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

Abstract

[Problem] To provide: a negative-type photosensitive resin composition which is soluble in an aqueous alkali solution, is capable of forming a fine pattern, is capable of achieving high resolution, and is capable of forming a fine pattern even when cured at a low temperature; the adhesive tape has excellent mechanical properties such as elongation at break and tensile strength, and does not deteriorate in adhesion force before and after a high-temperature and high-humidity test. [Solution] A negative photosensitive resin composition which is characterized by containing (A) a polymer that contains a structural unit represented by general formula (1) and / or (2) and that contains a structural unit represented by general formula (3) and / or (4), (B) a photoacid generator, (C) a crosslinking agent, and (D) a solvent. # imgabs0 #

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 Art

[0002] As various electronic devices such as personal computers, digital cameras, and mobile phones become smaller and more powerful, the demand for further miniaturization, thinning, and high density in semiconductor components is also increasing rapidly. As a result, the interlayer insulation film and surface protection film of semiconductor components are required to have better electrical properties, heat resistance, mechanical properties, etc.

[0003] In high-density mounting technologies such as three-dimensional stacking, polyimide films have been used as protective films and insulating layers for photosensitive insulating materials that can be patterned on substrates. Their insulation properties, mechanical properties, and adhesion to substrates continue to attract attention and are currently being actively developed.

[0004] Various studies have been conducted to further improve the above-mentioned required properties. As one of them, a photosensitive resin composition using a closed-ring polyimide resin has been proposed for the purpose of lowering the post-curing temperature (Patent Document 1, Patent Document 2). However, it is difficult to take into account the physical properties of the cured film such as clarity, mechanical properties (elongation, tensile strength), and adhesion, and there is still room for improvement.

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

[0006] Patent Document 4 proposes a polyamic acid comprising 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 obtained by ring-closing the polyamic acid, but there is no description of a photosensitive resin composition, and there is still room for improvement in terms of mechanical strength, particularly elongation.

[0007] In addition, as an improvement in the mechanical strength of the cured film, it has been proposed to add a (meth) acrylic resin to balance the photolithographic characteristics and the physical properties of the cured film (Patent Documents 5, 6, and 7). However, for the purpose of modifying the main resin, the value of the mechanical strength of the cured film still has room for improvement.

[0008] As described above, with the future increase in chip density and integration, it is expected that the pattern miniaturization in the rewiring technology of the insulating protective film will also become increasingly advanced. Therefore, for the photosensitive resin composition, there is a strong demand for a composition that can achieve a pattern shape with high resolution and good rectangularity without damaging the excellent characteristics of the obtained pattern and protective film such as mechanical properties and adhesion due to heating.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent No. 4530284

[0012] Patent Document 2: Japanese Patent Application Publication No. 2006-313237

[0013] Patent Document 3: Japanese Patent Application Publication No. 2020-152768

[0014] Patent Document 4: Japanese Patent Application Publication No. 2021-187934

[0015] Patent Document 5: Japanese Patent No. 5884837

[0016] Patent Document 6: Japanese Patent Application Publication No. 2015-129791

[0017] Patent Document 7: Japanese Patent Application Publication No. 2015-200819 Summary of the invention

[0018] Problem that the invention aims to solve

[0019] The present invention is made in view of the above situation, and its purpose is to provide a negative photosensitive resin composition that is soluble in an alkaline aqueous solution, can form a fine pattern, can obtain a high resolution, and has good mechanical properties such as elongation at break and tensile strength even when cured at low temperature, and further, the adhesion before and after a high temperature and high humidity test will not deteriorate; a pattern forming method, a cured film forming method, an interlayer insulating film, a surface protective film and an electronic component.

[0020] Solutions for solving problems

[0021] In order to solve the above problems, the present invention provides a negative photosensitive resin composition comprising (A) a polymer, (B) a photoacid generator, (C) a crosslinking agent, and (D) a solvent.

[0022] The polymer (A) includes structural units represented by the following general formula (1) and / or (2), and includes structural units represented by the following general formula (3) and / or (4).

[0023]

[0024] (In the formula, X1 is a tetravalent organic group; R1 to R4 are optionally the same or different, and are monovalent organic groups with 1 to 15 carbon atoms or hydrogen atoms, and at least one of them is a monovalent organic group with 1 to 15 carbon atoms and optionally containing heteroatoms; Es is a -OC(=O)- bond or a -C(=O)-O- bond.)

[0025]

[0026] (In the formula, X2 is a divalent organic group; R1 to R4 and Es are the same as above.)

[0027]

[0028] (In the formula, X3 is a tetravalent organic group which is the same as or different from the aforementioned X1; s is 0 or 1; Z is a divalent bonding group; when s=0, the two aromatic rings in the formula are directly bonded without the aid of a bonding group.)

[0029]

[0030] (In the formula, X4 is a divalent organic group that is the same as or different from the aforementioned X2; s and Z are the same as described above.)

[0031] If it is such a negative photosensitive resin composition, since the aforementioned general formula (3) or (4) has a phenolic hydroxyl group, it is soluble in an alkaline aqueous solution, can form a fine pattern, and can obtain a high resolution. Moreover, since the aforementioned general formula (1) or (2) has an ester group, the interaction between molecules is promoted by means of hydrogen bonds, etc., and it also interacts with the substrate. Therefore, even when curing is carried out at a low temperature, the mechanical properties and the adhesion to the substrate are good.

[0032] In the present invention, it is preferred that: in the general formulae (1) and (2), either 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, and R3 and R4 are hydrogen atoms.

[0033] Such a negative photosensitive resin composition has a substituent at the ortho position to the site bonded to the ester group, so that the free rotation of the polymer chain is suppressed by the steric hindrance of the substituent, and the interaction between molecules becomes moderate, so that the mechanical properties are good even when cured at low temperature.

[0034] In this case, it is preferred that either 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.

[0035] Such a negative photosensitive resin composition can provide better mechanical properties even when cured at low temperatures.

[0036] In the present invention, it is preferred that the Z in the general formulae (3) and (4) is at least one bonding group selected from the group represented by the following formulae (5), (6), (7) and (8).

[0037]

[0038] (In the formula, the dotted line represents the connecting bond.)

[0039] Such a negative photosensitive resin composition can improve solubility in an alkaline aqueous solution, can form a finer pattern, and can obtain a high resolution.

[0040] In addition, in the present invention, the aforementioned (C) component is preferably one or more crosslinking agents selected from amino condensates modified with formaldehyde or formaldehyde-alcohol, phenol compounds having an average of two or more hydroxymethyl groups or alkoxyhydroxymethyl groups in one molecule, compounds obtained by replacing the hydrogen atoms of the hydroxyl group of a polyphenol with a glycidyl group, compounds obtained by replacing the hydrogen atoms of the hydroxyl group of a polyphenol or a polyol with a substituent represented by the following formula (C-1), and compounds containing two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2).

[0041]

[0042] (In the formula, the dotted line represents a connecting bond; Rc is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; v is 1 or 2.)

[0043] Such a negative photosensitive resin composition can form a finer pattern and obtain a high resolution, and also has excellent mechanical properties and adhesion to a substrate even when cured at a low temperature.

[0044] In the present invention, the negative photosensitive resin composition preferably further comprises (E) a crosslinkable polymer compound comprising a structural unit represented by the following general formula (9) and having a group that crosslinks with the component (A).

[0045]

[0046] (In the formula, R5 is a hydrogen atom or a methyl group; R6 is a (n+1)-valent straight-chain, 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 naphthylmethyl group, and the carbon atoms of the aforementioned aliphatic saturated hydrocarbon group are optionally replaced by oxygen atoms. n is an integer from 1 to 5. Y1 is -C(=O)-O-, -C(=O)-NH- or -C(=O)-N(R7OH)-. R7 is a divalent straight-chain, 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 the carbon atoms of the aforementioned aliphatic saturated hydrocarbon group are optionally replaced by oxygen atoms. p1 is 0 or 1.).

[0047] Such a negative photosensitive resin composition can form a finer pattern and obtain a high resolution, and also has excellent mechanical properties and adhesion to a substrate even when cured at a low temperature.

[0048] In this case, the component (E) is preferably a crosslinkable polymer compound including 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 component (A).

[0049]

[0050] (In the formula, R8 is a hydrogen atom or a methyl group; Y2 is -C(=O)-O-, -C(=O)-NH- or -C(=O)-N(R9OH)-. R9 is a divalent straight-chain, 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 the carbon atoms of the aliphatic saturated hydrocarbon group may be optionally replaced by oxygen atoms. p2 is 0 or 1.)

[0051]

[0052] (Where 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 oxetane group or an epoxy group; Y3 is -C(=O)-O-, a phenylene group or a naphthylene group. p3 is 0 or 1.)

[0053] Such a negative photosensitive resin composition can maintain sufficient solubility in an alkaline aqueous solution, can obtain a pattern with good rectangularity, and has good mechanical properties and adhesion to a substrate even when cured at a low temperature.

[0054] In this case, the component (E) is preferably a cross-linkable polymer compound containing structural units represented by the following general formula (10) and the following general formula (12).

[0055]

[0056] (wherein, R8, Y2, p2 are the same as above; R 12 is a hydrogen atom or a methyl group; Y4 is -C(=O)-O-, a phenylene group or a naphthylene group. 13 is a hydroxyl group, an ester group, an ether group, or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may contain an aromatic hydrocarbon; R 14 is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, optionally with R 13 Bond 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, optionally with R 13 bonded to form a ring. m is 0 or 1. p4 is 0 or 1. <a1<1.0、0<a2<1.0、0<a1+a2≤1.0。)

[0057] If this negative photosensitive resin composition is added to the polymer of component (A), sufficient alkaline aqueous solution solubility can be maintained, and a pattern with good rectangularity can be obtained. In addition, due to the presence of a cross-linking group with excellent cross-linking properties, a cross-linking reaction occurs with the phenolic hydroxyl group in the structural unit represented by the aforementioned general formula (3) and / or (4) of component (A), and the adhesion to the substrate after the reliability test will not be deteriorated.

[0058] 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).

[0059]

[0060] (Where R 17 is a hydrogen atom or a methyl group; R 18 is a single bond, or a (1+1)-valent straight-chain, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms, wherein the carbon atoms of the aliphatic saturated hydrocarbon group may be substituted by oxygen atoms. 19 -, -C(=O)-NH-, -C(=O)-N(R 19 OH)-, phenylene or naphthylene. 19 A divalent straight-chain, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein the carbon atoms of the aliphatic saturated hydrocarbon group may be substituted by oxygen atoms. l is 0 or 1.)

[0061] Such a negative photosensitive resin composition can form a finer pattern and obtain a high resolution, and also has excellent mechanical properties and adhesion to a substrate even when cured at a low temperature.

[0062] In addition, in the present invention, the aforementioned (E) component is preferably a cross-linked polymer compound further comprising at least one structural unit selected from the 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).

[0063]

[0064] (Where R 20 , R 21 , R 22 , R 23 , R 24 and R 25 Each is independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

[0065] Such a negative photosensitive resin composition has a ring structure in the main chain, and therefore, even when cured at a low temperature, mechanical properties such as elongation at break and tensile strength are good, and further, heat resistance is improved.

[0066] In the present invention, it is preferred that the composition further contain at least one compound selected from the group consisting of (F) a basic compound, (G) a thermal acid generator, (H) an antioxidant, and (I) a silane compound.

[0067] By including such a component (F), not only can the dissolution contrast during photolithography patterning be improved, but also the pattern shape can be controlled.

[0068] In addition, the component (G) can further improve the mechanical strength, chemical resistance, adhesion, etc. of the obtained pattern or film by further advancing the crosslinking and curing reaction.

[0069] In addition, such a component (H) can suppress the degradation of physical properties of the cured film due to oxidation degradation during reliability tests such as high humidity tests and thermal shock tests, and can form a more suitable cured film.

[0070] In addition, the component (I) can further improve the adhesion of the obtained pattern or film to the substrate.

[0071] Furthermore, the present invention provides a pattern forming method, which comprises the following steps:

[0072] (1) coating the negative photosensitive resin composition described above on a substrate to form a photosensitive material coating;

[0073] (2) After the heat treatment, the photosensitive material coating is exposed to light through a photomask using high energy rays or electron beams with a wavelength of 190 to 500 nm;

[0074] (3) After the exposure, the substrate subjected to the heat treatment is developed using a developer of an alkaline aqueous solution.

[0075] According to such a pattern forming method, by using the above-mentioned negative photosensitive resin composition, it is soluble in an alkaline aqueous solution, and a fine pattern can be formed, and a high resolution can be obtained.

[0076] Furthermore, the present invention provides a method for forming a cured film, comprising the step of heating the photosensitive material film having a pattern formed thereon obtained by the above-mentioned pattern forming method at a temperature of 100 to 300° C. for post-curing.

[0077] According to such a cured film forming method, even when curing is performed at a low temperature, a cured film (pattern) having excellent mechanical properties can be formed.

[0078] In addition, the present invention provides an interlayer insulating film or a surface protective film, which includes a cured film, wherein the cured film is formed by curing the negative photosensitive resin composition described above.

[0079] The cured film formed by curing the negative photosensitive resin composition of the present invention has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance to alkaline stripping solutions, etc., and the reliability of the semiconductor element obtained by making it into a protective film is also excellent. Therefore, it is suitable as a protective film (interlayer insulating film or surface protective film) for electrical / electronic components, semiconductor elements, etc.

[0080] Furthermore, the present invention provides an electronic component including the above-mentioned interlayer insulating film or surface protective film.

[0081] Such protective coatings (interlayer insulating films or surface protective films) are effective as insulating films for semiconductor elements including rewiring applications, insulating films for multilayer printed circuit boards, etc., due to their heat resistance, chemical resistance, and insulating properties, and can be used to produce electronic components with excellent reliability.

[0082] Effects of the Invention

[0083] As described above, according to the present invention, there is provided a negative photosensitive resin composition which is soluble in an aqueous alkali solution, can form a fine pattern with high rectangularity, can obtain high resolution, and has excellent mechanical properties and adhesion to a substrate even when cured at a low temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] Figure 1 It is an explanatory diagram showing a method for measuring the close contact force.

[0085] Description of Reference Numerals

[0086] 1... SiN substrate (substrate), 2... cured film, 3... aluminum pin with adhesive, 4... support table, 5... fixture, 6... tensile direction. DETAILED DESCRIPTION

[0087] As described above, there is a demand for a photosensitive resin composition that is soluble in an aqueous alkali solution, can form a fine pattern with high rectangularity, can obtain high resolution, and has excellent mechanical properties and adhesion to a substrate even when cured at a low temperature.

[0088] The present inventors have conducted intensive studies to achieve the above object and have found that a pattern obtained using a negative photosensitive resin composition containing the following components (A) to (D) has a fine and rectangular pattern shape and the obtained cured film has good mechanical properties and adhesion to the substrate.

