claim 12 at a temperature of 100 to 300° C.

14. 12. An interlayer insulating film, comprising a cured film obtained by curing the negative photosensitive resin composition according to claim 1.

15. A surface protective film, comprising a cured coating formed by curing the negative photosensitive resin composition according to any one of claims 1 to 11.

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

17. An electronic component having the surface protective film according to claim 15.

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