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

Abstract

To provide a negative photosensitive resin composition that gives high resolution, has excellent characteristics such as mechanical strength and adhesion, and also excels in storage stability.SOLUTION: A negative photosensitive resin composition comprises: (A) one or more selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamide imide structure, and precursor structures thereof, (B) a photoacid generator, (C) one or more crosslinking agents selected from an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having, on average, two or more methylol groups or alkoxymethylol groups in one molecule, a compound in which a hydrogen atom of a hydroxyl group of polyvalent phenol is substituted with a glycidyl group or a group having the glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of the polyvalent phenol is substituted with a substituent represented by a glycidyl group derivative, and a compound containing two or more nitrogen atoms having a glycidyl group derivative, (D) an onium salt, and (E) a solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a negative photosensitive resin composition using an alkali-soluble resin containing at least one structure selected from the group consisting of a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof.

[0002] The present invention also provides a pattern forming method and a cured film forming method using this composition, and relates to an electronic component having a cured film. [Background technology]

[0003] As various electronic devices such as personal computers, digital cameras, and mobile phones become smaller and more powerful, there is a rapidly increasing demand for smaller, thinner, and higher-density semiconductor elements. Therefore, there is a need for the development of photosensitive insulating materials that can accommodate the increase in substrate area required for improved productivity and that can be fabricated with fine, high-aspect ratio patterns on substrates for high-density packaging technologies such as chip-size packages (CSPs) and three-dimensional stacking.

[0004] In high-density packaging technologies such as three-dimensional stacking, photosensitive insulating materials that can be patterned on substrates have long been used as protective coatings or insulating layers, and their insulating properties, mechanical strength, and adhesion to substrates have continued to attract attention, and development is still active today.

[0005] Conventionally, photosensitive polyimide-based materials have been proposed that utilize polyamic acid, a precursor of polyimide, such as those in which a photosensitive group is introduced into the carboxyl group of polyamic acid via an ester bond (Patent Documents 1 and 2). However, these proposals require an imidization treatment at a high temperature exceeding 300°C after forming a patterned film to obtain the desired polyimide film, which poses problems such as limitations on the base substrate that can withstand such high temperatures and oxidation of copper in the wiring.

[0006] To improve this, photosensitive polyimides using solvent-soluble resins that have already been imidized have been proposed to lower the post-curing temperature (Patent Documents 3 and 4). The negative-tone photosensitive resin composition using polyimide described in Patent Document 3 is developed using N-methyl-2-pyrrolidone (NMP) during pattern formation. However, N-methyl-2-pyrrolidone raises concerns about its environmental impact and health hazards, particularly aspiration hazards. In particular, N-methyl-2-pyrrolidone is included in the list of SVHCs (substances of concern for authorization) under the European REACH (Registration, Evaluation, Authorization, and Restriction of Chemicals) regulation. For these reasons, the use of N-methyl-2-pyrrolidone is a solvent that should be avoided whenever possible. Furthermore, Patent Document 3 does not provide any specific description of resolution performance during pattern formation.

[0007] Patent Document 4 describes a pattern formation method for a photosensitive resin composition using a material that utilizes polyamic acid, a polyimide precursor, such as a resin in which an ester bond is introduced into the carboxyl group of polyamic acid. Furthermore, after forming a film, heating to obtain the desired polyimide film can be performed at a relatively low temperature of 250°C. However, the solvent for this photosensitive resin composition is N-methyl-2-pyrrolidone, and the development process uses an organic solvent of N-methyl-2-pyrrolidone. As mentioned above, it is desirable to avoid using an organic solvent of N-methyl-2-pyrrolidone as a developer whenever possible. Furthermore, this patent document does not disclose specific resolution.

[0008] Patent Document 5 also describes patterning of a negative-tone photosensitive resin composition using a polyimide precursor. While the solvent for this photosensitive resin composition is N-methyl-2-pyrrolidone, cyclopentanone is used for developing the photosensitive resin composition. The resolution performance is specifically disclosed, stating that an aspect ratio of 1 or greater can be achieved. However, this aspect ratio does not represent the ratio of the finished film thickness or pattern height to the pattern dimensions, but rather the ratio of the film thickness to the dimensions after coating and drying. This resolution performance is not a practical value and requires improvement. While it is preferable to use a general-purpose organic solvent such as cyclopentanone as a developer, the use of organic solvents can sometimes result in the disadvantage of the film swelling during development, resulting in an overhanging pattern profile immediately after development.

[0009] On the other hand, the photosensitive resin composition proposed in Patent Document 6 uses a pre-imidized base resin designed for low-temperature curing. The solvent for the composition is cyclopentanone, and the development process also uses an alkaline aqueous solution, avoiding the use of N-methyl-2-pyrrolidone. However, the resolution performance still needs to be improved. Specifically, pattern formation using the photosensitive resin composition described in Patent Document 6 is performed using an extremely thin film, and the resolved pattern size is large. This lack of resolution performance is due to the poor solubility of the polyimide resin, the base resin disclosed in Patent Document 6, in the alkaline aqueous solution used as the developer. Increasing solubility in the developer is key to improving resolution performance in pattern formation.

[0010] In fact, in order to meet the resolution requirements of photosensitive insulating materials in high-density packaging technologies such as three-dimensional stacking, which have become increasingly common in recent years, the aspect ratio of the formed pattern (finished film thickness (or pattern height) / pattern dimensions) must be between 1 and 2. In other words, if the desired finished film thickness or pattern height is 10 μm, a pattern with dimensions of 10 μm or less, or close to 5 μm, must be formed.

[0011] Patent Documents 7 and 8 are examples of negative-tone photosensitive resin compositions with the high resolution required for high-density packaging technology. Patent Documents 7 and 8 disclose chemically amplified photosensitive resin compositions that undergo a crosslinking reaction catalyzed by an acid generated from a photoacid generator, resulting in a negative pattern when the composition becomes insoluble in an alkaline aqueous developer. Chemically amplified negative-tone photosensitive resin compositions can achieve high resolution, and have the advantage of being able to further increase resolution by adding a basic compound. However, the base resin used in the photosensitive resin composition of Patent Document 7 is a novolac resin, and the base resin used in the photosensitive resin composition of Patent Document 8 is a polymeric compound containing a silicone skeleton. These compositions do not represent polyimide-based base resins that possess the insulating properties, mechanical strength, adhesion to substrates, and other properties considered important in high-density packaging technology such as three-dimensional stacking.

[0012] In contrast to the above, when a polyimide-based polymer compound is used as the base resin of a chemically amplified negative-tone photosensitive resin composition, the photosensitive resin composition may sometimes exhibit a problem of poor storage stability, in that the thickness of the formed film increases over time after being applied to a substrate.

[0013] As described above, as chips become increasingly dense and highly integrated in the future, it is expected that patterns in rewiring techniques for insulating protective films will become increasingly finer. Therefore, there is a strong demand for photosensitive resin compositions that use polyimide or polymers having polyimide precursor structural units, and that can realize high resolution without impairing the excellent characteristics, such as mechanical strength and adhesion, of the polyimide patterns and protective films obtained by heating.

[0014] It is also highly desirable that the photosensitive resin composition be a stable composition that does not change during storage.

[0015] That is, there is a need for the rapid development of a photosensitive resin composition that has all of these characteristics without lacking any of them. [Prior art documents] [Patent documents]

[0016] [Patent Document 1] Japanese Unexamined Patent Publication No. 115541 / 1983 [Patent Document 2] Japanese Patent Application Publication No. 55-45746 [Patent Document 3] Patent No. 3232022 [Patent Document 4] Japanese Patent Application Laid-Open No. 2005-49504 [Patent Document 5] International Publication No. 2013 / 168675 [Patent Document 6] Patent No. 5417623 [Patent Document 7] Patent No. 5981465 [Patent Document 8] Patent No. 6352853 Summary of the Invention [Problem to be solved by the invention]

[0017] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an alkali-developable chemically amplified negative-tone photosensitive resin composition that is capable of forming a fine pattern and imparting high resolution, and that has excellent characteristics such as mechanical strength and adhesion, and that has excellent storage stability.

[0018] Furthermore, the polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor-containing polymer that can be used in the composition of the present invention are intended to provide a chemically amplified negative-tone photosensitive resin composition that is readily soluble in a general-purpose and safe organic solvent.