[0089] Furthermore, it was found that the protective film obtained by heating at low temperature after pattern formation using the negative photosensitive resin composition has excellent mechanical strength and adhesion. That is, it was found that the cured film obtained by forming a pattern using the negative photosensitive resin composition is excellent as an electrical and electronic component protective film and an insulating protective film, thereby completing the present invention. It should be noted that in this specification, electrical / electronic components are also collectively referred to as "electronic components".

[0090] That is, the present invention is a negative photosensitive resin composition, which comprises (A) a polymer, (B) a photoacid generator, (C) a crosslinking agent, and (D) a solvent, wherein the (A) polymer comprises a structural unit represented by the following general formula (1) and / or (2), and comprises a structural unit represented by the following general formula (3) and / or (4).

[0091]

[0092] (In the formula, X1 is a tetravalent organic group; R1 to R4 are optionally the same or different, and are monovalent organic groups with 1 to 15 carbon atoms or hydrogen atoms, and at least one of them is a monovalent organic group with 1 to 15 carbon atoms and optionally containing heteroatoms; Es is a -OC(=O)- bond or a -C(=O)-O- bond.)

[0093]

[0094] (In the formula, X2 is a divalent organic group; R1 to R4 and Es are the same as above.)

[0095]

[0096] (In the formula, X3 is a tetravalent organic group which is the same as or different from the aforementioned X1; s is 0 or 1; Z is a divalent bonding group; when s=0, the two aromatic rings in the formula are directly bonded without the aid of a bonding group.)

[0097]

[0098] (In the formula, X4 is a divalent organic group that is the same as or different from the aforementioned X2; s and Z are the same as described above.)

[0099] Hereinafter, the present invention will be described in detail, but the present invention is not limited to these.

[0100] [Negative photosensitive resin composition]

[0101] The negative photosensitive resin composition of the present invention contains the following (A) to (D) components. Hereinafter, each component will be described in detail.

[0102] [(A) Polymer]

[0103] The (A) polymer contained in the negative photosensitive resin composition of the present invention contains structural units represented by the following general formula (1) and / or (2) (hereinafter also referred to as structural unit (1), structural unit (2)), and contains structural units represented by the following general formula (3) and / or (4) (hereinafter also referred to as structural unit (3), structural unit (4)).

[0104]

[0105] (In the formula, X1 is a tetravalent organic group; R1 to R4 are optionally the same or different, and are monovalent organic groups with 1 to 15 carbon atoms or hydrogen atoms, and at least one of them is a monovalent organic group with 1 to 15 carbon atoms and optionally containing heteroatoms; Es is a -OC(=O)- bond or a -C(=O)-O- bond.)

[0106]

[0107] (In the formula, X2 is a divalent organic group; R1 to R4 and Es are the same as above.)

[0108]

[0109] (In the formula, X3 is a tetravalent organic group which is the same as or different from the aforementioned X1; s is 0 or 1; Z is a divalent bonding group; when s=0, the two aromatic rings in the formula are directly bonded without the aid of a bonding group.)

[0110]

[0111] (In the formula, X4 is a divalent organic group that is the same as or different from the aforementioned X2; s and Z are the same as described above.)

[0112] X1 in the above general formula (1) is a tetravalent organic group, and there is no limitation 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, optionally containing a siloxane skeleton. It is more preferably a tetravalent organic group represented by the following formula (18). In addition, the structure of X1 can be one type or a combination of two or more types.

[0113]

[0114]

[0115] (Where R a1 , R a2 Each is independently a methyl group or a phenyl group; q1 and q2 are integers of 1 to 20; and the dotted line represents a connecting bond. )

[0116] In the general formula (1), any one of R1 to R4 is a monovalent organic group having 1 to 15 carbon atoms and optionally containing a hetero atom. Preferably, any one of R1 and R2 is a monovalent organic group having 1 to 15 carbon atoms and optionally containing a hetero atom, the other is a hydrogen atom, and 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. Further preferably, any one of R1 and R2 is a monovalent organic group having 1 to 10 carbon atoms and optionally containing a hetero atom, the other is a hydrogen atom, and R3 and R4 are hydrogen atoms.

[0117] Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, and hexyl. Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentyloxy. Examples of the aromatic group having 6 to 12 carbon atoms include phenyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, butylphenyl, fluorophenyl, chlorophenyl, bromophenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, diethoxyphenyl, aminophenyl, nitrophenyl, cyanophenyl, phenethyl, phenylpropyl, phenylamino, diphenylamino, biphenyl, and naphthyl. Examples of the phenoxy group having 6 to 10 carbon atoms include methylphenoxy, ethylphenoxy, propylphenoxy, dimethylphenoxy, diethylphenoxy, methoxyphenoxy, ethoxyphenoxy, and dimethoxyphenoxy. Examples of the benzyl group having 7 to 10 carbon atoms include benzyl, methylbenzyl, ethylbenzyl, propylbenzyl, dimethylbenzyl, diethylbenzyl, methoxybenzyl, ethoxybenzyl, dimethoxybenzyl, diethoxybenzyl, aminobenzyl, nitrobenzyl, and cyanobenzyl. Examples of the benzyloxy group having 7 to 10 carbon atoms include benzyloxy, methylbenzyloxy, ethylbenzyloxy, propylbenzyloxy, dimethylbenzyloxy, diethylbenzyloxy, methoxybenzyloxy, and ethoxybenzyloxy.

[0118] 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, methylphenyl, dimethylphenyl, ethylphenyl, and diethylphenyl are further preferred. It is believed that if such an organic group is used, the free rotation of the polymer chain is suppressed by its large volume, thereby suppressing the stacking effect between molecules, and the interaction between molecules becomes moderate, thereby improving the mechanical properties of the cured film, especially the elongation at break.

[0119] X2 in the above general formula (2) is a divalent organic group, and there is no limitation 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 following formula (19). In addition, the structure of X2 can be one kind or a combination of two or more kinds.

[0120]

[0121] (Where R a3 Each is independently a hydrogen atom, a fluorine atom or an alkyl group having 1 to 6 carbon atoms; q3 is an integer from 1 to 30; and the dotted line represents a connecting bond.

[0122] R1 to R4 in the above general formula (2) are the same as R1 to R4 in the above general formula (1).

[0123] X3 in the above general formula (3) is a tetravalent organic group, which may be the same as or different from the above X1, 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, optionally containing a siloxane skeleton. It is further preferably a tetravalent organic group represented by the above formula (18). In addition, the structure of X3 may be one type or a combination of two or more types.

[0124] 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 without the aid of the divalent bonding group Z.

[0125] On the other hand, when s=1, the two aromatic rings in the general formula (3) are bonded via a divalent bonding group Z. Z is not particularly limited 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). In addition, the structure of Z may be one or a combination of two or more.

[0126]

[0127] (In the formula, q4, q5 and q6 represent integers of 1 to 6; q7 and q8 represent integers of 1 to 10. The dotted line represents a connecting bond.)

[0128] Particularly preferred divalent bonding groups Z are divalent groups represented by the following general formulae (5), (6), (7) and (8). That is, the aforementioned Z in the aforementioned general formulae (3) and (4) is preferably at least one bonding group selected from any of the groups represented by the following formulae (5), (6), (7) and (8).

[0129]

[0130] (In the formula, the dotted line represents the connecting bond.)

[0131] Furthermore, a preferred divalent bonding group Z is a divalent group represented by the above-mentioned general formula (5) or (6).

[0132] 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), it is preferably a structural unit represented by the following general formula (3-1), and when Z in the above general formula (3) is a group represented by the above formula (6), it is preferably a structural unit represented by the following general formula (3-2).

[0133]

[0134] (Wherein, X3 is the same as above.)

[0135] As in the above general formula (3-1), when Z as a divalent bonding group is a hexafluoropropylene group represented by the above formula (5) and is located at the para position of the phenolic hydroxyl group, since the hexafluoropropylene group is an electron-withdrawing group, the acidity of the above-mentioned phenolic hydroxyl group becomes higher and the solubility in the alkaline aqueous developer is improved, which is preferred.

[0136] Similarly, as in the above-mentioned general formula (3-2), when Z as a divalent bonding group is a sulfone group shown in the above-mentioned formula (6) and is located in the para position of the phenolic hydroxyl group, since the sulfone group is also an electron-withdrawing group, the acidity of the above-mentioned phenolic hydroxyl group becomes higher and the solubility in the alkaline aqueous developer is improved, which is preferred.

[0137] X4 in the above general formula (4) is a divalent organic group, which may be the same as or different from the above X2, and there is no limitation 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 X4 may be one kind or a combination of two or more kinds.

[0138] When X4 in the general formula (4) is a divalent organic group having an aliphatic chain length structure, the mechanical strength, especially the elongation, of the cured film of the negative photosensitive resin composition of the present invention is increased, which is preferred.

[0139] In the general formula (4), s and Z are the same as described above. From the viewpoint of solubility in an alkaline aqueous developer, Z is preferably the general formula (5) or (6).

[0140] The (A) polymer contained in the negative photosensitive resin composition of the present invention may contain any one or more of the structural units represented by the following general formulae (21) to (24) in addition to the structural units represented by the above general formulae (1), (2), (3) and (4).

[0141]

[0142] (In the formula, X5 is a tetravalent organic group that is the same as or different from the aforementioned X1; X6 is a divalent organic group.)

[0143]

[0144] (In the formula, X7 is a divalent organic group that is the same as or different from the aforementioned X2; X8 is a divalent organic group that is the same as or different from the aforementioned X6.)

[0145]

[0146] (wherein, X9 is a tetravalent organic group which is the same as or different from the aforementioned X1; X 10 is a divalent organic group that is the same as or different from the aforementioned X6; Rb is optionally the same as or different from each other, and is a hydrogen atom or an organic group having 1 to 10 carbon atoms, optionally containing a heteroatom therebetween, and optionally having a substituent. )

[0147]

[0148] (Where X 11 is a divalent organic group which is the same as or different from the aforementioned X2; 12 It is a tetravalent organic group.)

[0149] X5 in the above general formula (21) is a tetravalent organic group, which may be the same as or different from the above X1, 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 optionally contains a siloxane skeleton. It is further preferably a tetravalent organic group represented by the above formula (18). In addition, the structure of X5 may be one or a combination of two or more.

[0150] X6 in the above-mentioned general formula (21) is a divalent organic group, and there is no limitation as long as it is a divalent organic group, and it is preferably a divalent organic group having 6 to 40 carbon atoms, and more preferably a divalent cyclic organic group containing 1 to 4 aromatic rings or aliphatic rings with substituents, or a divalent aliphatic group without a cyclic structure, or a siloxane group. As more suitable X6, the structure shown in the following formula (25) or (26) can be listed. In addition, the structure of X6 can be one kind, or a combination of two or more kinds.

[0151]

[0152] (In the formula, q9 is an integer of 1 to 20; s1 is an integer of 1 to 40; s2 and s3 are each independently an integer of 0 to 40; and the dotted line represents a connecting bond.)

[0153]

[0154] (where q 10 is an integer from 1 to 4; R a4 is a fluorine atom, a methyl group, an ethyl group, a propyl group, a n-butyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a trifluoromethyl group; 10 When R is 2 or more, a4 Optionally the same or different from each other; q 11is an integer from 1 to 40; the dotted line represents a connecting bond. )

[0155] If it is a negative photosensitive resin composition containing a polymer containing a structural unit represented by the above general formula (21), the mechanical strength, adhesion to the substrate, and heat resistance of the cured film obtained by pattern formation can be improved, so it is preferred. In addition, the structural unit (21) does not need to undergo a ring-closing reaction during post-curing, which can relatively reduce the curing reaction temperature, so it is preferred.

[0156] X7 in the above general formula (22) is a divalent organic group, which may be the same as or different from the above X2, and is not limited as long as it is a divalent organic group. Preferably, it is a divalent organic group having an aliphatic chain length structure of 4 to 40 carbon atoms, a divalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a divalent aromatic group having 6 to 40 carbon atoms. More preferably, it is a divalent organic group represented by the above formula (19). In addition, the structure of X7 may be one kind or a combination of two or more kinds.

[0157] X8 in the above general formula (22) is a divalent organic group, which may be the same as or different from the above X6, and there is no limitation as long as it is a divalent organic group. Preferably, it is a divalent organic group having 6 to 40 carbon atoms, a divalent cyclic organic group containing 1 to 4 aromatic rings or aliphatic rings having substituents, or a divalent aliphatic group without a cyclic structure, or a siloxane group. Further preferred examples include the structures shown in the above formula (25) or (26). In addition, the structure of X8 may be one kind or a combination of two or more kinds.

[0158] A negative photosensitive resin composition containing a polymer having a structural unit represented by the general formula (22) is preferred because it can improve mechanical properties such as elongation of a cured film obtained by patterning and adhesion to a substrate.

[0159] X9 in the above general formula (23) is a tetravalent organic group, which may be the same as or different from the above X1, 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 optionally contains a siloxane skeleton. It is further preferably a tetravalent organic group represented by the above formula (18). In addition, the structure of X9 may be one or a combination of two or more.

[0160] In the above general formula (23), X 10is a divalent organic group, which may be the same as or different from the above X6, 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, a divalent cyclic organic group containing 1 to 4 aromatic rings or aliphatic rings having substituents, or a divalent aliphatic group without a cyclic structure, or a siloxane group. The structure represented by the above formula (25) or (26) is further preferably listed. In addition, X 10 The structure may be one kind or a combination of two or more kinds.

[0161] A negative photosensitive resin composition containing a polymer having a structural unit represented by the general formula (23) is preferred because the mechanical strength of the cured film and the adhesion to the substrate are improved.

[0162] In the above general formula (24), X 11 is a divalent organic group, which may be the same as or different from the above X2, and is not limited as long as it is a divalent organic group. Preferably, it is a divalent organic group having an aliphatic chain length structure of 4 to 40 carbon atoms, a divalent alicyclic aliphatic group having 4 to 40 carbon atoms, or a divalent aromatic group having 6 to 40 carbon atoms. More preferably, it is a divalent organic group represented by the above formula (19). In addition, X 11 The structure may be one kind or a combination of two or more kinds.

[0163] In the above general formula (24), X 12 It is a tetravalent organic group, and there is no limitation as long as it is a tetravalent organic group, and it 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 rings or aliphatic rings having substituents, or a tetravalent aliphatic group without a cyclic structure, or a siloxane group. 12 , the structure shown in the following formula (27) can be listed. 12 The structure may be one kind or a combination of two or more kinds.

[0164]

[0165] (where q 12 ,q 13 and q 14 is an integer from 1 to 10; q 15 is an integer from 1 to 20; the dotted line represents a connecting bond. )

[0166] If it is a negative photosensitive resin composition containing a polymer containing a structural unit represented by the above general formula (24), the mechanical strength, adhesion to the substrate, and heat resistance of the cured film obtained by pattern formation can be improved, so it is preferred. In addition, in the case of containing a structure represented by formula (27), it is not necessary to perform a ring closure reaction in post-curing, and the curing reaction temperature can be relatively lowered, so it is preferred.

[0167] The suitable molecular weight of the above-mentioned (A) polymer is preferably 5,000 to 100,000, and more preferably 7,000 to 50,000. If the molecular weight is 5,000 or more, it is easy to form a film of the negative photosensitive resin composition of the present invention containing the above-mentioned (A) polymer on a substrate to a desired film thickness. If the molecular weight is 100,000 or less, the viscosity of the above-mentioned negative photosensitive resin composition will not increase significantly, and there is no need to worry about the inability to form a film. It should be noted that in the present invention, the weight average molecular weight is a polystyrene conversion value based on gel permeation chromatography (GPC).

[0168] [(A) Method for producing polymer]

[0169] The polymer (A) contains the structural unit represented by the following general formula (1) and / or (2), and contains the structural unit represented by the following general formula (3) and / or (4).

[0170]

[0171] (Wherein, X1, R1 to R4 and Es are the same as above.)

[0172]

[0173] (Wherein, X2, R1 to R4 and Es are the same as above.)

[0174]

[0175] (Wherein, X3, Z and s are the same as above.)

[0176]

[0177] (Wherein, X4, Z and s are the same as above.)

[0178] A polymer containing a structural unit represented by the general formula (1) can be obtained by reacting a tetracarboxylic dianhydride represented by the general formula (28) with a diamine represented by the general formula (29). First, an amic acid is synthesized by reacting a tetracarboxylic dianhydride represented by the general formula (28) with a diamine represented by the general formula (29), and then, an imide ring is formed by heating and dehydrating, thereby obtaining a polymer containing a structural unit (1).

[0179] The production of the structural unit (1) can be carried out 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, reacting the mixture at 0 to 80°C, preferably 10 to 50°C to produce an amic acid, adding a non-polar solvent such as xylene, heating the mixture to 100 to 200°C, preferably 130 to 180°C, and carrying out an imidization reaction while removing water from the reaction system.

[0180]

[0181] (Wherein, X1 is the same as above.)

[0182]

[0183] (In the formula, R1 to R4 and Es are the same as above.)

[0184] Preferred examples of the tetracarboxylic dianhydride represented by the general formula (28) include aromatic acid dianhydrides, alicyclic acid dianhydrides, aliphatic acid dianhydrides, and siloxane skeleton-containing acid dianhydrides.

[0185] Examples of the aromatic acid dianhydride include pyromellitic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3,2',3'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-terphenyltetracarboxylic acid dianhydride, 3,3',4,4'-oxyphthalic acid dianhydride, 2,3,3',4'-oxyphthalic acid dianhydride, 2,3,2',3'-oxyphthalic acid dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic acid dianhydride, and benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride. '-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)phthalic dianhydride, p-phenylenebis(trimellitic acid monoester anhydride), bis(1,3-dioxo-1,3-dihydroisobenzofuran-5- carboxylic acid) 1,4-phenylene ester, 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, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzoyloxy)phenyl) )phenyl)hexafluoropropane dianhydride, 1,6-difluoropyromellitic acid dianhydride, 1-trifluoromethylpyromellitic acid dianhydride, 1,6-bis(trifluoromethyl)pyromellitic acid dianhydride, 2,2'-bis(trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, or acid dianhydride compounds obtained by replacing these aromatic rings with alkyl groups, alkoxy groups, halogen atoms, etc., but are not limited to them.

[0186] Examples of the alicyclic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cycloheptanetetracarboxylic dianhydride, 2,3,4,5-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, Hydrogen furan tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic 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]heptanetetracarboxylic dianhydride, bicyclo[2,2,1]heptane-5-carboxymethyl-2,3,6-tricarboxylic dianhydride, 7-oxabicyclo[2,2,1]heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecahydroanthracene-1,2,8 ,9-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride, 3,3',4,4'-oxydicyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride and "RIKACID" (registered trademark) BT-100 (the above are trade names, manufactured by Shin Nippon Chemical Co., Ltd.) and their derivatives, or acid dianhydride compounds obtained by replacing these alicyclic rings with alkyl groups, alkoxy groups, halogen atoms, etc., but are not limited to them.

[0187] Examples of the aliphatic acid dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and derivatives thereof, but the aliphatic acid dianhydride is not limited thereto.

[0188] Examples of the acid dianhydride containing a siloxane skeleton 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.

[0189] These aromatic acid dianhydrides, alicyclic acid dianhydrides, aliphatic acid dianhydrides and siloxane skeleton-containing acid dianhydrides may be used alone or in combination of two or more.

[0190] Examples of suitable diamines represented by the 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, (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, )phenyl-4-aminobenzoate, (2-isobutyl-4-amino)phenyl-4-aminobenzoate, (3-isobutyl-4-amino)phenyl-4-aminobenzoate, (2-pentyl-4-amino)phenyl-4-aminobenzoate, (3-pentyl-4-amino)phenyl-4-aminobenzoate, (2-hexyl-4-amino)phenyl-4-aminobenzoate, (3-hexyl-4-amino)phenyl-4-aminobenzoate, (2-methoxy-4-amino)phenyl-4-aminobenzoate, (3-methoxy-4-amino)phenyl-4-aminobenzoate, (2-ethoxy-4-amino)phenyl-4-aminobenzoate, (3-ethoxy-4-amino)phenyl-4-aminobenzoate formate, (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-pentyloxy-4-amino)phenyl-4-aminobenzoate, (3-pentyloxy-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-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 Acid ester, (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 Phenyl-4-aminobenzoate, (2-methylphenoxy-4-amino)phenyl-4-aminobenzoate, (3-methylphenoxy-4-amino)phenyl-4-aminobenzoate, (2-ethylphenoxy-4-amino)phenyl-4-aminobenzoate, (3-ethylphenoxy-4-amino)phenyl-4-aminobenzoate, (2-propylphenoxy-4-amino)phenyl-4-aminobenzoate, (3-propylphenoxy-4-amino)phenyl-4-aminobenzoate, (2-methoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (3-methoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (2-ethoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (3-ethoxyphenoxy-4-amino)phenyl-4-aminobenzoate, (2-benzyl-4-amino)phenyl-4-aminobenzoate, (3-benzyl-4-amino)phenyl-4-aminobenzoate, (2-methylbenzyl-4-amino)phenyl-4-aminobenzoate, (3-methylbenzyl-4-amino)phenyl-4-aminobenzoate, (2-ethylbenzyl-4-amino)phenyl-4-aminobenzoate, (3-ethylbenzyl-4-amino)phenyl-4-aminobenzoate, (2-propylbenzyl-4-amino)phenyl-4-aminobenzoate, (3-propylbenzyl-4-amino)phenyl-4-aminobenzoate, (2-methoxybenzyl-4-amino)phenyl-4-aminobenzoate,(3-methoxybenzyl-4-amino)phenyl-4-aminobenzoate, (2-ethoxybenzyl-4-amino)phenyl-4-aminobenzoate, (3-ethoxybenzyl-4-amino)phenyl-4-aminobenzoate, (2-aminobenzyl-4-amino)phenyl-4-aminobenzoate, (3-aminobenzyl-4-amino)phenyl-4-aminobenzoate, (2-nitrobenzyl-4-amino)phenyl-4-aminobenzoate, (3-nitrobenzyl-4-amino)phenyl-4-aminobenzoate, (2-cyanobenzyl-4-amino)phenyl-4-aminobenzoate, (3-cyanobenzyl-4-amino)phenyl-4-aminobenzoate, (2-benzyloxy-4-amino)phenyl-4-aminobenzoate, (3-benzyloxy-4-amino)phenyl-4-aminobenzoic acid Ester, (2-methylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-methylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (2-ethylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-ethylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (2-propylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-propylbenzyloxy-4-amino)phenyl-4-aminobenzoate, (2-methoxybenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-methoxybenzyloxy-4-amino)phenyl-4-aminobenzoate, (2-ethoxybenzyloxy-4-amino)phenyl-4-aminobenzoate, (3-ethoxybenzyloxy-4-amino)phenyl-4-aminobenzoate, but are not limited to these.

[0191] On the other hand, a polymer including the 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).

[0192]

[0193] (Wherein, X2 is the same as above.)

[0194] Here, the polymer containing the structural unit (2) can be obtained by, for example, reacting the dicarboxylic acid compound represented by the general formula (30) and 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 for the reaction in a state dissolved in a reaction solvent, and a known dehydration condensation agent (for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc.) is added to the reaction solution under ice cooling, and after the dicarboxylic acid compound represented by the general formula (30) is converted into an acid anhydride, a substance obtained by separately dissolving or dispersing the diamine represented by the general formula (29) in a solvent is added dropwise thereto, and the resulting mixture is polycondensed to obtain a polymer containing the structural unit (2).

[0195] In addition, as another method for reacting a dicarboxylic acid compound represented by the general formula (30) with a diamine (diamine compound) represented by the general formula (29) to obtain a polymer containing the structural unit (2), there can be listed a method 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) for synthesis.

[0196] In the reaction of converting the dicarboxylic acid compound into an acid chloride using a chlorinating agent, a basic compound may be used. Examples of the basic compound include pyridine, N,N-dimethyl-4-aminopyridine, and triethylamine.

[0197] Next, by reacting the acid chloride of the obtained dicarboxylic acid compound with the diamine represented by the above general formula (29) in the presence of a basic catalyst, a polymer containing the structural unit (2) as the target can be obtained. In this case, 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 can be used alone or in combination of two or more.

[0198] In the method of producing the polymer (A), the solvent used in the method of undergoing the acid chloride is preferably a solvent that fully dissolves the polymer obtained by the polycondensation reaction with the above-mentioned dicarboxylic acid compound and its acid chloride, and further with diamines. Specifically, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric acid triamide, γ-butyrolactone, etc. can be listed. In addition, in addition to polar solvents, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. can also be used. Examples thereof 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.

[0199] Preferred examples of X2 in the dicarboxylic acid compound represented by the general formula (30) include the same examples as described above.

[0200] Examples of the dicarboxylic acid compound represented by the 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, pimelic acid, 2,2,6,6-Tetramethyl pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid , Eicosanedioic acid, hexadecanedioic acid, docosanedioic acid, triposanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, hexadecanedioic acid, hexadecanedioic acid, diglycolic acid, etc.

[0201] Examples of the dicarboxylic acid compound 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'-dicarboxy diphenylamide, 1,4-phenylene diethanedioxane, bis(4-carboxyphenyl) sulfide, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-carboxyphenyl)tetraphenyldisiloxane, bis(4-carboxyphenyl)tetramethyldisiloxane, bis(4-carboxyphenyl)sulfone, bis(4-carboxyphenyl)methane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,2-bis-(p-carboxyphenyl)propane, 2,6-naphthalene dicarboxylic acid, etc., but not limited thereto. In addition, these substances can be used alone or in combination.

[0202] On the other hand, the polymer containing the structural unit (3) can be obtained by carrying out the same reaction steps as the structural unit (1). That is, it 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, after synthesizing amic acid by reacting a tetracarboxylic dianhydride represented by the following general formula (31) with a diamine represented by the following general formula (32), an imide ring is formed by heating and dehydrating, thereby obtaining a polymer containing the structural unit (3).

[0203]

[0204] (Wherein, X3 is the same as above.)

[0205]

[0206] (Wherein, s and Z are the same as above.)

[0207] Preferred examples of the tetracarboxylic dianhydride represented by the general formula (31) include those described for the tetracarboxylic dianhydride represented by the general formula (28).

[0208] On the other hand, s in the general formula (32) represents 0 or 1. When s=0, the two aromatic rings in the general formula (32) are directly bonded to each other without the aid of the divalent bonding group Z.

[0209] In addition, when s in the general formula (32) is s=1, Z in the 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 is more preferably a divalent bonding group represented by the above formula (20). In addition, the structure of Z may be one or a combination of two or more.

[0210] Furthermore, suitable examples of the diamine represented by the general formula (32) are compounds represented by the following formulas (33), (34), (35), and (36).

[0211]

[0212] Furthermore, particularly suitable examples of the diamine represented by the general formula (32) are compounds represented by the formulas (33) and (34).

[0213] 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) as a preferred structural unit.

[0214] On the other hand, a polymer obtained by reacting a diamine represented by the above formula (34) with a tetracarboxylic dianhydride represented by the above general formula (31) is a polymer including a structural unit represented by the above general formula (3-2) as a preferred structural unit.

[0215] On the other hand, the polymer containing the structural unit (4) can be obtained by carrying out the same reaction steps as the structural unit (2). That is, the dicarboxylic acid compound represented by the following general formula (37) can be reacted in the presence of a dehydrating condensation agent, converted into an acid chloride using a chlorinating agent, and then reacted with the diamine represented by the above general formula (32) to obtain the polymer.

[0216]

[0217] (Wherein, X4 is the same as above.)

[0218] Preferred examples of the dicarboxylic acid compound represented by the general formula (37) include those listed for the dicarboxylic acid compound represented by the general formula (30).

[0219] As described above, the polymer (A) contained in the negative photosensitive resin composition of the present invention may 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).

[0220]

[0221] (Wherein, X5 and X6 are the same as above.)

[0222] The polymer containing the structural unit represented by the general formula (21) can be obtained by performing the same reaction steps as the structural unit (1). That is, after the tetracarboxylic dianhydride represented by the general formula (38) is reacted with the diamine represented by the general formula (39) to synthesize the amic acid, the imide ring is formed by heating and dehydrating the tetracarboxylic dianhydride represented by the general formula (38) and the diamine represented by the general formula (39), the polymer containing the structural unit represented by the general formula (21) can be obtained.

[0223]

[0224] (Wherein, X5 is the same as above.)

[0225] NH2-X6-NH2 (39)

[0226] (Wherein, X6 is the same as above.)

[0227] Preferred examples of the tetracarboxylic dianhydride represented by the general formula (38) include those described for the tetracarboxylic dianhydride represented by the general formula (28).

[0228] Examples of the diamine represented by the general formula (39) include aromatic diamines, alicyclic diamines, aliphatic diamines, and polyether diamines.

[0229] Preferred aromatic diamines include, for example, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzidine, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2'3,3'-tetramethylbenzidine, 2,2'-dichlorobenzidine, 3,3'-dichlorobenzidine, 2,2 ... 3,3'-tetrachlorobenzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)fluorene, 2,2'-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminobenzanilide, or diamine compounds obtained by replacing the aromatic rings of these with alkyl groups, alkoxy groups, halogen atoms, etc., but are not limited to these.

[0230] Examples of the alicyclic diamine include cyclobutanediamine, isophoronediamine, bicyclo[2,2,1]heptanedimethylamine, 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- The invention also includes, but is not limited to, diamine compounds obtained by replacing alicyclic rings thereof with alkyl groups, alkoxy groups, halogen atoms, etc., and the like.

[0231] Examples of the aliphatic diamine include, but are not limited to, alkylenediamines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane; and siloxanediamines such as bis(aminomethyl)ether, bis(2-aminoethyl)ether, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, and α,ω-bis(3-aminopropyl)polydimethylsiloxane.

[0232] Examples of the polyether diamine 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 (these are trade names, manufactured by HUNTSMAN Co., Ltd.). These may be used alone or in combination.

[0233] These aromatic diamines, alicyclic diamines, aliphatic diamines and polyether diamines can be used alone or in combination of two or more.