[0019] A further object of the present invention is to provide a negative-type photosensitive resin composition that can be cured at a low temperature of 200°C or less and that can provide a cured film having a high glass transition temperature (Tg.) that is excellent in mechanical strength and heat resistance after pattern formation. [Means for solving the problem]

[0020] In order to solve the above problems, the present invention provides: A negative photosensitive resin composition, (A) an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof; (B) a photoacid generator; (C) one or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having two or more methylol groups or alkoxymethylol groups on average per molecule, a compound in which the hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which the hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), a compound having a substituent (C-1) represented by the following formula (C-15), and a compound having two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2), [ka] (In the formula, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, s represents 1 or 2, and u is a number satisfying 1≦u≦3.) (D) an onium salt represented by the following general formula (1), [ka] (In the formula, A represents iodine, sulfur, phosphorus, or nitrogen; Q may be the same or different, and each may be linked or substituted, and each may represent a monovalent hydrocarbon group having 1 to 100 carbon atoms, optionally interrupted by a heteroatom; E - represents the anion of an organic or inorganic acid salt, and m represents 2 when A is iodine, 3 when A is sulfur, and 4 when A is phosphorus or nitrogen. (E) a solvent; The present invention provides a negative photosensitive resin composition comprising:

[0021] In the present invention, the photoacid generator (B) generates an acid upon exposure in a film coated with the photosensitive resin composition. The generated acid acts as a catalyst to promote a crosslinking reaction between the crosslinker (C) and the alkali-soluble resin (A), rendering component (A) insoluble in an alkaline developer, thereby providing a chemically amplified photosensitive resin composition that enables the formation of a negative pattern.

[0022] In this case, the negative-type photosensitive resin composition containing component (D) in the composition exhibits excellent resolution performance and has excellent characteristics such as mechanical strength and adhesion, and can provide an alkali-developable negative-type photosensitive resin composition with excellent storage stability.

[0023] The component (D) is preferably a quaternary ammonium salt represented by the following general formula (1-1), in which A in the general formula (1) is nitrogen. [ka] (In the formula, Q1, Q2, Q3, and Q4 may be the same or different, may be linked to each other, may be substituted, and may be a monovalent hydrocarbon group having 1 to 100 carbon atoms, optionally interrupted by a heteroatom; E - represents the anion of the same organic acid salt or inorganic acid salt as above.

[0024] Such a negative photosensitive resin composition exhibits excellent resolution, and a suitable negative photosensitive resin composition can be obtained.

[0025] In addition, E in the general formula (1) in the component (D) - is preferably an anion of an organic carboxylic acid represented by the following general formula (6). [ka] (In the formula, R E represents a hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom.

[0026] Such a negative photosensitive resin composition can provide a more suitable negative photosensitive resin composition.

[0027] Furthermore, the component (A) is preferably an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, which is a reaction product of a diamine containing at least one diamine represented by the following general formula (2) or the following general formula (3) with at least one tetracarboxylic dianhydride represented by the following general formula (4) or a dicarboxylic acid or dicarboxylic acid halide represented by the following general formula (5). [ka] [ka] [ka] [ka] (In the formula, L1 represents a tetravalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. L2 represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. T represents a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, -OCOR T , -OSO2R T , -OSO3R T However, R T is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom.

[0028] The acid generated from the photoacid generator in the component (B) is preferably an organic sulfonic acid represented by the following general formula (7). [ka] (In the formula, RU represents a hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom.

[0029] Such a negative photosensitive resin composition can increase dissolution contrast and provide a negative photosensitive resin composition with high resolution.

[0030] Furthermore, the component (A) is preferably an alkali-soluble resin containing at least one structure selected from the group consisting of a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, which are reaction products of one or more of tetracarboxylic dianhydrides represented by the following general formula (8), or dicarboxylic acids or dicarboxylic acid halides represented by the following general formula (9): [ka] [ka] (wherein Z is an alicyclic structure having 3 to 20 carbon atoms, an alicyclic structure in which aromatic rings are linked, or an alicyclic structure containing or interposed with a heteroatom) structure or an alicyclic structure formed by linking aromatic rings. T is a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, -OCO2R T , -OSO2R T , -OSO3R T wherein j represents 0 or 1, and when j is 0, the phthalic anhydride structure in the general formula (8) and the cyclic structure Z, and the benzoic acid structure in the general formula (9) and the cyclic structure Z are directly bonded, and when j is 1, X1 and X2 represent a divalent linking group.

[0031] Such alkali-soluble resins can be easily dissolved in general-purpose, safe organic solvents, and are therefore useful for constructing negative-type photosensitive resin compositions.

[0032] In the present invention, the polymers characterized by having polyamide, polyamideimide, polyimide structure, polybenzoxazole structure, or precursor structural units thereof obtained by reacting one or more of the tetracarboxylic dianhydrides represented by the general formula (8) or the dicarboxylic acids or dicarboxylic acid halides represented by the general formula (9) have amide structural units or imide structural units formed in advance during polymer synthesis. Therefore, when a photosensitive resin composition using the polymer is heat-cured after pattern formation, a reaction such as an imide ring-closing reaction is not required, and therefore high heating temperatures such as those required for an imidization reaction are not required. Furthermore, since amide structural units or imide structural units are formed, no elimination reaction occurs, which has the advantage of minimizing film shrinkage during heat treatment.

[0033] The alicyclic structure Z in the general formulas (8) and (9) is preferably a structure represented by the following general formula (10) or (11). [ka] (In the formula, the dotted line represents a bond, and k represents an integer of 0 or 1 or more. When k=0, Y2 represents a divalent group selected from any one of the following general formulae (13), (14), (15) and (16). When k=1, Y1 represents a divalent group selected from any one of the following general formulae (17), (18), and (19), and Y2 represents a divalent group selected from any one of the following general formulae (13), (14), (15), and (16). When k is 2 or more, Y1 represents the following general formula (17), and Y2 represents a divalent group selected from the following general formulas (13), (14), (15) and (16). R 1 , R 2 , R 3 , R 4 and R in the following formula (16) 5 , R 6 represents the same or different substituents, and may be a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 12 carbon atoms, Condition or a cyclic alkyl group or R1 , R 2 , R 3 , R 4 , R 5 , R 6 are bonded to form an alicyclic or aromatic ring.) [ka] (wherein the dotted line represents a bond, R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 represents the same or different substituents, and may be a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 12 carbon atoms, Condition Or it represents a cyclic alkyl group. m and p each represent an integer of 0 or 1 to 9; n represents 0 or 1; Y3 represents a divalent group selected from any one of the following general formulae (12), (13), (14), (15), (16), (17), (18), and (19). [ka] (wherein the dotted line represents a bond, R 5 , R 6 is the same as above. R 7 is a methyl group, an ethyl group, a linear or branched chain with 3 to 12 carbon atoms Condition or a cyclic alkyl group.

[0034] The use of such an alkali-soluble resin can be easily dissolved in a general-purpose, safe organic solvent, and is therefore useful for constructing a negative-type photosensitive resin composition, thereby enabling the production of a more suitable negative-type photosensitive resin composition.

[0035] Furthermore, the divalent linking groups X1 and X2 in the general formulae (8) and (9) preferably have a structure represented by any one of the following general formulae (20), (21), (22), (23), (24) and (25). [ka] (In the formula, the dotted line represents a bond.)

[0036] The use of such an alkali-soluble resin can be easily dissolved in a general-purpose, safe organic solvent, and is therefore useful for constructing a negative-type photosensitive resin composition, thereby enabling the production of a more suitable negative-type photosensitive resin composition.

[0037] The diamine represented by the general formula (2) is preferably a diamine represented by the following general formula (26). [ka]

[0038] In the case of such a negative photosensitive resin composition, an alkaline aqueous solution can be used as a developer in the development step during pattern formation.

[0039] Furthermore, the component (A) is preferably an alkali-soluble resin containing at least one structure selected from the group consisting of a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, which is a reaction product containing a tetracarboxylic acid diester compound represented by the following general formula (27): [ka] (Wherein W1 is a tetravalent organic group, R 16 is represented by the following general formula (28): [ka] (In the formula, the dotted line represents a bond, V1 represents an (r+1)-valent organic group, Rf represents a linear, branched or cyclic alkyl group or aromatic group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms, r represents 1, 2 or 3, and q represents 0 or 1.)

[0040] By using such an alkali-soluble resin, it is possible to obtain a preferable negative photosensitive resin composition which is more easily soluble in a general-purpose, safe organic solvent.

[0041] In addition, R in the general formula (27) 16 is preferably an organic group selected from the groups represented by the following general formulas (29), (30), (31) and (32). [ka] [ka] [ka] [ka] (In the formula, the dotted line represents a bond. Rf is the same as defined above. Ra and Rb represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. V2 and V3 represent a linear or branched alkylene group having 1 to 6 carbon atoms. n1 represents an integer of 0 to 6, n2 represents an integer of 1 to 6, n3 represents an integer of 0 to 6, n4 represents an integer of 1 to 6, n5 represents an integer of 0 to 6, and n6 represents 0 or 1.)

[0042] If such an alkali-soluble resin is used, a more suitable negative photosensitive resin composition can be obtained.

[0043] In addition, R in the general formula (27) 16 is preferably a group represented by the following general formula (28-1). [ka] (In the formula, the dotted line represents a bond. Rf is the same as above.)