[0234] In addition, siloxane diamines can also be suitably used.

[0235] As described above, the polymer (A) contained in the negative photosensitive resin composition of the present invention may 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).

[0236]

[0237] (Wherein, X7 and X8 are the same as above.)

[0238] The polymer containing the structural unit represented by the general formula (22) can be obtained by carrying out the same reaction steps as the structural unit (2). That is, the dicarboxylic acid compound represented by the general formula (40) below can be reacted in the presence of a dehydrating condensation agent, converted into an acid chloride using a chlorinating agent, and then reacted with a diamine represented by the general formula (41) below to obtain the polymer.

[0239]

[0240] (Wherein, X7 is the same as above.)

[0241] NH2-X8-NH2 (41)

[0242] (Wherein, X8 is the same as above.)

[0243] Preferred examples of the dicarboxylic acid compound represented by the general formula (40) include those listed for the dicarboxylic acid compound represented by the general formula (30).

[0244] Moreover, as a diamine represented by the said general formula (41), the example shown for the diamine represented by the said general formula (39) is mentioned as a suitable example.

[0245] As described above, the polymer (A) contained in the negative photosensitive resin composition of the present invention may 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).

[0246]

[0247] (Where X9, X 10 and R b Same as above.)

[0248] The polymer containing the structural unit represented by the general formula (23) can be obtained by carrying out the same reaction steps as the structural unit (2). That is, the tetracarboxylic acid diester compound represented by the general formula (42) can be reacted in the presence of a dehydration condensation agent, converted into an acid chloride using a chlorinating agent, and then reacted with a diamine represented by the general formula (43) to obtain the polymer.

[0249]

[0250] (Where R b Same as above for X9.)

[0251] H2N-X 10 -NH2 (43)

[0252] (Where X 10 Same as above.)

[0253] As a method for producing the tetracarboxylic acid diester compound represented by the general formula (42), there is mentioned a method of introducing R by reacting a tetracarboxylic acid dianhydride represented by the general formula (44) below with a compound having a hydroxyl group at the terminal represented by the general formula (45) below in the presence of a basic catalyst such as pyridine. b Here, the tetracarboxylic dianhydride represented by the following general formula (44) is the source of X9 (for example, the tetravalent organic group represented by the above formula (18)) in the above general formula (23).

[0254]

[0255] (Wherein, X9 is the same as above.)

[0256] HO——Rb (45)

[0257] (Where R b Same as above.)

[0258] Preferred examples of the tetracarboxylic dianhydride represented by the general formula (44) include those described for the tetracarboxylic dianhydride represented by the general formula (28).

[0259] In the reaction of the tetracarboxylic dianhydride represented by the general formula (44) and the compound having a hydroxyl group at the terminal represented by the general formula (45), the tetracarboxylic dianhydride represented by the general formula (44) and the compound having a hydroxyl group at the terminal represented by the general formula (45) are stirred, dissolved and mixed for 4 to 10 hours in the presence of a basic catalyst such as pyridine and at a reaction temperature of 20 to 50° C. in a reaction solvent, thereby conducting a half-esterification reaction of the acid dianhydride, thereby being able to obtain the desired tetracarboxylic acid diester compound represented by the general formula (42) in the form of a solution obtained by dissolving it in a reaction solvent.

[0260] The obtained tetracarboxylic acid diester compound may be isolated, or the obtained solution may be directly used for the reaction with diamine in the above-mentioned subsequent step.

[0261] As the above-mentioned reaction solvent, it is preferred to fully dissolve the above-mentioned tetracarboxylic acid diester compound and the polymer having the structural unit of the polyimide precursor obtained by the polycondensation reaction of the above-mentioned tetracarboxylic acid diester compound and diamines that is then carried out, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, etc. can be listed. In addition, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. can also be used, specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. They can be used alone as needed, or two or more can be mixed and used.

[0262] Moreover, as a diamine represented by the said general formula (43), the example shown for the diamine represented by the said general formula (39) is mentioned as a suitable example.

[0263] As described above, the polymer (A) contained in the negative photosensitive resin composition of the present invention may further contain a structural unit represented by the following general formula (24) in addition to the structural units represented by the above general formulas (1), (2), (3) and (4).

[0264]

[0265] (Where X 11 and X 12 Same as above.)

[0266] Regarding the polymer containing the structural unit represented by the above general formula (24), a dicarboxylic acid compound represented by the following general formula (46) is reacted in the presence of a dehydration condensation agent and converted into an acid chloride using a chlorinating agent, and then reacted with a dihydroxydiamine compound represented by the following general formula (47) to synthesize a hydroxyamide (polyoxazole precursor), and then subjected to a heating dehydration step to form an oxazole ring, thereby obtaining a polymer containing the structural unit represented by the above general formula (24).

[0267]

[0268] (Where X 11 Same as above.)

[0269]

[0270] (Where X 12 Same as above.)

[0271] Preferred examples of the dicarboxylic acid compound represented by the general formula (46) include those listed for the dicarboxylic acid compound represented by the general formula (30).

[0272] Examples of the dihydroxydiamine compound represented by the 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 not limited to them. In addition, these substances can be used alone or in combination.

[0273] (Polymer Molecular Weight and Introduction of Terminal Capping Agent)

[0274] The suitable molecular weight of the polymer is preferably 5,000 to 100,000, more preferably 7,000 to 50,000. If the molecular weight is 5,000 or more, it is easy to form a film of the negative photosensitive resin composition of the present invention obtained by using the polymer into a desired film thickness on a substrate. If the molecular weight is 100,000 or less, the viscosity of the negative photosensitive resin composition does not increase significantly, and there is no worry that the film cannot be formed.

[0275] For the purpose of controlling the molecular weight in the polycondensation reaction and suppressing the molecular weight change of the obtained polymer over time, i.e., gelation, the above-mentioned polymer can be capped at both ends using an end-capping agent. As the end-capping agent that reacts with the acid dianhydride, monoamines, monohydric alcohols, etc. can be listed. In addition, as the end-capping agent that reacts with the diamine compound, acid anhydrides, monocarboxylic acids, monoacyl chloride compounds, monoactive ester compounds, dicarbonates, vinyl ethers, etc. can be listed. In addition, by reacting the end-capping agent, various organic groups can be introduced as terminal groups.

[0276] Examples of the monoamine used as a sealing agent for the acid anhydride terminal group include aniline, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy 4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, cyanuric acid monoamide, 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-aminobenzenesulfonic acid phenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2,4-diethyl Alkynylaniline, 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, 2,4,6-trifluoroaniline, 2,3,4-trifluoroaniline, pentafluoroaniline, etc., but not limited to them. These may be used alone or in combination of two or more.

[0277] On the other hand, examples of the monohydric alcohol used as a sealing agent for the acid anhydride group terminal include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, 2-nonanol, 1-decanol, 2-decanol, 1-undecanol, 2-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 2-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 2-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2-heptadecanol, 1-octadecanol, 2-octadecanol, 1-nonadecanol, 2-nonadecanol, 1-eicosanol, 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, isononanol, 3,7-dimethyl-3- Octanol, 2,4-dimethyl-1-heptanol, 2-heptylundecanol, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol-1-methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, cyclopentanol, cyclohexanol, cyclopentane monomethylol, dicyclopentane monomethylol, tricyclodecane monomethylol, norbornene, terpineol, etc., but are not limited to them. In addition, they can be used alone or in combination of two or more.

[0278] Examples of the acid anhydride, monocarboxylic acid, monoacyl chloride compound and monoactive ester compound used as the sealing agent for the amino terminal include 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, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl-1-naphthoic acid, 3 -ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid, 8-ethynyl-2-naphthoic acid and the like monocarboxylic acids; and monoacyl chloride compounds obtained by chlorinating the carboxyl groups thereof; and terephthalic acid, phthalic acid, maleic acid, cyclopentane Monoacyl chloride compounds obtained by chlorinating only one carboxyl group of dicarboxylic acids such as hexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, and 2,7-dicarboxynaphthalene; monoactive ester compounds obtained by reacting the monoacyl chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide, etc.

[0279] Examples of the dicarbonate compound used as a sealing agent for the amino terminal include di-tert-butyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.

[0280] Examples of the vinyl ether compound used as a sealant for the amino 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.

[0281] Other compounds used as sealants for the amino terminal include chloroformates such as benzoyl chloride, fluorenylmethyl chloroformate, 2,2,2-trichloroethyl chloroformate, tert-butyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, benzyl chloroformate, allyl chloroformate, ethyl chloroformate, and isopropyl chloroformate; isocyanate compounds such as butyl isocyanate, 1-naphthyl isocyanate, octadecyl isocyanate, and phenyl isocyanate; methanesulfonyl chloride, p-toluenesulfonyl chloride, and the like.

[0282] The introduction ratio of the sealing agent at the end of the acid anhydride group is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, and further preferably 5 to 20 mol% relative to the total amount of the tetracarboxylic dianhydride component and the dicarboxylic acid component. In addition, the introduction ratio of the sealing agent at the amino terminal is preferably in the range of 0.1 to 100 mol%, particularly preferably 5 to 90 mol%, relative to the diamine component. In addition, by reacting a plurality of end-capping agents, a plurality of different terminal groups can be introduced.

[0283] [(B) Photoacid generator]

[0284] The (B) photoacid generator contained in the negative photosensitive resin composition of the present invention is not particularly limited, and a substance that generates acid by irradiation with light of a wavelength of 190 to 500 nm and serves as a curing catalyst can be used. Examples thereof include onium salts, diazomethane derivatives, oxime derivatives, oxime sulfonate derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonate derivatives, imido-sulfonate derivatives, iminosulfonate derivatives, triazine derivatives, etc. These are described in detail below, and they can be used alone or in combination of two or more.

[0285] Examples of the onium salt include compounds represented by the following general formula (48).

[0286] (R 26 ) j M + K - (48)

[0287] (Where R 26 is 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, + is an iodonium ion or a sulfonium ion, K -is a non-nucleophilic counterion, and j is 2 or 3. )

[0288] The above R 26 In the above, examples of the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, cyclohexyl, 2-oxocyclohexyl, norbornyl, and adamantyl. Examples of the aryl group having 6 to 12 carbon atoms include phenyl; alkoxyphenyl groups such as o-, m- or p-methoxyphenyl, ethoxyphenyl, and m- or p-tert-butyloxyphenyl; and alkylphenyl groups such as 2-, 3- or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl, phenethyl, and the like.

[0289] As K - Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkyl sulfonates such as trifluoromethanesulfonate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; aryl sulfonates such as toluenesulfonate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; and alkyl sulfonates such as methanesulfonate and butanesulfonate.

[0290] Examples of the diazomethane derivative include compounds represented by the following general formula (49).

[0291]

[0292] (Where R 27 ) are optionally the same or different and represent a linear, branched or cyclic alkyl or halogenated alkyl group having 1 to 12 carbon atoms, an aryl or halogenated aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

[0293] The above R 27 In the above, examples of the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Examples of the linear, branched or cyclic halogenated alkyl group having 1 to 12 carbon atoms include trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, and nonafluorobutyl. Examples of the aryl group having 6 to 12 carbon atoms include phenyl; alkoxyphenyl groups such as o-, m- or p-methoxyphenyl, ethoxyphenyl, and m- or p-tert-butyloxyphenyl; and alkylphenyl groups such as 2-, 3- or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl. Examples of the halogenated aryl group having 6 to 12 carbon atoms include fluorophenyl, chlorophenyl, and 1,2,3,4,5-pentafluorophenyl. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl and phenethyl.

[0294] 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) oxyphenyl)diphenylsulfonium, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tri(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, Onium salts such as dicyclohexylphenylsulfonium p-toluenesulfonate and diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate; 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 Diazomethane derivatives such as (isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, and 1-tert-pentylsulfonyl-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-pentanedioneglyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedioneglyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione Glyoxime, bis-o-(methylsulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butylsulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexylsulfonyl)-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 and other glyoxime derivatives; oxime sulfonate derivatives such as α-(phenylsulfonyloxyimino)-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; sulfonate derivatives such as 1,2,3-tris(methylsulfonyloxy)benzene, 1,2,3-tris(trifluoromethylsulfonyloxy)benzene and 1,2,3-tris(p-toluenesulfonyloxy)benzene; phthalate Imido-sulfonate derivatives such as imino-trifluoromethanesulfonate, phthalimido-toluenesulfonate, 5-norbornene-2,3-dicarboximido-trifluoromethanesulfonate, 5-norbornene-2,3-dicarboximido-toluenesulfonate, 5-norbornene-2,3-dicarboximido-n-butanesulfonate, and n-trifluoromethylsulfonyloxynaphthyl imide; iminosulfonate derivatives such as (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile and (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, imido-sulfonate derivatives, iminosulfonate derivatives, oximesulfonate derivatives, etc. can be suitably used. The above-mentioned photoacid generator can be used alone or in combination. ;

[0295] The amount of the photoacid generator as the component (B) is preferably 0.05 to 20 parts by mass, particularly preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the component (A) in the negative photosensitive resin composition of the present invention, from the viewpoint of light absorption of the photoacid generator itself and photocurability in thick films.

[0296] [(C) Cross-linking agent]

[0297] The (C) crosslinking agent contained in the negative photosensitive resin composition of the present invention may be any composition as long as it is a compound having a group that crosslinks with the (A) component. The aforementioned (C) component is preferably selected from one or more crosslinking agents selected from amino condensates modified with formaldehyde or formaldehyde-alcohol, phenol compounds having an average of more than two hydroxymethyl groups or alkoxyhydroxymethyl groups in one molecule, compounds obtained by replacing the hydrogen atoms of the hydroxyl groups of polyphenols with glycidyl groups, compounds obtained by replacing the hydrogen atoms of the hydroxyl groups of polyphenols or polyols 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).

[0298]

[0299] (In the formula, the dotted line represents a connecting bond; Rc is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; v is 1 or 2.)

[0300] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include melamine condensate modified with formaldehyde or formaldehyde-alcohol, and urea condensate modified with formaldehyde or formaldehyde-alcohol.

[0301] In the preparation of the above-mentioned melamine condensate modified by formaldehyde or formaldehyde-alcohol, for example, the melamine monomer is first modified by hydroxymethylation with formaldehyde according to a known method, or it is further modified by alkoxylation with alcohol to prepare a modified melamine represented by the following general formula (50).

[0302] In addition, as the above-mentioned alcohol, a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms is preferable.

[0303]

[0304] (Where R 28They are optionally the same or different and are hydroxymethyl, alkoxymethyl containing an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, and at least one of them is a hydroxymethyl or the above alkoxymethyl.

[0305] As the above R 28 Examples of the group include a hydroxymethyl group, an alkoxymethyl group including an alkoxy group having 1 to 4 carbon atoms such as a methoxymethyl group and an ethoxymethyl group, and a hydrogen atom.

[0306] Specific examples of the modified melamine represented by the general formula (50) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethylol melamine, etc. Next, the modified melamine represented by the general formula (50) or a polymer thereof (e.g., an oligomer such as a dimer or trimer) is subjected to addition polycondensation with formaldehyde according to a conventional method until the desired molecular weight is reached, thereby obtaining a melamine condensate modified with formaldehyde or formaldehyde-alcohol.

[0307] In the preparation of the urea condensate modified with formaldehyde or formaldehyde-alcohol, for example, a urea condensate of a desired molecular weight is modified by methylolation with formaldehyde, or further modified by alkoxylation with an alcohol according to a known method.

[0308] Specific examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, propoxymethylated urea condensate, and the like.

[0309] In addition, these modified melamine condensates and modified urea condensates may be used alone or in combination of two or more.

[0310] Next, examples of phenol compounds having an average of two or more methylol groups or alkoxymethylol groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and compounds represented by the following formulae (C-3) to (C-7).

[0311]

[0312] (In the formula, Me is a methyl group.)

[0313] The phenol compound having an average of two or more hydroxymethyl groups or alkoxymethylol groups in one molecule may be used alone or in combination of two or more.

[0314] On the other hand, as a compound obtained by replacing the hydrogen atom of the hydroxyl group of a polyphenol with a glycidyl group, there can be mentioned a compound obtained by reacting the hydroxyl group of bisphenol A, tris(4-hydroxyphenyl)methane, or 1,1,1-tris(4-hydroxyphenyl)ethane with epichlorohydrin in the presence of a base. As a suitable example of a compound obtained by replacing the hydrogen atom of the hydroxyl group of a polyphenol with a glycidyl group, there can be mentioned compounds represented by the following formulas (C-8) to (C-14).

[0315]

[0316] (Wherein, t is 2≤t≤3.)

[0317] One or more compounds obtained by replacing the hydroxyl group of these polyphenols with a glycidyl group (compounds obtained by replacing the hydrogen atom of the hydroxyl group of the polyphenol with a glycidyl group) may be used as a crosslinking agent.

[0318] Examples of the compound obtained by replacing the hydrogen atom of the hydroxyl group of a polyphenol or a polyol with a substituent represented by the following formula (C-1) include compounds having two or more of the substituents and represented by the following general formula (C-15).

[0319]

[0320] (In the formula, the dotted line represents the connecting bond.)

[0321]

[0322] (Where 1≤u≤3.)

[0323] One or more compounds obtained by replacing hydrogen atoms of hydroxyl groups of polyphenols or hydroxyl groups of polyols with substituents represented by the above formula (C-1) may be used as a crosslinking agent.

[0324] On the other hand, examples of the compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2) include compounds represented by the following general formula (C-16).

[0325]

[0326] (In the formula, the dotted line represents a connecting bond; Rc is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; v is 1 or 2.)

[0327]

[0328] (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.)

[0329] Examples of the compound represented by the general formula (C-16) include compounds represented by the following formulae (C-17) to (C-20).

[0330]

[0331] 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 preferably used.

[0332]

[0333] These compounds containing two or more nitrogen atoms having a glycidyl group represented by the above formula (C-2) can be used as a crosslinking agent alone or in combination of two or more.

[0334] As described above, the component (C) of the negative photosensitive resin composition of the present invention is a component that uses the acid generated by the component (B) as a catalyst to crosslink the crosslinking group of the component (C) with the polymer of the component (A), so that it is needless to say that a negative pattern can be formed. After the pattern is formed, a crosslinking reaction also occurs during post-curing, further improving the strength of the cured product. From the viewpoint of photocurability and heat resistance, the weight average molecular weight of the component (C) is preferably 150 to 10,000, and particularly preferably 200 to 3,000.

[0335] (C) The compounding quantity of a component is preferably 0.5-50 mass parts with respect to 100 mass parts of (A) components in the negative photosensitive resin composition of this invention, and 1-30 mass parts is especially preferable.

[0336] [(D) Solvent]

[0337] The solvent of component (D) in the present invention is not limited as long as it dissolves component (A), component (B) and component (C). Examples of the solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol-mono-tert-butyl ether acetate, and γ-butyrolactone, and one or more of these can be used. Particularly preferred are ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, or a mixed solvent thereof.

[0338] The amount of the component (D) is preferably 50 to 2,000 parts by mass, and particularly preferably 100 to 1,000 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (B).

[0339] [(E) Cross-linkable polymer compound]

[0340] The negative photosensitive resin composition of the present invention may contain (E) a crosslinkable polymer compound. That is, the negative photosensitive resin composition preferably further contains:

[0341] (E) A cross-linkable polymer compound comprising a structural unit represented by the following general formula (9) and having a group capable of forming a cross-link with the component (A).

[0342]

[0343] (In the formula, R5 is a hydrogen atom or a methyl group; R6 is a (n+1)-valent straight-chain, 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 naphthylmethyl group, wherein the carbon atoms of the aforementioned aliphatic saturated hydrocarbon group may be substituted by oxygen atoms. n is an integer from 1 to 5. Y1 is -C(=O)-O-, -C(=O)-NH- or -C(=O)-N(R7OH)-. R7 is a divalent straight-chain, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein the carbon atoms of the aforementioned aliphatic saturated hydrocarbon group may be substituted by oxygen atoms. p1 is 0 or 1.)

[0344] In addition, as examples that can be preferably used in the structure represented by the above general formula (9), the following examples can be specifically exemplified.

[0345]

[0346] (Wherein, R5 is as described above.)

[0347]

[0348] (Wherein, R5 is as described above.)

[0349]

[0350]

[0351] (Wherein, R5 is as described above.)

[0352] In order to increase the crosslinking density while maintaining alkali solubility, the (E) crosslinkable polymer compound contained in the negative photosensitive resin composition of the present invention is more preferably a crosslinkable polymer compound which further includes 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 aforementioned (A) component.

[0353]

[0354] (In the formula, R8 is a hydrogen atom or a methyl group; Y2 is -C(=O)-O-, -C(=O)-NH- or -C(=O)-N(R9OH)-. R9 is a divalent straight-chain, 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 the carbon atoms of the aliphatic saturated hydrocarbon group may be optionally replaced by oxygen atoms. p2 is 0 or 1.)

[0355]

[0356] (Where 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 oxetane group or an epoxy group, and Y3 is -C(=O)-O-, a phenylene group or a naphthylene group. p3 is 0 or 1.)

[0357] 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.

[0358] When reacting with the hydroxyl group or carboxyl group in the above-mentioned (A) component, the blocking agent is released, and the hydroxyl group or carboxyl group reacts with the isocyanate group to form a crosslinked structure. The blocking agent is a compound containing active hydrogen that can react with isocyanate, and examples thereof include alcohols, phenols, polycyclic phenols, amides, imides, imides, thiols, oximes, lactams, heterocycles containing active hydrogen, and compounds containing active methylene groups.

[0359] Suitable blocked isocyanate groups are described in paragraphs

[0015] to

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

[0360] On the other hand, in the structure shown in general formula (10), when there is a carbonyl group or an amide group as an electron-withdrawing group at the para position of the phenolic hydroxyl group, the acidity of the phenolic hydroxyl group becomes high, and the solubility in the developer of the alkaline aqueous solution is improved. As examples that can be preferably used, specifically, the following examples can be illustrated. However, it is not limited to them.

[0361]

[0362] (Wherein, R8 is as described above.)

[0363]

[0364] (Wherein, R8 is as described above.)

[0365] The general formula (10) is effective as a unit that promotes crosslinking in addition to promoting alkali solubility, and can further improve curability by using it in combination with a crosslinking group.

[0366] In order to further increase the crosslinking density, the (E) crosslinkable polymer compound contained in the negative photosensitive resin composition of the present invention preferably contains a structural unit having an epoxy group or an oxetanyl group represented by the following general formula (12).

[0367]

[0368] Here, in the general formula (12), R 12 is a hydrogen atom or a methyl group; Y4 is -C(=O)-O-, a phenylene group or a naphthylene group. 13 is a hydroxyl group, an ester group, an ether group, or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may contain an aromatic hydrocarbon; R 14 is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, optionally with R 13 Bond 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, optionally with R 13 m is 0 or 1. p4 is 0 or 1.

[0369] Examples of the unit of the general formula (12) include the following.

[0370]

[0371] (Where R 12 As described above.)

[0372]

[0373] (Where R 12 As described above.)

[0374]

[0375] (Where R 12As described above.)

[0376] In addition, some of the monomers for obtaining the repeating unit having an epoxy group and an oxetanyl group are disclosed in Japanese Patent Application Laid-Open Nos. 2003-055362, 2005-008847, and 2005-018012.

[0377] The structural unit represented by the general formula (10) has excellent solvent solubility and alkali solubility, but has no crosslinking property, and therefore, it is preferably copolymerized with the structural unit represented by the general formula (12) having crosslinking property. The polymer composed only of the epoxy group and oxetanyl group represented by the general formula (12) having crosslinking property has excellent crosslinking property, but has no alkali solubility, and therefore, it is preferably copolymerized with the structural unit represented by the general formula (10).

[0378] 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).

[0379]

[0380] (In the formula, R8~R 16 , Y2, Y4, m, p2 and p4 are the same as above, 0 <a1<1.0、0<a2<1.0、0<a1+a2≤1.0。)

[0381] From the viewpoint of further improving the crosslinking reactivity during photolithography patterning and improving the dissolution contrast of the unexposed / exposed parts relative to the alkaline developer, 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).

[0382]

[0383] (Where R 17 is a hydrogen atom or a methyl group; R 18 is a single bond, or a (1+1)-valent straight-chain, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms, wherein the carbon atoms of the aliphatic saturated hydrocarbon group may be substituted by oxygen atoms. 19 -, -C(=O)-NH-, -C(=O)-N(R 19 OH)-, phenylene or naphthylene. 19A divalent straight-chain, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein the carbon atoms of the aliphatic saturated hydrocarbon group may be substituted by oxygen atoms. l is 0 or 1.)

[0384] Examples of the unit of the general formula (13) include units that do not contain an aromatic hydrocarbon group among the units listed as examples of the unit of the general formula (9).

[0385] From the viewpoint of improving adhesion to the 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 comprising at least one structural unit selected from the 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).

[0386]

[0387] (Where R 20 , R 21 , R 22 , R 23 , R 24 and R 25 Each is independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

[0388] Particularly preferred are structural units obtained by cyclopolymerization of monomer units represented by the following general formulae (51) and (52). These monomers may be used alone or in combination of two or more.

[0389]

[0390] (Where R 23 , R 24 and R 25 As described above.)

[0391] In particular, specific examples of commercially available products that can be used include ACRYCURE RD series and ACRYCURE RE series (trade names, manufactured by Nippon Shokubai Co., Ltd.).

[0392] In particular, from the viewpoint of polymerizability and stability, the monomer unit (51) that undergoes cyclopolymerization to form a structural unit of the general formula (16) is more preferred.

[0393] Here, in order to take into account all of the mechanical properties, alkali solubility, and crosslinkability, the component (E) is preferably 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).

[0394]

[0395] 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.

[0396] 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 may further contain a structural unit represented by the following general formula (53).

[0397]

[0398] Here, in the above general formula (53), R 28 is a hydrogen atom or a methyl group; R 29 is a monovalent organic group having a primary amino group, a secondary amino group, or a 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-.

[0399] The following specific examples are given as monomers for obtaining the repeating unit represented by the general formula (53). They include 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-diethylaminoethyl (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, 2-(piperidin-4-yl)ethyl (meth)acrylate, etc.

[0400] Furthermore, specific examples of the alkyl (meth)acrylate include butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate.

[0401] Furthermore, in order to improve the mechanical strength of the cured film, olefins having aromatic groups such as styrenes, vinylnaphthalenes, vinylanthracenes, vinylcarbazoles, acenaphthylenes, and indenes; and alicyclic olefins such as norbornenes and norbornadienes may be copolymerized.

[0402] The cross-linkable polymer compound (E) contained in the negative photosensitive resin composition of the present invention preferably has a polystyrene conversion weight average molecular weight based on gel permeation chromatography (GPC) of 1,000 to 500,000, and particularly preferably 2,000 to 30,000. If the weight average molecular weight is 1,000 or more, the glass transition temperature becomes high, and the pattern will not be deformed during the thermal crosslinking after the development of the negative photosensitive resin composition. If it is 500,000 or less, pinhole defects will not be caused during coating. It should be noted that two or more polymers with different composition ratios, molecular weight distributions, and molecular weights can also be blended.

[0403] In addition, at this time, the addition amount of the cross-linked polymer compound (E) is preferably 10 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the (A) polymer. If the addition amount is 10 parts by mass or more, then in the cured film of the (A) polymer as described above, the toughness is high, and if it is 100 parts by mass or less, the tensile strength of the cured film will not decrease, therefore, the addition amount of the cross-linked polymer compound (E) is preferably set to the above range. The addition amount of the (E) cross-linked polymer compound is more preferably 10 parts by mass or more and 70 parts by mass or less, and further preferably 30 parts by mass or more and 50 parts by mass or less. By setting to this range, the balance between the photolithography patterning performance and the cured film physical properties becomes good.

[0404] The negative photosensitive resin composition of the present invention may contain 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 in addition to the above-mentioned (A), (B), (C), (D) components and preferably (E) component as essential components. Components (F), (G), (H), and (I) are described in detail below.

[0405] [(F) Basic compound]

[0406] The basic compound of the component (F) is preferably a compound that can suppress the diffusion rate of the acid generated by the photoacid generator (B) when diffusing into the photosensitive resin composition. By adding such a basic compound (F), the diffusion rate of the acid in the photosensitive resin composition is suppressed, the resolution is improved, the sensitivity change after exposure is suppressed, the substrate or environment dependency is reduced, and the exposure margin, pattern profile, etc. can be improved.

[0407] Examples of the above-mentioned (F) basic compound include ammonia, aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, and the like.

[0408] Specifically, examples of the aliphatic primary amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, and the like. Examples of the aliphatic secondary amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, and didecylamine. , didodecylamine, dicetylamine, N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, N,N-dimethyltetraethylenepentamine, etc., and as the aliphatic tertiary amines, 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, etc. can be exemplified.

[0409] Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine.

[0410] Specific examples of the 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, etc. , 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, pyrrolidone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, picoline, 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-pyrrolidinylpyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, dimethylpyridine, Hydrogen pyrazole derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoleline derivatives, 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, uridine derivatives, etc.

[0411] Furthermore, examples of nitrogen-containing compounds having a carboxyl group include aminobenzoic acid, indolecarboxylic 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.

[0412] Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate.

[0413] Examples of the nitrogen-containing compound having a hydroxyl group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol 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, and 2-(2-hydroxyethyl)pyridine. , 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidineethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidone, 3-piperidinyl-1,2-propanediol, 3-pyrrolidinyl-1,2-propanediol, 8-hydroxyjulolidine, 3-quinuclidine, 3-tropine, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N-(2-hydroxyethyl)phthalimide, N-(2-hydroxyethyl)isonicotinamide, etc.

[0414] Examples of the amide derivatives include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, and benzamide.

[0415] Examples of the imide derivative include phthalimide, succinimide, and maleimide.