[0044] If such an alkali-soluble resin is used, a more suitable negative photosensitive resin composition can be obtained.

[0045] Furthermore, the component (A) is preferably an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, in which the alicyclic structure Z of the general formula (8) is a reaction product with one or more of a tetracarboxylic dianhydride of the following general formula (33) or (34) and / or a dicarboxylic acid or a dicarboxylic acid halide selected from structures represented by the following formulas (35), (36), (37), (38), (39), and (40). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (wherein the dotted line represents a bond, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 represents the same or different substituents, and may be a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 12 carbon atoms, Condition or a cyclic alkyl group or R 1 , R 2 , R 3 , R 4 , R 5 , R 6R represents an alicyclic or aromatic ring. 7 is a methyl group, an ethyl group, a linear or branched chain with 3 to 12 carbon atoms Condition or a cyclic alkyl group. 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 represents the same or different substituents, and may be a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 12 carbon atoms, Condition or a cyclic alkyl group.

[0046] If such an alkali-soluble resin is used, a more suitable negative photosensitive resin composition can be obtained.

[0047] The present invention also provides (1) applying the negative photosensitive resin composition onto a substrate to form a photosensitive film; (2) a step of exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask after heat-treating the photosensitive film; (3) developing the exposed photosensitive film using an alkaline aqueous developer; The present invention provides a pattern formation method comprising the steps of:

[0048] Such a pattern formation method allows alkaline development using an alkaline aqueous solution.

[0049] Furthermore, the present invention provides the pattern forming method, further comprising: (4) A step of post-curing the developed photosensitive film by heating at a temperature of 100 to 300°C. It is preferred that the compound contains:

[0050] Such a pattern formation method can increase the crosslink density of the film of the photosensitive resin composition, remove remaining volatile components, and is preferable from the viewpoints of adhesion to the substrate, heat resistance, strength, and electrical properties.

[0051] The present invention also provides an interlayer insulating film comprising a cured product of the negative photosensitive resin composition.

[0052] Such an interlayer insulating film is excellent in adhesion to the substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance to alkaline stripping solutions and the like.

[0053] The present invention also provides a surface protection film comprising a cured product of the negative photosensitive resin composition.

[0054] Such a surface protective film is excellent in adhesion to the substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance to alkaline stripping solutions and the like.

[0055] The present invention also provides an electronic component having an interlayer insulating film made of the above negative photosensitive resin composition.

[0056] Such an electronic component can provide an electronic component with excellent reliability.

[0057] The present invention also provides an electronic part having a surface protective film made of the above negative photosensitive resin composition.

[0058] Such an electronic component can provide an electronic component with excellent reliability.

[0059] After forming a pattern from the photosensitive resin composition of the present invention, the cured film and cured pattern obtained by heat curing become very stable polyimide resin films, and therefore it is possible to form cured coatings that have extremely improved chemical resistance, particularly resistance to the very strong alkaline stripping solution used to strip plating resist patterns used in metal wiring processes. These patterned cured coatings can then be used as excellent protective coatings for electrical and electronic components and insulating protective coatings. [Effects of the Invention]

[0060] The present invention can provide an alkali-developable chemically amplified negative-tone photosensitive resin composition that is capable of forming fine patterns and imparting high resolution, and that has excellent characteristics such as mechanical strength and adhesion, and that has excellent storage stability.

[0061] Furthermore, the polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor-containing polymer that can be used in the composition of the present invention can provide a chemically amplified negative-tone photosensitive resin composition that is readily soluble in a general-purpose and safe organic solvent. DETAILED DESCRIPTION OF THE INVENTION

[0062] As described above, there has been a demand for a photosensitive resin composition that uses a polymer resin having at least one structure selected from the group consisting of a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, which has excellent characteristics such as mechanical strength and adhesion, and which exhibits high resolution and excellent storage stability.

[0063] In order to achieve the above object, the present inventors first analyzed the factors behind why, when a polyimide-based polymer compound is used in a chemically amplified negative-tone photosensitive resin composition that provides high resolution, the problem of poor storage stability occurs, such that the film thickness of the photosensitive resin composition formed when coated on a substrate increases over time. As a result of further intensive research, they found that by using an onium salt represented by the above general formula (1) in a chemically amplified negative-tone photosensitive resin composition, a composition with good storage stability can be obtained without impairing resolution performance.

[0064] That is, in chemically amplified photosensitive resin compositions, basic compounds added for the purpose of obtaining high resolution exhibit behavior that causes molecular condensation with polyimide polymer compounds during storage, and the molecular weight of the polymer compounds appears to increase. This causes a problem in that the film thickness formed when the composition is applied to a substrate increases over time. The present inventors have considered the causes of this problem and have thoroughly investigated solutions, leading to the completion of the present invention.

[0065] In a chemically amplified negative-tone photosensitive resin composition, a polymer compound resin, a photoacid generator, and a crosslinking agent capable of causing a crosslinking reaction with the polymer compound using, as a catalyst, an acid generated from the photoacid generator upon irradiation with light, cause the crosslinking reaction to proceed in the exposed areas, making the polymer compound insoluble in a developer, thereby forming a negative-tone photosensitive resin composition.

[0066] In this case, a small amount of a basic compound capable of reacting with the acid generated by the photoacid generator is often further added. By adding a small amount of the basic compound, the crosslinking reaction does not proceed at low exposure doses because the basic compound neutralizes the acid generated by the photoacid generator. However, at exposure doses where the amount of acid generated exceeds the amount neutralized by the addition of the basic compound, the amount of acid generated increases, and the crosslinking reaction proceeds, thereby promoting insolubilization in the developer. In other words, by adding a small amount of the basic compound, the solubility in the developer can be significantly changed with changes in exposure dose, making it possible to increase the so-called dissolution contrast. The addition of a small amount of the basic compound can increase the dissolution contrast in the developer, thereby achieving high resolution performance for the chemically amplified photosensitive resin composition.

[0067] However, when a basic compound is added to a photosensitive resin composition using a polymer compound that is a polymer having at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, the basic compound and the imide structure or amide structure exhibit very strong interactions, which is thought to cause intermolecular aggregation to progress in the composition solution. As a result, the polymer compound behaves in such a way that the apparent molecular weight of the polymer compound increases during storage of the solution, and when the photosensitive resin composition is applied to a substrate, the thickness of the formed film increases over time, resulting in a problem of poor storage stability.

[0068] Therefore, the present inventors have conducted extensive research in light of the above and have found that a photosensitive resin composition using a polymer of polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, or polybenzoxazole precursor, which is characterized by containing a specific onium salt, has good storage stability, is soluble in a general-purpose, safe organic solvent as a solvent for the composition, and can be used as a base resin for the photosensitive resin composition, thereby completing the present invention.

[0069] That is, the present invention provides: A negative photosensitive resin composition, (A) an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof; (B) a photoacid generator; (C) one or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having two or more methylol groups or alkoxymethylol groups on average per molecule, a compound in which the hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which the hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), a compound having a substituent (C-1) represented by the following formula (C-15), and a compound having two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2), [ka] (In the formula, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, s represents 1 or 2, and u is a number satisfying 1≦u≦3.) (D) an onium salt represented by the following general formula (1), [ka] (In the formula, A represents iodine, sulfur, phosphorus, or nitrogen; Q may be the same or different, and each may be linked or substituted, and each may represent a monovalent hydrocarbon group having 1 to 100 carbon atoms, optionally interrupted by a heteroatom; E - represents the anion of an organic or inorganic acid salt, and m represents 2 when A is iodine, 3 when A is sulfur, and 4 when A is phosphorus or nitrogen. (E) a solvent; The negative photosensitive resin composition comprises:

[0070] The present invention will be described in detail below, but the present invention is not limited thereto.

[0071] [(D) Onium salt] In order to solve the above problems, the present inventors have conducted extensive research into compounds that can replace basic compounds added to chemically amplified photosensitive resin compositions for the purpose of increasing the dissolution contrast thereof, and have investigated compositions that do not impair storage stability. As a result, they have found that an onium salt represented by the following general formula (1) can be used. [ka] (In the formula, A represents iodine, sulfur, phosphorus, or nitrogen; Q may be the same or different, and each may be linked or substituted, and each may represent a monovalent hydrocarbon group having 1 to 100 carbon atoms, optionally interrupted by a heteroatom; E - represents the anion of an organic or inorganic acid salt, and m represents 2 when A is iodine, 3 when A is sulfur, and 4 when A is phosphorus or nitrogen.

[0072] When the onium salt represented by the general formula (1) of the component (D) of the present invention is added to a negative photosensitive resin composition, the anion of the acid generated from the photoacid generator at low exposure doses is the E -The acidity of the generated acid can be reduced by anion exchange with the anion of the organic acid salt or inorganic acid salt, thereby preventing the acid-catalyzed crosslinking reaction from proceeding. On the other hand, at an exposure dose that generates more acid than the amount of onium salt represented by the general formula (1) added, more acid is generated than undergoes anion exchange, increasing the amount of acid that acts as a catalyst, and the crosslinking reaction proceeds, thereby causing insolubilization in the developer.