[0416] It should be noted that the basic compound (F) may be used alone or in combination of two or more, and when the amount thereof is 0 to 2 parts by mass relative to 100 parts by mass of the polymer of the component (A), 0.01 to 2 parts by mass, and particularly 0.01 to 1 part by mass, is preferably mixed. If the amount is 2 parts by mass or less, the sensitivity will not be reduced.

[0417] [(G) Thermal acid generator]

[0418] The negative photosensitive resin composition of the present invention may further contain (G) a thermal acid generator. The thermal acid generator of the component (G) may be added for the purpose of thermally accelerating the crosslinking reaction of the component (A) with the component (C) and the component (E) in the step of heating at a temperature of 100 to 300° C. applied after pattern formation and post-curing described later.

[0419] In particular, as the (G) component, it is preferred that the component does not promote the curing of the film and does not hinder the formation of the pattern until the pattern is formed by development. In order to achieve this purpose, the (G) component is preferably: after the photosensitive resin composition is made into a coating film, it does not generate acid at the temperature of the process of removing the solvent and drying, and generates acid for the first time by the heat treatment after the pattern is formed, and promotes the curing of the pattern and coating of the negative photosensitive resin composition. Specifically, it is preferably 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, in the process of heating and post-curing the pattern and coating of the negative photosensitive resin composition at a temperature of 100 to 300°C applied after pattern formation, it can be changed into a pattern and coating in which the crosslinking and curing reaction are further promoted. The (G) component can further improve the mechanical strength, chemical resistance, adhesion, etc. of the obtained pattern or coating by further promoting the crosslinking and curing reaction.

[0420] As suitable (G) thermal acid generators, compounds described in paragraphs

[0061] to

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

[0421] 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 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. By setting the amount to 0.1 parts by mass or more, the crosslinking reaction is promoted. In addition, by setting the amount to 30 parts by mass or less, the alkali developability of the composition is not deteriorated, and development residue is not generated.

[0422] [(H) Antioxidant]

[0423] The negative photosensitive resin composition of the present invention may further contain (H) an antioxidant. By containing the antioxidant of the component (H), the oxidative degradation of the aliphatic group and the phenolic hydroxyl group of the component (A) is suppressed. In addition, by preventing the metal material from rusting, the metal oxidation caused by external moisture, photoacid generators, thermal acid generators, etc., and the associated reduction in adhesion and peeling can be suppressed.

[0424] If specific examples of the (H) antioxidant that can be used here are listed, hindered phenol antioxidants, phosphorus antioxidants and sulfur antioxidants are preferably listed. However, they are not limited to them. In addition, these (H) antioxidants can be used alone or in combination of two or more.

[0425] Among the specific examples of the above-mentioned (H) antioxidant, if hindered phenol-based antioxidants are further exemplified, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Japan, Irganox 1010 (trade name)), thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Japan, Irganox 1035 (trade name)), octadecyl[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Japan, Irganox 1076 (trade name)), octyl 3,5-di-tert-butyl-4-hydroxy-hydrocinnamate (manufactured by BASF Japan, Irganox 1135 (trade name)), 4,6-bis(octylthiomethyl-o-cresol) (manufactured by BASF Japan, Irganox 1136 (trade name)), JAPAN Co., Ltd., Irganox 1520L), SUMILIZER GA80 (manufactured by Sumitomo Chemical Co., Ltd., trade name), ADEKASTAB AO-20 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-30 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-40 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-50 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-60 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-80 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-330 (manufactured by ADEKA Co., Ltd., trade name), hindered phenol-based antioxidants described in International Publication No. 2017 / 188153, and the like.

[0426] Among the specific examples of the above-mentioned (H) antioxidants, if further examples of phosphorus-based antioxidants are given, there can be mentioned triphenyl phosphite, tris(methylphenyl) phosphite, tri(isooctyl) phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tris(nonylphenyl) phosphite, tris(octylphenyl) phosphite, tris[decylpoly(oxyethylene)] phosphite, tris(cyclohexylphenyl) phosphite, tricyclohexyl phosphite, tridecylthiophosphite, tris(2-ethylhexyl)thio ...2-ethylhexyl)thiophosphite, tris(2-octylphenyl)thiophosphite, tris(2-decylpoly(oxyethylene)thiophosphite), tris(2-ethylhexyl)thiophosphite, tris(2-octylphenyl)thiophosphite, tris(2-decylpoly(oxyethylene)thiophosphite), tris(2-ethylhexyl)thiophosphite, tris(2-ethylhexyl)thiophosphite, tris(2-ethylhexyl)thiophosphite, tris(2-ethylhexyl)thiophosphite, tris(2-ethylhexyl)thiophosphite, tris(2-ethylhexyl)thiophosphite, tris(2-ethylhexyl)thiophosphite, tris(2-ethylhexyl)thiophosphite, tris(2-ethylhexyl)thiophosphite, tris Isodecyl ester, phenyl phosphite-bis (2-ethylhexyl) ester, phenyl diisodecyl phosphite, tetradecyl poly (oxyethylene) bis (ethylphenyl) phosphite, phenyl dicyclohexyl phosphite, phenyl diisooctyl phosphite, phenyl di (tridecyl) phosphite, diphenyl cyclohexyl phosphite, diphenyl isooctyl phosphite, diphenyl-2-ethylhexyl phosphite, diphenyl isodecyl phosphite, diphenyl cyclohexyl phenyl phosphite, diphenyl (tridecyl) thiophosphite, etc.

[0427] Specific examples of the above-mentioned (H) antioxidant include sulfur-based antioxidants such as ADEKASTAB AO-412S (trade name, manufactured by ADEKA Corporation), AO-503S (trade name, manufactured by ADEKA Corporation), and SUMILIZER TP-D (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

[0428] Sulfur-based antioxidants and phosphorus-based antioxidants are expected to have the effect of decomposing peroxides.

[0429] In addition, the content of the (H) antioxidant is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass, relative to 100 parts by mass of the polymer of the (A) component. By making the content 0.1 parts by mass or more, the adhesion to the metal material is improved and peeling is suppressed. In addition, by making the content 10 parts by mass or less, the alkali developability of the composition and the toughness of the cured film will not deteriorate.

[0430] [(I) Silane compound]

[0431] The negative photosensitive resin composition of the present invention may further contain (I) a silane compound. The silane compound of component (I) can not only improve adhesion to metal materials but also suppress peeling of the cured film in reliability tests such as thermal shock tests and high temperature and high humidity tests.

[0432] The (I) silane compound that can be used here is not particularly limited, and preferably has an alkoxysilyl group. In addition, suitable specific examples are shown below. They include: γ-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, bis(2-hydroxyethyl)-3-aminopropyl-triethoxysilane, γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, γ-acryloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, bis(2-hydroxyethyl)-3-aminopropyl triethoxysilane, Triethoxysilylpropylethylcarbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, silane compounds containing amide groups recorded in Japanese Patent No. 6414060, silane compounds containing thiourea groups recorded in International Publication No. 2016 / 140024 and Japanese Patent No. 5987984, silane compounds containing thiol groups recorded in Japanese Patent No. 2017-044964, etc. But it is not limited to them. Furthermore, these (I) silane compounds can be used alone or in combination of two or more.

[0433] In addition, 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 further preferably 3 to 6 parts by mass relative to 100 parts by mass of the polymer of the component (A). If it is 0.1 parts by mass or more, it is possible to impart more sufficient adhesion to the substrate, and if it is 20 parts by mass or less, it is possible to further suppress the problem of viscosity increase during storage at room temperature. In addition, by making the content 10 parts by mass or less, the alkali developability of the composition will not deteriorate, and will not cause development residues.

[0434] [Other ingredients]

[0435] In addition, the negative photosensitive resin composition of the present invention may further contain components other than component (A), component (B), component (C), component (D), component (E), component (F), component (G), component (H) and component (I). Other components include, for example, (J) surfactants and (K) dissolution inhibitors. The compounds exemplified below may be suitably used. However, they are not limited thereto.

[0436] [(J) Surfactant]

[0437] The surfactant (J) is preferably a nonionic surfactant, and examples thereof include fluorine-based surfactants, and specific examples thereof include perfluoroalkyl polyoxyethylene ethanol, fluoroalkyl esters, perfluoroalkyl amine oxides, fluorine-containing organosiloxane compounds, and non-fluorine-containing organosiloxane compounds.

[0438] As these (J) surfactants, commercially available products can be used, and examples thereof include Fluorad FC-4430 (trade name, manufactured by Sumitomo 3M Co., Ltd.), PF-6320 (trade name, manufactured by OMNOVA Co., Ltd.), PF-636 (trade name, manufactured by OMNOVA Co., Ltd.), Surflon S-141 and S-145 (both manufactured by Asahi Glass Co., Ltd., trade names), UNIDYNE DS-401, DS-4031 and DS-451 (both manufactured by Daikin Industries, Ltd., trade names), 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 Co., Ltd.), PF-6320 (trade name, manufactured by OMNOVA Co., Ltd.), PF-636 (trade name, manufactured by OMNOVA Co., Ltd.), and KP-341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) are preferred.

[0439] The amount of the surfactant (J) is preferably 0.01 to 0.05 parts by mass based on 100 parts by mass of the polymer (A). Within this range, the coating properties on the substrate can be improved without impairing the patterning performance or the properties of the cured film.

[0440] [(K) Dissolution inhibitor]

[0441] As (K) dissolution inhibitors, the following compounds can be listed: compounds 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, wherein the hydrogen atoms of the phenolic hydroxyl groups are replaced by acid-labile groups at an average ratio of 0 to 100 mol % on the whole; or compounds having a carboxyl group in the molecule, wherein the hydrogen atoms of the carboxyl group are replaced by acid-labile groups at an average ratio of 50 to 100 mol % on the whole.

[0442] It should be noted that the substitution rate of the hydrogen atoms of the phenolic hydroxyl group based on the acid-labile group is on average more than 0 mol% of the overall phenolic hydroxyl group, preferably more than 30 mol%, and its upper limit is 100 mol%, more preferably 80 mol%. The substitution rate of the hydrogen atoms of the carboxyl group based on the acid-labile group is on average more than 50 mol% of the overall carboxyl group, preferably more than 70 mol%, and its upper limit is 100 mol%.

[0443] In this case, the compound having two or more phenolic hydroxyl groups or the compound having a carboxyl group is preferably a compound represented by the following formulas (K1) to (K14).

[0444]

[0445] Among them, 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 Represents -(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 or alkenyl group having 1 to 8 carbon atoms, or a phenyl group or naphthyl group 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 satisfy t1+u1=8, t2+u2=5, and t3+u3=4, respectively, and are numbers such that each phenyl skeleton has at least one hydroxyl group. aa is a number such that the molecular weight of the compound of formula (K8) or (K9) is 100 to 1,000.

[0446] The amount of the dissolution inhibitor (K) is greater than 0 and less than 50 parts by mass, preferably 5 to 50 parts by mass, and more preferably 5 to 20 parts by mass relative to 100 parts by mass of the polymer of the component (A). The dissolution inhibitor may be used alone or in combination of two or more. The clarity is improved by adding the component (K), and the film weight loss of the pattern is not caused by setting the amount to less than 50 parts by mass, and the resolution is not reduced.

[0447] (Pattern Formation Method)

[0448] The present invention provides a pattern forming method, which comprises the following steps:

[0449] (1) coating the negative photosensitive resin composition described above on a substrate to form a photosensitive material coating;

[0450] (2) After the heat treatment, the photosensitive material coating is exposed to light through a photomask using high energy rays or electron beams with a wavelength of 190 to 500 nm;

[0451] (3) After the exposure, the substrate subjected to the heat treatment is developed using a developer of an alkaline aqueous solution.

[0452] Hereinafter, a pattern forming method using the negative photosensitive resin composition of the present invention will be described.

[0453] In the negative photosensitive resin composition of the present invention, in order to form a pattern, a known photolithography technology can be used. For example, the negative photosensitive resin composition is applied by a spin coating method (spin coating method) on a substrate having a pattern such as a silicon wafer or a SiO2 substrate, a SiN substrate, or a copper wiring, and pre-baked at 80 to 130° C. for about 50 to 600 seconds to form a photosensitive material coating with a thickness of 1 to 50 μm, preferably 1 to 30 μm, and more preferably 5 to 20 μm.

[0454] In the spin coating method, about 5 mL of the photosensitive resin composition is dispensed on a silicon substrate, and then the substrate is rotated to apply the photosensitive resin composition on the substrate. At this time, the thickness of the photosensitive material coating on the substrate can be easily adjusted by adjusting the rotation speed.

[0455] Next, a photomask for forming a target pattern is placed on the photosensitive material film, and the exposure dose is 1 to 5,000 mJ / cm 2 About 100 to 2,000 mJ / cm 2 In the left-right method, exposure is performed by irradiating high-energy rays such as i-rays and g-rays with a wavelength of 190 to 500 nm or electron rays.

[0456] Next, the film is exposed 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, and then subjected to heat treatment (post-exposure bake (PEB)).

[0457] Thereafter, development is performed. In the negative photosensitive resin composition of the present invention, alkali development can be performed using a developer of an alkali aqueous solution.

[0458] On the other hand, a suitable alkaline aqueous solution developer that can be used for alkali development is a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution. Development can be performed by a common method such as a spray method, a paddle method, or by immersing in a developer. Thereafter, washing, rinsing, drying, etc. are performed as needed to obtain a photosensitive material coating having a desired pattern.

[0459] (Method for forming a cured film)

[0460] The present invention also provides a method for forming a cured film, comprising the step of heating the photosensitive material film having a pattern formed thereon obtained by the above-mentioned pattern forming method at a temperature of 100 to 300° C. for post-curing.

[0461] That is, the photosensitive material coating formed with the pattern obtained by the above-mentioned pattern forming method is heated and post-cured at 100 to 300° C., preferably 150 to 300° C., and more preferably 180 to 250° C. using an oven or a hot plate, thereby forming a cured coating. If the post-curing temperature is 100 to 300° C., the cross-linking density of the coating of the photosensitive resin composition can be increased, and the remaining volatile components can be removed, which is preferred from the viewpoint of adhesion to the substrate, heat resistance, strength, and further electrical properties. In addition, the post-curing time can be set to 10 minutes to 10 hours.

[0462] The patterns formed as described above are used for the purpose of forming a protective coating for covering wiring, circuits, substrates, etc. These formed patterns and protective coatings have excellent insulation properties and exhibit excellent adhesion to metal layers such as Cu of the wiring and circuits they cover, metal electrodes present on the substrate, or insulating substrates such as SiN present on the wiring or circuits they cover. They also have mechanical strength suitable for use as a protective coating, and can significantly improve the resolution performance for enabling fine pattern formation.

[0463] (Curing film)

[0464] The cured film obtained by such operation has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength and chemical resistance to alkaline stripping solutions, etc. The reliability of the semiconductor element obtained by using it as a protective film is also excellent. In particular, it can prevent the occurrence of cracks during temperature cycle tests and is suitable for use as a protective film (interlayer insulating film or surface protective film) for electrical / electronic components, semiconductor elements, etc.