[0073] That is, by adding the onium salt represented by the above general formula (1) to a negative-tone chemically amplified photosensitive resin composition, it is possible to significantly change the solubility in the developer with changes in exposure dose, similar to the effect obtained by adding a small amount of a basic compound, and it is possible to increase the so-called dissolution contrast. By adding the onium salt represented by the above general formula (1), it is possible to increase the dissolution contrast, and as a result, it is possible to realize high resolution performance of the chemically amplified photosensitive resin composition.

[0074] Furthermore, a photosensitive resin composition using an onium salt represented by the above general formula (1) and a polymer compound having at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, Nisoe When a photosensitive resin composition is added, the onium salt represented by the general formula (1) does not interact with the imide structure or amide structure, and therefore intermolecular aggregation does not proceed in the composition solution, and the polymer compound does not behave in a manner that causes an increase in the apparent molecular weight during storage of the solution. Therefore, it has been found that poor storage stability, such as an increase in the thickness of the formed film over time when the photosensitive resin composition is applied to a substrate, can be avoided.

[0075] When the onium salt represented by the above general formula (1) is an iodonium salt in which A is iodine, the onium salt of the above general formula (1) preferably has the following structure for Q in view of ease of availability and stability of the compound. [ka]

[0076] When the onium salt represented by the general formula (1) is a sulfonium salt in which A is sulfur, Q is preferably a phenyl group having a substituent in view of availability and compound stability. Particularly preferred sulfonium salts include triphenylsulfonium salts containing a phenyl group having a substituent.

[0077] Furthermore, in the case of a sulfonium salt in which A in the formula (1) above is sulfur, the sulfonium salts having the following structure can be preferably used. [ka]

[0078] In the case of a phosphonium salt in which A in the onium salt represented by the above general formula (1) is phosphorus, Q may be the same or different and each Q may be linked, may be substituted, or is a monovalent hydrocarbon group having 1 to 100 carbon atoms which may be interrupted by a heteroatom, preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms, and more preferably a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. In view of ease of availability and stability of the compound, preferred examples include tetraphenylphosphonium salts and tetratolylphosphonium salts which have a substituent.

[0079] Suitable examples of E in the above general formula (1) will be described later.

[0080] (ammonium salt) On the other hand, when the onium salt represented by the above general formula (1) is an ammonium salt in which A in the formula is nitrogen, a quaternary ammonium salt represented by the following general formula (1-1) is more preferred. [ka] (In the formula, Q1, Q2, Q3, and Q4 may be the same or different, may be linked to each other, may be substituted, and may be a monovalent hydrocarbon group having 1 to 100 carbon atoms, optionally interrupted by a heteroatom; E- represents the anion of the same organic acid salt or inorganic acid salt as above.

[0081] Specific examples of preferred structures that can be represented by the above general formula (1-1) include those shown below, but are not limited to these.

[0082] In the formula of the quaternary ammonium salt represented by the general formula (1-1) above, Q1, Q2, Q3, and Q4 may be the same or different, and each may be linked, may be substituted, or represent a monovalent hydrocarbon group having 1 to 100 carbon atoms, optionally interrupted by a heteroatom.

[0083] In the formula, suitable hydrocarbon groups for Q1, Q2, Q3, and Q4 may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, and tricyclo[5.2.1.0]. 2,6 ] cyclic saturated hydrocarbyl groups having 4 to 10 carbon atoms such as decanyl group, adamantyl group, and adamantylmethyl group; alkenyl groups such as vinyl group and allyl group; aryl groups having 6 to 10 carbon atoms such as phenyl group and naphthyl group; and groups obtained by combining these.

[0084] In addition, some or all of the hydrogen atoms of these groups may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and some of the -CH2- constituting these groups may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, the group may contain a hydroxy group, a cyano group, a halogen atom, a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride, or the like.

[0085] Furthermore, the following can be preferably used as the cation of the quaternary ammonium salt represented by the above general formula (1-1). [ka]

[0086] Furthermore, E in the above general formula (1) or the above general formula (1-1) - is preferably an anion of an organic carboxylic acid represented by the following general formula (6). [ka] In the formula, R E is preferably a hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a hetero atom and which may be interposed by a hetero atom.

[0087] R in the above general formula (6) E Preferable examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a tert-pentyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, and an n-decyl group; a cyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclopentylbutyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylbutyl group, a norbornyl group, and a tricyclo[5.2.1.0] 2,6]C4-10 cyclic saturated hydrocarbyl groups such as decanyl group, adamantyl group, and adamantylmethyl group; alkenyl groups such as vinyl group and allyl group; aryl groups having 6 to 10 carbon atoms such as phenyl group and naphthyl group; and groups obtained by combining these.

[0088] As the anion of the organic carboxylic acid represented by the general formula (6), Examples of the anions of fatty acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15)-linolenic acid, (6,9,12)-linolenic acid, eleostearic acid, arachidic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and sorbic acid.

[0089] Furthermore, as the anion of the organic carboxylic acid represented by the above general formula (6), Carboxylic acids with hydroxyl groups such as lactic acid, malic acid, and citric acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, cinnamic acid, 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, and 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-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 Aromatic carboxylic acids such as tonic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic 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,Examples include anions of dicarboxylic acids such as 7-dicarboxynaphthalene.

[0090] Specific examples of the onium salt represented by the general formula (1) or the ammonium salt represented by the general formula (1-1) include any combination of the anions and cations described above. These onium salts or ammonium salts can be easily prepared by ion exchange reactions using known organic chemistry methods.

[0091] The content of component (D) in the negative-type photosensitive resin composition of the present invention containing the onium salt represented by general formula (1) or the ammonium salt represented by general formula (1-1) is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the alkali-soluble polymer as component (A). The onium salt represented by general formula (1) or the ammonium salt represented by general formula (1-1) may be used alone or in combination of two or more.

[0092] [(A) Alkali-soluble resin] Next, the component (A) of the polymer compound, which is a polymer having at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, used in the negative-tone chemically amplified photosensitive resin composition of the present invention, will be specifically described.

[0093] In pattern formation, development using N-methyl-2-pyrrolidone (NMP) is to be avoided due to concerns about its environmental impact and health hazards, particularly aspiration hazards. Furthermore, while the use of a general-purpose organic solvent such as cyclopentanone as a developer reduces concerns about harmful effects, from the perspective of environmental impact, it is preferable to use an alkaline aqueous solution, such as a 2.38% aqueous solution of tetramethylammonium hydroxide, which is often used in semiconductor manufacturing.

[0094] Therefore, the component (A) of the polymer compound is an alkali-soluble resin that can be developed with an alkaline aqueous solution. In this case, it is preferable that the component (A) is an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, which is a reaction product of a diamine containing at least one diamine represented by the following general formula (2) or the following general formula (3) with at least one tetracarboxylic dianhydride represented by the following general formula (4) or a dicarboxylic acid or dicarboxylic acid halide represented by the following general formula (5). [ka] [ka] [ka] [ka] (In the formula, L1 represents a tetravalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. L2 represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. T represents a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, -OCOR T , -OSO2R T , -OSO3R T However, R T is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom.

[0095] Furthermore, in this case, the component (A) is preferably an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, obtained by reacting a diamine containing at least one of the diamines represented by the above general formula (2) or the diamines represented by the general formula (3) with at least one of a tetracarboxylic dianhydride represented by the following general formula (8), or a dicarboxylic acid or dicarboxylic acid halide represented by the following general formula (9). [ka] [ka] (wherein Z is an alicyclic structure having 3 to 20 carbon atoms, an alicyclic structure in which aromatic rings are linked, or an alicyclic structure containing or interposed with a heteroatom) structure or an alicyclic structure formed by linking aromatic rings. T is a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, -OCO2R T , -OSO2R T , -OSO3R T wherein j represents 0 or 1, and when j is 0, the phthalic anhydride structure in the general formula (8) and the cyclic structure Z, and the benzoic acid structure in the general formula (9) and the cyclic structure Z are directly bonded, and when j is 1, X1 and X2 represent a divalent linking group.

[0096] When an alkali-soluble resin (polymer) having a polyamide, polyamideimide, polyimide structure, polybenzoxazole structure, or precursor structural unit thereof obtained by reacting one or more of the tetracarboxylic dianhydride represented by the above general formula (8) or the dicarboxylic acid or dicarboxylic acid halide represented by the above general formula (9) is used as the base resin of a photosensitive resin composition, the polymer is readily soluble in a general-purpose, safe organic solvent, and is therefore useful in constructing the composition.