[0465] That is, the present invention provides an interlayer insulating film or a surface protective film including a cured film formed by curing the negative photosensitive resin composition.

[0466] The protective film is effective in applications such as insulating films for semiconductor elements including redistribution applications, insulating films for multilayer printed circuit boards, solder masks, and cover films due to its heat resistance, chemical resistance, and insulating properties.

[0467] (Electronic Components)

[0468] Furthermore, the present invention provides an electronic component having the above interlayer insulating film or the above surface protective film. Such an electronic component has a protective film (interlayer insulating film or surface protective film) having heat resistance, chemical resistance, and insulation properties, and therefore has excellent reliability.

[0469] Example

[0470] The present invention is 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 conversion value based on gel permeation chromatography (GPC).

[0471] I. Synthesis of polymer (resin)

[0472] The chemical structural formulas and names of the compounds used in the following synthesis examples are shown below.

[0473]

[0474] DA-1: 4-aminophenyl-4-amino-2-methylbenzoate

[0475] DA-2: (2-phenyl-4-aminophenyl)-4-aminobenzoate

[0476] 6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0477] BPS: Bis(3-amino-4-hydroxyphenyl)sulfone

[0478] BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane

[0479] BAHF: 9,9-bis(3-amino-4-hydroxyphenyl)fluorene

[0480] ODA: 4,4'-diaminodiphenyl ether

[0481] APB: 1,3-bis(3-aminophenoxy)benzene

[0482] s-ODPA: 3,3',4,4'-oxydiphthalic anhydride

[0483] s-BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

[0484] DC-1: Sebacoyl chloride

[0485] PAP: 4-aminophenol

[0486] X-1: The tetracarboxylic acid diester compound synthesized in the following Synthesis Example 14

[0487] In addition to the above, D-400 and RT-1000 (both diamines manufactured by HUNTSMAN) were used.

[0488] [Synthesis Example 1] Synthesis of polyimide resin (A-1)

[0489] DA-1 2.5g (9.6mmol), 6FAP 30.0g (81.9mmol), PAP 1.0g (9.6mmol), and N-methyl-2-pyrrolidone 134g were added to a 1L flask equipped with a stirrer and a thermometer, and stirred and dissolved at room temperature. Next, a solution obtained by dissolving 29.9g of s-ODPA (96.4mmol) in N-methyl-2-pyrrolidone 269g was added dropwise at room temperature, and after the addition was completed, the mixture was stirred at room temperature for 1 hour. Thereafter, 20g of xylene was added to the reaction solution, and the water generated at 170°C was discharged to the outside of the system while being heated and refluxed for 3 hours. After cooling to room temperature, the reaction solution was added dropwise under stirring with 2L of ultrapure water, and the precipitate was filtered and appropriately washed with water, and then dried under reduced pressure at 40°C for 48 hours to obtain a polyimide resin (A-1). When the molecular weight of this polymer was measured by GPC, the weight average molecular weight was 34,000 in terms of polystyrene.

[0490] [Synthesis Example 7] Synthesis of polyamide-imide resin (A-7)

[0491] DA-1 2.5g (9.6mmol), 6FAP 30.0g (81.9mmol), PAP 1.0g (9.6mmol), and N-methyl-2-pyrrolidone 134g were added to a 1L flask equipped with a stirrer and a thermometer, and stirred and dissolved at room temperature. Next, a solution obtained by dissolving 23.9g of s-ODPA (77.1mmol) in N-methyl-2-pyrrolidone 215g was added dropwise at room temperature, and after the addition was completed, the mixture was stirred at room temperature for 1 hour. Thereafter, xylene 20g was added to the reaction solution, and the mixture was heated and refluxed for 3 hours while the water generated at 170°C was discharged to the outside of the system. After cooling to room temperature, pyridine 3.1g (38.6mmol) was added, and 4.6g of DC-1 (19.3mmol) was added dropwise while maintaining the temperature below 20°C. After the addition was completed, the reaction solution was added dropwise with stirring to 2 L of ultrapure water, and the precipitate was filtered and washed with water as appropriate, and then dried under reduced pressure at 40° C. for 48 hours to obtain a polyamideimide resin (A-7). The molecular weight of the polymer was measured by GPC, and the weight average molecular weight was 33,000 in terms of polystyrene.

[0492] [Synthesis Example 13] Synthesis of polyamide resin (A-13)

[0493] DA-2 2.9 g (9.6 mmol), 6FAP 30.0 g (81.9 mmol), PAP 1.0 g (9.6 mmol), and N-methyl-2-pyrrolidone 136 g were added to a 1 L flask equipped with a stirrer and a thermometer, and stirred and dissolved at room temperature. Next, pyridine 15.3 g (192.8 mmol) was added, and 23.1 g of DC-1 (96.4 mmol) was added dropwise while maintaining the temperature below 20°C. After the addition was completed, the reaction solution was added dropwise while stirring 2 L of ultrapure water, and the precipitate was filtered and appropriately washed with water, and then dried under reduced pressure at 40°C for 48 hours to obtain a polyamide resin (A-13). When the molecular weight of the polymer was measured by GPC, the weight average molecular weight was 38,000 in terms of polystyrene.

[0494] [Synthesis Example 14] Synthesis of Tetracarboxylic Acid Diester Compound (X-1)

[0495] In a 3L flask equipped with a stirrer and a thermometer, s-ODPA 100g (322mmol), triethylamine 65.2g (644mmol), N,N-dimethyl-4-aminopyridine 39.3g (322mmol), and γ-butyrolactone 400g were added. While stirring at room temperature, hydroxyethyl methacrylate (HEMA) 83.8g (644mmol) was added dropwise, and the mixture was stirred at room temperature for 24 hours. Thereafter, 370g of 10% aqueous hydrochloric acid solution 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 6 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).

[0496] [Synthesis Example 15] Synthesis of polyimide resin (A-15)

[0497] In a 1L flask equipped with a stirrer and a thermometer, 44.0 g (77.1 mmol) of X-1 and 176 g of N-methyl-2-pyrrolidone were added and dissolved by stirring at room temperature. Then, 18.8 g (158.1 mmol) of thionyl chloride was added dropwise under ice cooling so as to keep the temperature of the reaction solution at 10°C or lower. After the addition was completed, the mixture was stirred for 2 hours under ice cooling. Next, 4.6 g of DC-1 (19.3 mmol) was added, and a solution prepared by dissolving 2.9 g of DA-2 (9.6 mmol), 30.0 g of 6FAP (81.9 mmol), 1.0 g of PAP (9.6 mmol), and 15.3 g (192.8 mmol) of pyridine in 136 g of N-methyl-2-pyrrolidone was added dropwise under ice cooling so as to keep the temperature of the reaction solution at 10°C or lower. After the addition was completed, the temperature was restored to room temperature, and the reaction solution was added dropwise with stirring to 3 L of water. The precipitate was filtered and washed with water as appropriate, and then dried under reduced pressure at 40° C. for 48 hours to obtain a polyimide resin (A-15). The molecular weight of the polymer was measured by GPC, and the weight average molecular weight was 35,000 in terms of polystyrene.

[0498] [Synthesis Example 2] to [Synthesis Example 6], [Synthesis Example 8] to [Synthesis Example 12], [Comparative Synthesis Examples 1 and 2] Synthesis of polyimide resin or polyamide-imide resin (A-2) to (A-6), (A-8) to (A-12), (A-16), (A-17)

[0499] As diamine compounds, monoamine compounds, tetracarboxylic dianhydrides, and dicarboxylic acid dichlorides, the compounds of weights shown in the following Table 1 were used, and in the case of polyimide resins, the same proportions as in Synthesis Example 1 were used, and in the case of polyamide-imide resins, the same proportions as in Synthesis Example 7 were used to obtain resins (A-2) to (A-6), (A-8) to (A-12), (A-16), and (A-17). The molecular weights of various polymers were measured by GPC, and the weight average molecular weights calculated in terms of polystyrene are shown in the following Table 1.

[0500] [Table 1]

[0501]

[0502] II. Synthesis of cross-linkable polymer compound (E)

[0503] As a cross-linkable polymer compound (polymer additive), various monomers were combined, copolymerized in the presence of tetrahydrofuran solvent, crystallized in hexane, and dried to obtain polymer compounds (polymers E1 to E8) with the following compositions. The composition of the obtained polymer compound was confirmed by 1H-NMR, and the molecular weight was confirmed by gel permeation chromatography.

[0504] [Synthesis Example 16] Polymer E1

[0505] Molecular weight (Mw) = 11,600

[0506]

[0507] [Synthesis Example 17] Polymer E2 molecular weight (Mw) = 11,800

[0508]

[0509] [Synthesis Example 18] Polymer E3 molecular weight (Mw) = 11,300

[0510]

[0511] [Synthesis Example 19] Polymer E4 molecular weight (Mw) = 12,300

[0512]

[0513] [Synthesis Example 20] Polymer E5 molecular weight (Mw) = 11,400

[0514]

[0515] [Synthesis Example 21] Polymer E6 molecular weight (Mw) = 12,000

[0516]

[0517] [Synthesis Example 22] Polymer E7 molecular weight (Mw) = 11,500

[0518]

[0519] [Synthesis Example 23] Polymer E8 molecular weight (Mw) = 12,000

[0520]

[0521] III. Preparation of Photosensitive Resin Composition

[0522] The resins synthesized in the above-mentioned 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, and a resin composition having a resin conversion of 20% by mass was prepared according to the composition and compounding amount described in Table 2. Thereafter, after stirring, mixing, and dissolving, the mixture was precisely filtered using a 0.5 μm filter made of Teflon (registered trademark) to obtain a photosensitive resin composition. In Table 2, PGMEA of the solvent represents propylene glycol monomethyl ether acetate, and GBL represents γ-butyrolactone.

[0523] [Table 2]

[0524]

[0525] In Table 2, the details of the photoacid generator (PAG-1) as an oxime sulfonate compound, the crosslinking agent (CL-1), (CL-2), (CL-3), the basic compound (F-1), the thermal acid generator (G-1), (G-2), the antioxidant (H-1), the silane compound (I-1), the dissolution inhibitor (K-1), and the surfactant (J-1) are as follows. In addition, parts by weight have the same meaning as parts by mass.

[0526] Photoacid generator (PAG-1)

[0527]

[0528] Crosslinking agent (CL-1)

[0529]

[0530] Crosslinking agent (CL-2)

[0531]

[0532] Crosslinking agent (CL-3)

[0533] Epoxy resin: Made by ADEKA, EP4000L

[0534] Basic compound (F-1)

[0535]

[0536] Thermal acid generator (G-1)

[0537]

[0538] Thermal acid generator (G-2)

[0539]

[0540] Antioxidant (H-1)

[0541] Hindered phenol antioxidant: Sumitomo Chemical Co., Ltd., SUMILIZER GA-80 silane compound (I-1)

[0542] Aminosilane coupling agent: Shin-Etsu Chemical Co., Ltd., KBM-573 dissolution inhibitor (K-1)

[0543]

[0544] Surfactant (J-1)

[0545] Fluorine-based surfactant: OMNOVA, PF-6320

[0546] IV. Patterning

[0547] 5 mL of the photosensitive resin compositions 1 to 23 and comparative photosensitive resin compositions 1 to 3 were dispensed on a silicon substrate treated with hexamethylsilazane, and then the substrate was rotated, i.e., by spin coating, so that the film thickness after heating for post-curing performed after pattern formation was 2 μm. That is, the rotation speed during coating was adjusted so that the film thickness would decrease after the post-curing step and the final film thickness after post-curing would be 2 μm, based on the preliminarily studied study.

[0548] Next, pre-bake is performed on a hot plate at 100°C for 2 minutes. And then, i-ray exposure is performed using an i-ray stepper AP300E manufactured by VEECO. After exposure, post-exposure baking (PEB) is performed at 110°C for 2 minutes, followed by cooling. In pattern formation, a negative pattern mask is used. The mask has a pattern that can form a 2μm line and space pattern (hereinafter referred to as an LS pattern) arranged in a 1:1 ratio vertically and horizontally, and can form an LS pattern with a scale of 1μm up to 10μm to 2μm.

[0549] Thereafter, paddle development was performed for 1 minute using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution as a developer until the coating film in the unexposed portion was dissolved, and then rinsed with ultrapure water.

[0550] Next, the patterned substrate was post-cured using an oven while nitrogen purging was performed at 180° C. for 2 hours.

[0551] Next, in order to observe the shape of the obtained LS pattern, each substrate was cut out 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, these results are shown in Table 3 together with the sensitivity and the number of development times that can form a 2 μm pattern.

[0552] It should be noted that the shape of the LS pattern was evaluated according to the following criteria, and the evaluation results are shown in Table 3. The pattern cross section of the LS pattern that reached the minimum was observed, and the widths of the uppermost and lowermost parts of the pattern cross section were compared. The pattern whose difference was 0 μm or more and 0.2 μm or less was designated as A, the pattern whose width was greater than 0.2 μm and less than 0.5 μm was designated as B, the pattern whose width was greater than 0.5 μm and less than 1.0 μm was designated as C, and the pattern whose width was greater than 1.0 μm was designated as D.

[0553] V. Elongation at break and tensile strength

[0554] The 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, and then pre-baked on a hot plate at 100° C. for 4 minutes to obtain a photosensitive resin film.

[0555] Then, a contact lithography machine UL-7000 manufactured by Quintel was used to perform the lithography at a wide wavelength and 500 mJ / cm 2 The entire surface of the substrate was contact exposed with an exposure amount of. After exposure, PEB treatment was performed at 110°C for 4 minutes, followed by cooling. Thereafter, curing was performed using an oven while nitrogen purging at 190°C for 2 hours 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 immersed in 20% by mass hydrochloric acid, thereby peeling the cured film from the substrate. Using Autograph AGX-1KN manufactured by Shimadzu Corporation, the elongation at break and tensile strength of the obtained cured film were measured. The measurement was performed 10 times for each sample, and the average value is shown in Table 3.

[0556] [Table 3]

[0557]

[0558] VI. Adhesion

[0559] According to the same steps as the above-mentioned pattern formation, the above-mentioned photosensitive resin compositions 1 to 23 and comparative photosensitive resin compositions 1 and 2 are used to expose a 1 cm square pattern on the SiN substrate with i-rays in such a way that the final film thickness after curing becomes 5 μm, and a pattern is obtained in such a way that the entire surface becomes a grid on the substrate. It should be noted that the exposure amount is set to the exposure amount that can form the minimum pattern obtained in the above-mentioned LS pattern evaluation. In addition, the pre-bake is treated at 100°C for 4 minutes, and the PEB is treated at 110°C for 4 minutes. In addition, the development is set to 1 minute of paddle development until the coating film of the unexposed part is dissolved, and it is performed a specified number of times.