[0097] Furthermore, polyamide, polyamideimide, polyimide structure, polybenzoxazole structure, or polymers having precursor structural units thereof, such as polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor, which are obtained by reacting a diamine containing at least one of the diamines represented by the general formula (2) or the diamines represented by the general formula (3) with at least one of the tetracarboxylic dianhydride represented by the general formula (4) or the dicarboxylic acid or dicarboxylic acid halide represented by the general formula (5), or obtained by reacting a tetracarboxylic dianhydride represented by the general formula (8) or the dicarboxylic acid or dicarboxylic acid halide represented by the general formula (9), are resins that are soluble in alkaline aqueous solutions, but the coating obtained after pattern formation and heating using a photosensitive resin composition containing this polymer has excellent resistance to strongly alkaline plating stripper solutions.

[0098] Furthermore, a protective coating obtained by pattern formation and heating using a photosensitive resin composition containing the above-mentioned polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, or polybenzoxazole precursor polymer as a base resin has excellent mechanical strength and adhesion. That is, a cured coating obtained by pattern formation using the above-mentioned polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, or polybenzoxazole precursor polymer as a base resin is excellent as a surface protective coating, insulating protective coating, or interlayer insulating film for electric and electronic components.

[0099] Furthermore, the present invention preferably includes an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, obtained by reacting the alicyclic structure Z of the above general formula (8) or (9) with one or more of tetracarboxylic dianhydrides, dicarboxylic acids, and dicarboxylic acid halides represented by the structure of the following general formula (10) or (11): [ka] (In the formula, the dotted line represents a bond, and k represents an integer of 0 or 1 or more. When k=0, Y2 represents a divalent group selected from any one of the following general formulae (13), (14), (15) and (16). When k=1, Y1 represents a divalent group selected from any one of the following general formulae (17), (18), and (19), and Y2 represents a divalent group selected from any one of the following general formulae (13), (14), (15), and (16). When k is 2 or more, Y1 represents the following general formula (17), and Y2 represents a divalent group selected from the following general formulas (13), (14), (15) and (16). R 1 , R 2 , R 3 , R 4 and R in the following formula (16) 5 , R 6 represents the same or different substituents, and may be a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 12 carbon atoms, Condition or a cyclic alkyl group or R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are bonded to form an alicyclic or aromatic ring.) [ka] (wherein the dotted line represents a bond, R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 represents the same or different substituents, and may be a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 12 carbon atoms, Condition Or it represents a cyclic alkyl group. m and p each represent an integer of 0 or 1 to 9; n represents 0 or 1; Y3 represents a divalent group selected from any one of the following general formulae (12), (13), (14), (15), (16), (17), (18), and (19). [ka] (wherein the dotted line represents a bond, R 5 , R 6 is the same as above. R 7 is a methyl group, an ethyl group, a linear or branched chain with 3 to 12 carbon atoms Condition or a cyclic alkyl group.

[0100] Furthermore, the alkali-soluble resin of the component (A) may contain a divalent linking group X 1、 X2 is preferably a polymer containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof obtained by reacting one or more of tetracarboxylic dianhydrides, dicarboxylic acids, and dicarboxylic acid halides, each of which has a structure represented by the following general formulas (20), (21), (22), (23), (24), and (25): [ka] (In the formula, the dotted line represents a bond.)

[0101] In the alkali-soluble resin of component (A), in the alicyclic structure Z of general formulas (8) and (9), preferred structures that can be represented by general formula (10) include, but are not limited to, the following:

[0102] [ka] (In the formula, the dotted line represents a bond.)

[0103] In the alkali-soluble resin of component (A), in the alicyclic structure Z of general formulas (8) and (9), preferred structures that can be represented by general formula (11) include, but are not limited to, the following: [ka] (In the formula, the dotted line represents a bond.)

[0104] In the alkali-soluble resin of component (A), when j is 0 in the general formulas (8) and (9), the phthalic anhydride structure in general formula (8) and the cyclic structure Z, and the benzoic acid structure in general formula (9) and the cyclic structure Z are directly bonded. Therefore, preferred structures in which the phthalic anhydride structure or the benzoic acid structure is directly bonded at the dotted line portion representing the bond between the structures listed above are represented by the following general formulas (8-1), (8-2), (8-3), and (9-1) to (9-6). [ka] [ka] (wherein Z and T are the same as above.)

[0105] In the above general formula (8), the above general formula (8-1) is particularly preferred in terms of synthesis method and ease of availability, while in the above general formula (9), the above general formula (9-1) is particularly preferred in terms of synthesis method and ease of availability.

[0106] On the other hand, in the alkali-soluble resin of the component (A), when j is 1 in the general formulas (8) and (9), X 1、 X2 represents a divalent linking group, and the linking group X 1、X2 is preferably a polymer containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, which are obtained by reacting one or more of tetracarboxylic dianhydrides, dicarboxylic acids, and dicarboxylic acid halides having a structure represented by any of the following general formulas (20), (21), (22), (23), (24), and (25): [ka] (In the formula, the dotted line represents a bond.)

[0107] In the above general formula (8), when j is 1, specific preferred structures include those shown below, although they are not limited thereto. [ka] (wherein Z is the same as above.)

[0108] Among the compounds of the general formulae (8-4) to (8-9), the compounds of the general formulae (8-5), (8-7), and (8-8) are preferred in terms of synthesis method and availability, with the compounds of the general formulae (8-5) and (8-7) being particularly preferred.

[0109] Next, in the above general formula (9), when j is 1, specific examples of preferred structures include those shown below, although the invention is not limited to these. [ka]

[0110] Among the compounds of the general formulae (9-7) to (9-12), the compounds of the general formulae (9-8), (9-10), and (9-11) are preferred in terms of synthesis method and availability, with the compounds of the general formulae (9-8) and (9-10) being particularly preferred.

[0111] Furthermore, the component (A) is preferably an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, in which the alicyclic structure Z in the above general formula (8) is a reaction product with one or more of a tetracarboxylic dianhydride represented by the following general formula (33) or (34) and / or a dicarboxylic acid or dicarboxylic acid halide selected from structures represented by the following formulas (35), (36), (37), (38), (39), and (40). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (wherein the dotted line represents a bond, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 represents the same or different substituents, and may be a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 12 carbon atoms, Condition or a cyclic alkyl group or R 1 , R 2 , R 3 , R 4 , R 5 , R 6R represents an alicyclic or aromatic ring. 7 is a methyl group, an ethyl group, a linear or branched chain with 3 to 12 carbon atoms Condition or a cyclic alkyl group. 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 represents the same or different substituents, and may be a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 12 carbon atoms, Condition or a cyclic alkyl group.

[0112] Tetracarboxylic acid dianhydrides in which the alicyclic structure Z in the general formula (8) is selected from any one of the general formulas (33) and (34) are readily available or can be synthesized. Dicarboxylic acids in which the alicyclic structure Z in the general formula (9) is selected from any one of the general formulas (35), (36), (37), (38), (39), and (40) are also readily available or can be synthesized. Dicarboxylic acid halides can be easily obtained by reacting these dicarboxylic acids with a halide agent.

[0113] Furthermore, the alkali-soluble resin of the component (A) is preferably a polymer containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, obtained by reacting a diamine represented by the above general formula (2) with one or more of the following general formula (26): a tetracarboxylic dianhydride represented by the above general formula (4), or a dicarboxylic acid or dicarboxylic acid halide represented by the above general formula (5). [ka]

[0114] In the component (A), if the diamine represented by general formula (2) is the diamine represented by general formula (26) and the resin obtained by the reaction contains a polymer having polyamide, polyamideimide, or polyimide structural units, such as polyamide, polyamideimide, polyimide precursor, polybenzoxazole, or polybenzoxazole precursor, then an alkaline aqueous developer can be used in the development step during pattern formation. The ability to use an alkaline aqueous developer helps improve the resolution of the photosensitive resin composition because the dissolution rate of the base resin in the alkaline aqueous developer can be easily measured and controlled.

[0115] Furthermore, if the alkali-soluble resin of component (A) is a polymer containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof obtained by reaction with a tetracarboxylic acid diester compound represented by the following general formula (27), this is preferred because it is more easily soluble in commonly used and safe organic solvents. [ka] (Wherein W1 is a tetravalent organic group, R 16 is represented by the following general formula (28): [ka] (In the formula, the dotted line represents a bond, V1 represents an (r+1)-valent organic group, Rf represents a linear, branched or cyclic alkyl group or aromatic group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms, r represents 1, 2 or 3, and q represents 0 or 1.)

[0116] Furthermore, the present invention is directed to a method for preparing an alkali-soluble resin (A) represented by the general formula (27) R 16is an organic group selected from groups represented by the following general formulas (29), (30), (31), and (32): [ka] [ka] [ka] [ka] (In the formula, the dotted line represents a bond. Rf is the same as defined above. Ra and Rb represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. V2 and V3 represent a linear or branched alkylene group having 1 to 6 carbon atoms. n1 represents an integer of 0 to 6, n2 represents an integer of 1 to 6, n3 represents an integer of 0 to 6, n4 represents an integer of 1 to 6, n5 represents an integer of 0 to 6, and n6 represents 0 or 1.)

[0117] Furthermore, the present invention is directed to a method for preparing an alkali-soluble resin (A) represented by the general formula (27) R 16 The present invention provides a negative-type photosensitive resin composition, which is a polymer containing at least one structure selected from the group consisting of a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, obtained by reacting a tetracarboxylic acid diester compound represented by the following general formula (28-1): [ka] (In the formula, the dotted line represents a bond. Rf is the same as above.)

[0118] Specific examples of organic groups that can be preferably used in the organic group represented by the general formula (29) include, but are not limited to, the following:

[0119] [ka]

[0120] [ka] (In the formula, the dotted line represents a bond.)

[0121] Specific examples of organic groups that can be preferably used in the organic group represented by the general formula (30) include, but are not limited to, the following:

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka] (In the formula, the dotted line represents a bond. n2 represents an integer of 1 to 6, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.)

[0126] Specific examples of organic groups that can be preferably used in the organic group represented by the general formula (31) include, but are not limited to, the following:

[0127] [ka]

[0128] [ka]

[0129] [ka]

[0130] [ka]

[0131] [ka]

[0132] [ka] (In the formula, the dotted line represents a bond. n4 represents an integer of 1 to 6, preferably an integer of 1 to 3, more preferably 1 or 2, and most preferably 1.)

[0133] Specific examples of organic groups that can be preferably used in the organic group represented by the general formula (32) include, but are not limited to, the following:

[0134] [ka] (In the formula, the dotted line represents a bond.)

[0135] Here, after patterning is performed using a photosensitive resin composition using the above-described polymer obtained by reaction containing a tetracarboxylic acid diester compound represented by general formula (27) as a base resin, during heating for post-curing, a ring-closing reaction for imidization proceeds in the structural unit of the polyimide precursor. At this time, the introduced R 16 Since R is released and removed from the system, a decrease in the thickness of the formed film is observed. Therefore, in order to minimize the film loss during post-curing, a more suitable R 16 The molecular weight of the polymer is small.

[0136] A suitable method for producing the tetracarboxylic acid diester compound represented by the general formula (27) is to react a tetracarboxylic acid dianhydride represented by the following general formula (41) with a compound having a terminal hydroxyl group represented by the following general formula (42) in the presence of a basic catalyst such as pyridine to give R 16 One way to do this is to introduce [ka] (Wherein W1 is the same as above.) [ka] (In the formula, V1, Rf, q, and r are the same as above.)

[0137] Suitable examples of the tetracarboxylic acid dianhydride represented by the above general formula (41) include aromatic acid dianhydrides, alicyclic acid dianhydrides, aliphatic acid dianhydrides, etc. Examples of aromatic acid dianhydrides include pyromellitic 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, diphenylsulfone-3,3',4,4'-tetracarboxylic acid dianhydride, and the like. carboxylic acid dianhydride, benzophenone-3,3',4,4'-tetracarboxylic acid 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) 1) Benzene dianhydride, p-phenylenebis(trimellitic acid monoester acid anhydride), bis(1,3-dioxo-1,3-dihydroisobenzfuran-5-carboxylic acid) 1,4-phenylene, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9, 10-Perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzoyloxy)phenyl)hexafluoropropane dianhydride, 1,6-difluoropromellitic dianhydride, 1-trifluoromethylpyromellitic dianhydride, 1,6-ditrifluoromethylpyromellitic dianhydride, 2,2'-bis(trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,Examples of the dianhydride include, but are not limited to, 2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, and acid dianhydride compounds in which the aromatic ring of these dianhydrides is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

[0138] Examples of the alicyclic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,4,5-cyclopentanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride. , 1,2,3,4-cycloheptanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0 ]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic dianhydride, tricyclo[6,3,0,0<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 methyl-2,3,6-tricarboxylic dianhydride, 7-oxabicyclo[2,2,1]heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecahydroanthracene-1,2,8,9-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride, 3,3',4,4'-oxydicyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,Examples of suitable dianhydrides include, but are not limited to, 2-dicarboxylic acid anhydrides, "Rikacid" (registered trademark) BT-100 (all trade names, manufactured by New Japan Chemical Co., Ltd.), and derivatives thereof, as well as acid dianhydrides in which the alicyclic ring of these dianhydrides is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

[0139] Examples of the aliphatic acid dianhydride include, but are not limited to, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and derivatives thereof.

[0140] These aromatic acid dianhydrides, alicyclic acid dianhydrides, and aliphatic acid dianhydrides can be used alone or in combination of two or more kinds.

[0141] The reaction of the tetracarboxylic dianhydride represented by the general formula (41) with the compound having a terminal hydroxyl group represented by the general formula (42) can be carried out by stirring, dissolving, and mixing the tetracarboxylic dianhydride represented by the general formula (41) and the compound having a terminal hydroxyl group represented by the general formula (42) in a reaction solvent in the presence of a basic catalyst such as pyridine at a reaction temperature of 20 to 50°C for 4 to 10 hours, thereby causing a half-esterification reaction of the acid dianhydride to proceed, and the desired tetracarboxylic diester compound represented by the general formula (27) can be obtained as a solution dissolved in the reaction solvent.

[0142] The resulting tetracarboxylic acid diester compound may be isolated, or the resulting solution may be used as is in the reaction with a diamine in the next step described below.

[0143] The reaction solvent is preferably one that can dissolve the tetracarboxylic acid diester compound and the polymer having structural units of a polyimide precursor obtained by the subsequent polycondensation reaction of the tetracarboxylic acid diester compound with a diamine. Examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and γ-butyrolactone. Ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons can also be used. Specific examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, and xylene. These solvents may be used alone or in combination as needed. However, as explained above, it is desirable to avoid the use of N-methyl-2-pyrrolidone.

[0144] On the other hand, the polymer of component (A) in the present invention may contain a diamine represented by the following general formula (43) as another diamine, or may be a polymer having a structure obtained by reacting a diamine containing at least one of the diamines represented by the general formula (2) above or the diamines represented by the general formula (3) above with at least one of the tetracarboxylic dianhydride represented by the general formula (4) above or the dicarboxylic acid or dicarboxylic acid halide represented by the general formula (5) above, or at least one of the tetracarboxylic dianhydride represented by the general formula (8) above or the dicarboxylic acid or dicarboxylic acid halide represented by the formula (9) above. [ka]

[0145] G in the structural unit (43) is a divalent organic group, and is not limited as long as it is a divalent organic group, but is preferably a divalent organic group having 6 to 40 carbon atoms, and more preferably a cyclic organic group containing 1 to 4 substituted aromatic or aliphatic rings, or an aliphatic group or siloxane group without a cyclic structure. More preferred examples of G include structures represented by the following formulas (44) or (45). The structure of G may be one type or a combination of two or more types. [ka] (In the formula, the dotted line represents a bond to an amino group.)

[0146] [ka] (In the formula, the dotted line represents a bond to an amino group, and R 17 each independently represents a methyl group, an ethyl group, a propyl group, an n-butyl group, or a trifluoromethyl group, and a represents a positive number of 2 to 20.

[0147] On the other hand, the alkali-soluble resin of component (A) may be a polymer having a structure obtained by reacting a diamine containing at least one of the diamines represented by general formula (2) and the diamines represented by general formula (3) with at least one tetracarboxylic dianhydride represented by general formula (4). [ka] (In the formula, L1 represents a tetravalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with or interrupted by a heteroatom.)

[0148] In the tetracarboxylic dianhydride represented by the general formula (4), L1 is preferably a tetravalent organic group similar to W1 in the general formula (41). In addition, a suitable example of the tetracarboxylic dianhydride represented by the general formula (4) is the tetracarboxylic dianhydride represented by the general formula (41).

[0149] Furthermore, the alkali-soluble resin of the component (A) is a diamine containing at least one of the diamines represented by the general formula (2) and the diamines represented by the general formula (3), and a dicarboxylic acid or dicarboxylic acid halide represented by the following general formula (5): 、 It may also be a polymer having a structure obtained by reacting one or more other dicarboxylic acids or dicarboxylic acid halides represented by the following general formula (5). [ka] (In the formula, L2 represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. T represents a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, -OCOR T , -OSO2R T , -OSO3R T However, R T is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom.

[0150] In the formula, L2 is a divalent organic group having an aliphatic chain structure or an alicyclic aliphatic group or an aromatic group having 4 to 40 carbon atoms. More preferably, it is a divalent organic group represented by the following formula (46). Furthermore, the structure of L2 may be one type or a combination of two or more types. [ka] (In the formula, R 18 , R 19 are each independently hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms, s is an integer of 1 to 30, and the dotted line represents a bond to a carboxy group or a carboxy halide group.