[0560] After that, nitrogen was purged at 190°C for 2 hours to post-cure the substrate with the pattern. Next, the cured substrate was singulated along the 1 cm square pattern to obtain a chip with a cured film. Aluminum pins with epoxy resin were placed on the obtained chip and heated at 150°C for 1 hour to adhere the aluminum pins to the chip to prepare a measurement sample. After cooling, the ROMULUS manufactured by Quad Group was used to Figure 1The adhesion force was measured by the method shown in the figure (hereinafter referred to as the Stud-pull method). The measurement was carried out at a measurement speed of 20 N / sec. Figure 1 : is an explanatory diagram showing a method for measuring the close contact force. Figure 1 1 represents SiN substrate (substrate), 2 represents cured film, 3 represents aluminum pin with adhesive, 4 represents support table, 5 represents fixture, and 6 represents stretching direction. The obtained value is the average value of 10 points. The higher the value, the higher the adhesion of the cured film relative to the SiN substrate. In addition, when the peeling interface is cured film / adhesive, the adhesion is greater than when the peeling interface is substrate / cured film. The adhesion is evaluated by comparing the obtained value and the peeling interface.

[0561] Furthermore, as a high temperature and high humidity test (PCT test), the obtained chip was placed in a saturated pressure cooker at 2 atmospheres, 120°C, and 100% RH for 168 hours. Thereafter, the adhesion after the test was evaluated using the Stud-pull method, and the adhesion to the substrate is shown in Table 4 together with the results before the test.

[0562] [Table 4]

[0563]

[0564] As shown in Tables 3 and 4, Examples 1 to 23 obtained using the negative photosensitive composition of the present invention can provide cured films having good mechanical properties and high temperature and high humidity resistance even when cured at a low temperature of 200° C. or lower.

[0565] In contrast, Comparative Examples 1 to 3 in which the polymers containing no structural unit represented by the general formula (1) and / or (2) were used in the compositions showed poor elongation at break when cured at a low temperature of 200° C. or lower.

[0566] Based on the above results, the following results can be obtained: the compositions of Examples 1 to 23 have good rectangularity, show excellent resolution for distinguishing fine patterns of 2 μm, show sufficient properties as photosensitive materials, and their cured films have substrate adhesion and good high temperature and high humidity resistance, and are useful as protective films for circuits and electronic components.

[0567] This specification includes the following aspects.

[0568] [1]: A negative photosensitive resin composition, characterized by comprising (A) a polymer, (B) a photoacid generator, (C) a crosslinking agent, and (D) a solvent.

[0569] The polymer (A) includes structural units represented by the following general formula (1) and / or (2), and includes structural units represented by the following general formula (3) and / or (4).

[0570]

[0571] (In the formula, X1 is a tetravalent organic group; R1 to R4 are optionally the same or different, and are monovalent organic groups with 1 to 15 carbon atoms or hydrogen atoms, and at least one of them is a monovalent organic group with 1 to 15 carbon atoms and optionally containing heteroatoms; Es is a -OC(=O)- bond or a -C(=O)-O- bond.)

[0572]

[0573] (In the formula, X2 is a divalent organic group; R1 to R4 and Es are the same as above.)

[0574]

[0575] (In the formula, X3 is a tetravalent organic group which is the same as or different from the aforementioned X1; s is 0 or 1; Z is a divalent bonding group; when s=0, the two aromatic rings in the formula are directly bonded without the aid of a bonding group.)

[0576]

[0577] (In the formula, X4 is a divalent organic group that is the same as or different from the aforementioned X2; s and Z are the same as above.)

[0578] [2]: The negative photosensitive resin composition according to the above [1] is characterized in that any one of the above R1 and R2 in the above 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 the above R3 and R4 are hydrogen atoms.

[0579] [3]: The negative photosensitive resin composition according to [2] above, wherein 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.

[0580] [4]: A negative photosensitive resin composition according to any one of [1] to [3], characterized in that the Z in the general formulae (3) and (4) is at least one bonding group selected from any of the groups represented by the following formulae (5), (6), (7) and (8).

[0581]

[0582] (In the formula, the dotted line represents the connecting bond.)

[0583] [5]: A negative photosensitive resin composition according to any one of [1] to [4], characterized in that the component (C) is one or more crosslinking agents selected from amino condensates modified with formaldehyde or formaldehyde-alcohol, phenol compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups in one molecule, compounds obtained by replacing hydrogen atoms of hydroxyl groups of polyphenols with glycidyl groups, compounds obtained by replacing hydrogen atoms of hydroxyl groups of polyphenols or polyols 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).

[0584]

[0585] (In the formula, the dotted line represents a connecting bond; Rc is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; v is 1 or 2.)

[0586] [6]: The negative photosensitive resin composition according to any one of [1] to [5], wherein the negative photosensitive resin composition further comprises (E) a crosslinkable polymer compound.

[0587] The (E) crosslinkable polymer compound includes a structural unit represented by the following general formula (9) and has a group that crosslinks with the component (A).

[0588]

[0589] (In the formula, R5 is a hydrogen atom or a methyl group; R6 is a (n+1)-valent straight-chain, 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 naphthylmethyl group, wherein the carbon atoms of the aforementioned aliphatic saturated hydrocarbon group may be substituted by oxygen atoms. n is an integer from 1 to 5. Y1 is -C(=O)-O-, -C(=O)-NH- or -C(=O)-N(R7OH)-. R7 is a divalent straight-chain, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein the carbon atoms of the aforementioned aliphatic saturated hydrocarbon group may be substituted by oxygen atoms. p1 is 0 or 1.)

[0590] [7]: The negative photosensitive resin composition according to the above-mentioned [6] is characterized in that the aforementioned (E) component is a cross-linked polymer compound, and the cross-linked polymer compound contains a structural unit represented by the following general formula (10) and contains a structural unit represented by the following general formula (11) having a group that can be cross-linked with the aforementioned (A) component.

[0591]

[0592] (In the formula, R8 is a hydrogen atom or a methyl group; Y2 is -C(=O)-O-, -C(=O)-NH- or -C(=O)-N(R9OH)-. R9 is a divalent straight-chain, 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 the carbon atoms of the aliphatic saturated hydrocarbon group may be optionally replaced by oxygen atoms. p2 is 0 or 1.)

[0593]

[0594] (Where 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 oxetane group or an epoxy group, and Y3 is -C(=O)-O-, a phenylene group or a naphthylene group. p3 is 0 or 1.)

[0595] [8]: The negative photosensitive resin composition according to [7] above, wherein the component (E) is a crosslinkable polymer compound comprising structural units represented by the following general formula (10) and the following general formula (12).

[0596]

[0597] (wherein, R8, Y2, p2 are the same as above; R 12 is a hydrogen atom or a methyl group; Y4 is -C(=O)-O-, a phenylene group or a naphthylene group. 13 is a hydroxyl group, an ester group, an ether group, or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may contain an aromatic hydrocarbon; R 14 is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, optionally with R 13 Bond 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, optionally with R 13 bonded to form a ring. m is 0 or 1. p4 is 0 or 1. <a1<1.0、0<a2<1.0、0<a1+a2≤1.0。)

[0598] [9]: The negative photosensitive resin composition according to any one of [6] to [8], wherein the component (E) is a crosslinkable polymer compound further comprising a structural unit represented by the following general formula (13).

[0599]

[0600] (Where R 17 is a hydrogen atom or a methyl group; R18 is a single bond, or a (1+1)-valent straight-chain, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms, wherein the carbon atoms of the aliphatic saturated hydrocarbon group may be substituted by oxygen atoms. 19 -, -C(=O)-NH-, -C(=O)-N(R 19 OH)-, phenylene or naphthylene. 19 A divalent straight-chain, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein the carbon atoms of the aliphatic saturated hydrocarbon group may be substituted by oxygen atoms. l is 0 or 1.)

[0601]

[10] : The negative photosensitive resin composition according to any one of [6] to [9], wherein the component (E) is a crosslinkable polymer compound further comprising a structural unit represented by the following general formula (13).

[0602]

[0603] (Where R 20 , R 21 , R 22 , R 23 , R 24 and R 25 Each is independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

[0604]

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

[10] , 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.

[0605]

[12] : A pattern forming method, characterized in that it comprises the following steps:

[0606] (1) a step of coating the negative photosensitive resin composition according to any one of [1] to

[11] on a substrate to form a photosensitive material coating;

[0607] (2) After the heat treatment, the photosensitive material coating is exposed to light through a photomask using high energy rays or electron beams with a wavelength of 190 to 500 nm;

[0608] (3) After the exposure, the substrate subjected to the heat treatment is developed using a developer of an alkaline aqueous solution.

[0609]

[13] : A method for forming a cured film, characterized in that it comprises the following steps:

[0610] The photosensitive material coating film having a pattern formed thereon obtained by the pattern forming method of the above-mentioned

[12] is heated at a temperature of 100 to 300° C. and post-cured.

[0611]

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

[11] .

[0612]

[15] : A surface protection film, characterized in that it comprises a cured film, wherein the cured film is formed by curing the negative photosensitive resin composition according to any one of [1] to

[11] above.

[0613]

[16] : An electronic component characterized by having the interlayer insulating film of

[14] or the surface protective film of

[15] .

[0614] It should be noted that the present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are for illustration only, and any technical solution having substantially the same structure and exerting the same effect as the technical idea described in the claims of the present invention falls within the protection scope of the present invention.

Claims

1. A negative photosensitive resin composition, characterized in that: comprising (A) a polymer, (B) a photoacid generator, (C) a crosslinking agent, and (D) a solvent, The polymer (A) comprises 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), In formula (1), X1 is a tetravalent organic group; R1 to R4 are optionally the same or different, and are monovalent organic groups with 1 to 15 carbon atoms and optionally containing heteroatoms or hydrogen atoms, and at least one of them is a monovalent organic group with 1 to 15 carbon atoms and optionally containing heteroatoms; Es is a -OC(=O)- bond or a -C(=O)-O- bond, In formula (2), X2 is a divalent organic group; R1 to R4 and Es are the same as above, In formula (3), X3 is a tetravalent organic group that is the same as or different from X1; s is 0 or 1; Z is a divalent bonding group; when s=0, the two aromatic rings in the formula are directly bonded without the aid of a bonding group, In formula (4), X4 is a divalent organic group which is the same as or different from X2; s and Z are the same as described above.

2. The negative photosensitive resin composition according to claim 1, characterized in that In the general formulae (1) and (2), either R1 or R2 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.

3. The negative photosensitive resin composition according to claim 2, characterized in that: In the general formulae (1) and (2), either R1 or R2 is an aromatic group having 1 to 10 carbon atoms, and the other is a hydrogen atom.

4. The negative photosensitive resin composition according to claim 1, characterized in that: The Z in the general formulae (3) and (4) is at least one bonding group selected from any of the groups represented by the following formulae (5), (6), (7) and (8), In the formula, the dotted line represents the connecting bond.

5. The negative photosensitive resin composition according to claim 1, characterized in that: The component (C) is one or more crosslinking agents selected from amino condensates modified with formaldehyde or formaldehyde-alcohol, phenol compounds having an average of two or more methylol groups or alkoxymethylol groups in one molecule, compounds obtained by replacing hydrogen atoms of hydroxyl groups of polyphenols with glycidyl groups, compounds obtained by replacing hydrogen atoms of hydroxyl groups of polyphenols or polyols 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), In the formula, the dotted line represents a connecting 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 according to claim 1, characterized in that: The negative photosensitive resin composition further comprises (E) a cross-linkable polymer compound, The crosslinkable polymer compound (E) comprises a structural unit represented by the following general formula (9) and has a group that crosslinks with the component (A). In formula (9), R5 is a hydrogen atom or a methyl group; R6 is a (n+1)-valent straight-chain, 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 naphthylmethyl group, wherein the carbon atoms of the aliphatic saturated hydrocarbon group are optionally replaced by oxygen atoms; n is an integer from 1 to 5; Y1 is -C(=O)-O-, -C(=O)-NH- or -C(=O)-N(R7OH)-; R7 is a divalent straight-chain, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein the carbon atoms of the aliphatic saturated hydrocarbon group are optionally replaced by oxygen atoms; p1 is 0 or 1.

7. The negative photosensitive resin composition according to claim 6, characterized in that: The component (E) is a cross-linkable polymer compound, which includes 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 can be cross-linked with the component (A). In formula (10), R8 is a hydrogen atom or a methyl group; Y2 is -C(=O)-O-, -C(=O)-NH- or -C(=O)-N(R9OH)-; R9 is a divalent straight-chain, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein the carbon atoms of the aliphatic saturated hydrocarbon group may be optionally replaced by oxygen atoms; p2 is 0 or 1, In formula (11), 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; Y3 is -C(=O)-O-, a phenylene group or a naphthylene group; p3 is 0 or 1.

8. The negative photosensitive resin composition according to claim 7, characterized in that: The component (E) is a cross-linkable polymer compound comprising structural units represented by the following general formula (10) and the following general formula (12), Wherein, R8, Y2, p2 are the same as above; R 12 is a hydrogen atom or a methyl group; Y4 is -C(=O)-O-, a phenylene group or a naphthylene group; R 13 is a hydroxyl group, an ester group, an ether group, or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may contain an aromatic hydrocarbon; R 14 is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, optionally with R 13 Bond to form a ring; R 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, optionally with R 13 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。 9. The negative photosensitive resin composition according to claim 6, characterized in that: The component (E) is a cross-linkable polymer compound further comprising a structural unit represented by the following general formula (13), In formula (13), R 17 is a hydrogen atom or a methyl group; R 18 is a single bond, or a (1+1)-valent straight-chain, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms, wherein the carbon atoms of the aliphatic saturated hydrocarbon group are optionally replaced by oxygen atoms; Y5 is -C(=O)-O-, -C(=O)-OR 19 -, -C(=O)-NH-, -C(=O)-N(R 19 OH)-, phenylene or naphthylene; R 19 It 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, wherein the carbon atoms of the aliphatic saturated hydrocarbon group are optionally replaced by oxygen atoms; l is 0 or 1.

10. The negative photosensitive resin composition according to claim 6, characterized in that: The component (E) is a cross-linkable polymer compound further comprising at least one structural unit selected from the group consisting of structural units obtained 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), In the formula, R 20 , R 21 , R 22 , R 23 , R 24 and R 25 Each is 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 claim 1, characterized in that: The composition further contains at least one compound 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, characterized in that: Including the following processes: (1) a step of coating a negative photosensitive resin composition according to any one of claims 1 to 11 on a substrate to form a photosensitive material coating; (2) Next, after the heat treatment, the photosensitive material coating is exposed to light via a photomask using high energy rays or electron beams having a wavelength of 190 to 500 nm; (3) After the exposure, the substrate subjected to the heat treatment is developed using a developer of an alkaline aqueous solution.

13. A method for forming a cured film, characterized in that: Including the following processes: A step of heating and post-curing the patterned photosensitive material coating obtained by the pattern forming method according to claim 12 at a temperature of 100 to 300°C.

14. An interlayer insulating film, characterized in that: The negative photosensitive resin composition comprises a cured film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 11.

15. A surface protection film, characterized in that: The negative photosensitive resin composition comprises a cured film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 11.

16. An electronic component, characterized in that: A method of providing an interlayer insulating film according to claim 14.

17. An electronic component, characterized in that: A surface protection film according to claim 15.

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