[0151] When L2 in the dicarboxylic acid or dicarboxylic acid halide represented by the above general formula (5) is a divalent organic group having an aliphatic chain structure, a photosensitive resin composition using a polymer that is the polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, or polybenzoxazole precursor of the present invention as the base resin is preferred because the mechanical strength, particularly the elongation, of the cured film is high.

[0152] Examples of the dicarboxylic acid compound represented by the general formula (5) include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, Examples of the diglycolic acid include pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosaneedioic acid, heneicosaneedioic acid, docosaneedioic acid, tricosaneedioic acid, tetracosaneedioic acid, pentacosaneedioic acid, hexacosaneedioic acid, heptacosaneedioic acid, octacosaneedioic acid, nonacosaneedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, and diglycolic acid.

[0153] Furthermore, examples of dicarboxylic acid compounds having an aromatic ring include phthalic acid, isophthalic acid, terephthalic acid, 4,4'-diphenyl ether dicarboxylic acid, 3,4'-diphenyl ether dicarboxylic acid, 3,3'-diphenyl ether dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 3,4'-biphenyl dicarboxylic acid, 3,3'-biphenyl dicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylic acid, 3,3'-benzophenone dicarboxylic acid, 4,4'-hexafluoroisopropylidene dibenzoic acid, 4,4'-dicarboxydiphenylamide, 1,4-phenylenediacetic acid, bis(2-methyl-2-propanol), ... Examples of suitable carboxylic acids include, but are not limited to, bis(4-carboxyphenyl)sulfide, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-carboxyphenyl)tetraphenyldisiloxane, bis(4-carboxyphenyl)tetramethyldisiloxane, bis(4-carboxyphenyl)sulfone, bis(4-carboxyphenyl)methane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,2-bis(p-carboxyphenyl)propane, and 2,6-naphthalenedicarboxylic acid. These may be used alone or in combination.

[0154] (Production method of component (A) alkali-soluble resin) Next, a method for producing the alkali-soluble resin, which is the component (A) of the photosensitive resin composition of the present invention, will be described. The alkali-soluble resin, which is component (A) of the photosensitive resin composition of the present invention, is a polymer having at least one structure selected from polyamide, polyamideimide, polyimide, polybenzoxazole structures and precursor structural units thereof, which are obtained by reacting a diamine containing at least one of the diamines represented by the general formula (2) above or the diamines represented by the general formula (3) with at least one of the tetracarboxylic dianhydrides represented by the general formula (4) or the general formula (8) above, or the dicarboxylic acids or dicarboxylic acid halides represented by the general formula (5) or the general formula (9) above.

[0155] The polyamide structural unit may be a diamine obtained by reacting at least one diamine represented by the general formula (2) or at least one diamine represented by the general formula (3) with at least one dicarboxylic acid or dicarboxylic acid halide represented by the general formula (5) or at least one diamine represented by the general formula (9). The polyamide structural units of the following general formulae (47), (48), (49), and (50) are shown below. [ka]

[0156] The polyimide structural unit is a polyamide or polyimide structural unit of the following general formulas (51), (52), (53), and (54) obtained by reacting a diamine containing at least one of the diamines represented by the general formula (2) above or the diamines represented by the general formula (3) with a tetracarboxylic dianhydride represented by the general formula (4) above or the general formula (8) above. [ka]

[0157] Polymers containing the polyamide structural units (47), (48), (49), and (50) can be obtained by reacting a dicarboxylic acid in which T in the general formula (5) is a hydrogen atom or a dicarboxylic acid in which T in the general formula (9) is a hydrogen atom in the presence of a dehydration condensation agent or by converting the dicarboxylic acid into an acid halide compound using a halogenating agent, followed by reaction with a diamine. Alternatively, they can be obtained by reacting a dicarboxylic acid halide in which T in the general formula (5) is a halogen atom or a dicarboxylic acid halide in which T in the general formula (9) is a halogen atom with a diamine.

[0158] Here, examples of a halogenating agent for converting the above-mentioned dicarboxylic acid into an acid halide compound include a method of converting the dicarboxylic acid into an acid chloride using a chlorinating agent such as thionyl chloride or dichlorooxalic acid, and then reacting the acid chloride with a diamine to synthesize the compound.

[0159] In the reaction of converting the dicarboxylic acid into an acid chloride using a chlorinating agent, a basic compound such as pyridine, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, or 1,5-diazabicyclo[4.3.0]non-5-ene may be used.

[0160] In this case, the solvent used in the method using an acid chloride, or the solvent used in the reaction to obtain a polyamide structure using a previously prepared dicarboxylic acid halide of the above general formula (5) where T represents a halogen atom or a dicarboxylic acid halide of the above general formula (9) where T represents a halogen atom, is preferably one that well dissolves the polymer having a polyamide structure obtained by polycondensation reaction with the acid chloride, dicarboxylic acid halide, and further diamines, and specific examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, etc. In addition to polar solvents, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. can also be used. Examples of the organic solvent include acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, etc. These organic solvents may be used alone or in combination of two or more.

[0161] On the other hand, it can be obtained by reacting a diamine containing at least one of the diamines represented by the general formula (2) or the diamines represented by the general formula (3) with a dicarboxylic acid in which T in the general formula (5) is a hydrogen atom or a dicarboxylic acid in which T in the general formula (9) is a hydrogen atom in the presence of a dehydration condensation agent. That is, the dicarboxylic acid in which T in the general formula (5) is a hydrogen atom or the dicarboxylic acid in which T in the general formula (9) is a hydrogen atom is used in the reaction in a state dissolved in a reaction solvent similar to the above, and a known dehydration condensation agent (e.g., dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disulfonyldibenzoylbenzoyl) is added to this reaction solution under ice cooling. Then, a diamine represented by the general formula (2) or a diamine represented by the general formula (3) dissolved or dispersed in a solvent is added dropwise to the resulting polyanhydride, and polycondensation is carried out to obtain a polymer containing structural units (47), (48), (49), and (50).

[0162] In the production of a polymer containing the above structural units (47), (48), (49), or (50), a diamine other than the diamine represented by the above general formula (2) or the diamine represented by the general formula (3), for example, a diamine other than the above general formula (43), can also be used simultaneously to obtain a polymer containing the polyamide structural unit of the present invention.

[0163] Next, a method for producing the polyimide structure represented by the above general formulas (51), (52), (53), and (54) will be described. The polyimide structure represented by the above general formulas (51), (52), (53), and (54) can be produced by first synthesizing an amic acid by reacting a diamine containing at least one of the diamine represented by the above general formula (2) and the diamine represented by the general formula (3) with a tetracarboxylic dianhydride represented by the above general formula (4) or the general formula (8), and then forming the polyimide structure by thermal dehydration.

[0164] The polyimide structure can be produced by dissolving a diamine in a solvent with a high boiling point and high polarity, such as γ-butyrolactone or N-methyl-2-pyrrolidone, adding an acid anhydride, and reacting the mixture at 0 to 80°C, preferably 10 to 50°C, to form an amide acid. Thereafter, a non-polar solvent, such as xylene, is added, and the mixture is heated to 100 to 200°C, preferably 130 to 180°C, to carry out an imidization reaction while removing water from the reaction system.

[0165] In the production of a polymer containing a polyimide structure represented by the above general formulas (37) and (38), a tetracarboxylic dianhydride other than the tetracarboxylic dianhydride represented by the above general formula (4), i.e., the tetracarboxylic dianhydride represented by the above general formula (41), can also be used simultaneously to obtain a polymer containing the polyamide structural unit of the present invention.

[0166] In addition, in the production of a polymer containing a polyimide structure represented by the above general formulas (51), (52), (53), and (54), a diamine other than the diamine containing at least one of the diamine represented by the above general formula (2) and the diamine represented by the general formula (3), i.e., for example, another diamine represented by the above general formula (43), can also be used simultaneously to obtain a polymer containing a polyamide structural unit of the present invention.

[0167] As a method for producing a polymer containing a polyamideimide structure having at least one of the structures of the above general formulas (47), (48), (49), and (50) and / or at least one of the structures of (51), (52), (53), and (54), a diamine containing at least one of the diamines represented by the above general formula (2) or the diamines represented by the general formula (3) is reacted with a tetracarboxylic dianhydride represented by the above general formula (4) or the general formula (8) to form an amic acid, and a dicarboxylic acid represented by the above general formula (5) or the general formula (9) is added to the same system as this amic acid and subjected to thermal dehydration to form a polyamideimide structure.

[0168] Another method for producing a polyamideimide structure is to use an excess of a diamine containing at least one of the diamines represented by general formula (2) or (3) in the production of a polymer containing a polyimide structure represented by the above-mentioned general formulas (47), (48), (49), and (50), and to react the diamine with a tetracarboxylic dianhydride represented by general formula (4) or (8) to synthesize an amic acid oligomer having an amino group at the end, and then react the terminal amino group of the amic acid oligomer with a dicarboxylic acid represented by general formula (5) or (9) using a method similar to the production method for obtaining the above-mentioned polyamide structure, thereby obtaining a polyamideimide structure.

[0169] Similarly to the above, in the production of a polymer containing a polyamideimide structure, a diamine other than the diamine represented by the general formula (2) or the diamine represented by the general formula (3), for example, another diamine represented by the general formula (43), may be used simultaneously.

[0170] Next, a method for introducing the tetracarboxylic acid diester compound represented by the above general formula (27) will be described. The tetracarboxylic acid diester compound represented by the general formula (27) can be introduced into a polymer having a polyamide, polyamideimide, or polyimide structural unit obtained by reacting a diamine containing at least one of the diamines represented by the general formula (2) or the diamines represented by the general formula (3) with at least one of the tetracarboxylic acid dianhydrides represented by the general formula (4) or the general formula (8), or at least one of the dicarboxylic acids or dicarboxylic acid halides represented by the general formula (5) or the general formula (9). The tetracarboxylic acid diester compound represented by the general formula (27) can be introduced into the polymer by using an excess of a diamine containing at least one of the diamines represented by the general formula (2) or the diamines represented by the general formula (3) and reacting it with the tetracarboxylic acid dianhydride represented by the general formula (4) or the general formula (8) to synthesize an amic acid oligomer having an amino group at the terminal, and then reacting the terminal amino group of the amic acid oligomer with the tetracarboxylic acid diester compound represented by the general formula (27) using a method similar to that used to obtain the polyamide structure.

[0171] Alternatively, an amide oligomer having an amino group at the terminal is synthesized by using an excess amount of a diamine containing at least one of the diamines represented by the general formula (2) or the diamines represented by the general formula (3) and reacting it with at least one of the dicarboxylic acids or dicarboxylic acid halides represented by the general formula (5) or the general formula (9), and then reacting the terminal amino group of the amide oligomer with the tetracarboxylic acid diester compound represented by the general formula (27) using a method similar to the production method for obtaining the polyamide structure, thereby introducing the tetracarboxylic acid diester compound represented by the general formula (27).

[0172] The alkali-soluble resin of component (A) of the photosensitive resin composition of the present invention is a diamine containing at least one of the diamines represented by the general formula (2) or the diamines represented by the general formula (3), and a tetracarboxylic acid dianhydride represented by the general formula (4) or the general formula (8), or is aboveThe polymer of the present invention, characterized by having a polyamide, polyamideimide, polyimide, or polybenzoxazole structural unit obtained by reacting one or more of the dicarboxylic acids or dicarboxylic acid halides represented by the general formula (5) or the general formula (9), preferably has a molecular weight of 5,000 to 100,000, more preferably 7,000 to 30,000. If the molecular weight is 5,000 or more, it becomes easy to form a film of a desired thickness on a substrate from a photosensitive resin composition using the polyimide precursor polymer as a base resin, and if the molecular weight is 100,000 or less, the viscosity of the photosensitive resin composition does not become extremely high, and there is no risk of it being impossible to form a film.

[0173] The polymer of the present invention may be capped at both ends with an end-capping agent for the purposes of controlling the molecular weight in the condensation polymerization reaction and suppressing changes in the molecular weight of the resulting polymer over time, i.e., gelation. Examples of end-capping agents that react with acid dianhydrides include monoamines and monohydric alcohols. Examples of end-capping agents that react with diamine compounds include acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds, dicarbonates, vinyl ethers, and the like. By reacting with an end-capping agent, various organic groups can be introduced as end groups.

[0174] Monoamines used as a terminal blocking agent for the acid anhydride group include aniline, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6- Aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-Dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene, 2-mercapto 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-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline Nylaniline, 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 Examples of the ethynyl-2-aminonaphthalene include, but are not limited to, 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, and 4,8-diethynyl-2-aminonaphthalene. These may be used alone or in combination of two or more.

[0175] On the other hand, examples of monohydric alcohols that can be used as a terminal blocking agent for the acid anhydride group include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, 2- Nonanol, 1-decanol, 2-decanol, 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, Isononyl Alcohol, 3,7Dimethyl-3-octanol, 2,4Dimethyl-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 、 Examples of the alcohol include, but are not limited to, cyclopentanol, cyclohexanol, cyclopentane monomethylol, dicyclopentane monomethylol, tricyclodecane monomethylol, norborneol, terpineol, etc. These may be used alone or in combination of two or more.

[0176] Examples of acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds that can be used as the amino group terminal capping agents include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-Hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene Phthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid Monocarboxylic acids such as 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid, and 8-ethynyl-2-naphthoic acid, and monoacid chloride compounds in which the carboxyl group of these acids is converted into an acid chloride, as well as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,Examples of such compounds include monoacid chloride compounds in which only the monocarboxyl groups of dicarboxylic acids such as 3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, and 2,7-dicarboxynaphthalene are converted to acid chlorides, and activated ester compounds obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide.

[0177] Examples of dicarbonate compounds used as a terminal amino group capping agent include di-tert-butyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.

[0178] Examples of vinyl ether compounds used as a capping agent for amino group terminals include chloroformates such as 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; 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.

[0179] Other compounds that can be used as a terminal amino group capping agent include benzyl chloroformate, benzoyl chloride, fluorenylmethyl chloroformate, 2,2,2-trichloroethyl chloroformate, allyl chloroformate, methanesulfonyl chloride, p-toluenesulfonyl chloride, and phenyl isocyanate.

[0180] The proportion of the acid anhydride end-capping agent introduced is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, and even more preferably 5 to 20 mol%, relative to the tetracarboxylic dianhydride component represented by the general formula (4) or (8) above, or the carboxylic acid component represented by the general formula (5) or (9) above. The proportion of the amino end-capping agent introduced is preferably in the range of 0.1 to 100 mol%, particularly preferably 5 to 90 mol%, relative to the diamine component containing at least one of the diamine represented by the general formula (2) or the diamine represented by the general formula (3) above, or the diamine component represented by the general formula (43) above. Multiple different end-capping agents may be reacted to introduce multiple different end groups.

[0181] [(B) Photoacid generator] Next, the photoacid generator, which is the component (B) of the negative photosensitive resin composition of the present invention, will be described. The photoacid generator can be one that generates an acid upon irradiation with light having a wavelength of 190 to 500 nm, and the acid acts as a crosslinking catalyst. Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonate ester derivatives, imido-yl-sulfonate derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, and triazine derivatives.

[0182] The onium salt includes, for example, a compound represented by the following general formula (60). [ka] (In the formula, R 20 represents a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, which may have a substituent; M + represents an iodonium cation or a sulfonium cation, U - represents a non-nucleophilic counterion, and n is 2 or 3.

[0183] Above R 20 In the formula (I), examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a 2-oxocyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the aryl group include a phenyl group; an alkoxyphenyl group such as an o-, m-, or p-methoxyphenyl group, an ethoxyphenyl group, or an m- or p-tert-butoxyphenyl group; and an alkylphenyl group such as a 2-, 3-, or 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, or a dimethylphenyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, and the like.

[0184] U - Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkylsulfonates such as triflate, 1,1,1-trifluoroethanesulfonate and nonafluorobutanesulfonate; arylsulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate and 1,2,3,4,5-pentafluorobenzenesulfonate; and alkylsulfonates such as mesylate and butanesulfonate.

[0185] In this case, as described above, the anion of the acid generated from the photoacid generator can undergo anion exchange with an organic carboxylic acid anion that is suitable as the anion of the onium salt of component (D), thereby increasing the dissolution contrast and achieving high resolution. Therefore, it is particularly preferable that component (B) is an organic sulfonic acid represented by the following general formula (7): [ka] (In the formula, R U represents a hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom.

[0186] That is, U - As the non-nucleophilic counter ion of the formula (I), a sulfonate is preferred.

[0187] The diazomethane derivative of the photoacid generator, which is the component (B) of the present invention, includes the compound represented by the following general formula (60). [ka] (In the formula, R 21 may be the same or different and represent a linear, branched, or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

[0188] Above R 21 In the above, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. Examples of the aryl group include a phenyl group; an alkoxyphenyl group such as an o-, m-, or p-methoxyphenyl group, an ethoxyphenyl group, or a m- or p-tert-butoxyphenyl group; and an alkylphenyl group such as a 2-, 3-, or 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, and a 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0189] Specific examples of such photoacid generators include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate )phenylsulfonium, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, and other onium salts;Bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane diazomethane derivatives such as bis(n-amylsulfonyl)diazomethane, bis(isoamylsulfonyl)diazomethane, bis(sec-amylsulfonyl)diazomethane, bis(tert-amylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-amylsulfonyl)diazomethane, and 1-tert-amylsulfonyl-1-(tert-butylsulfonyl)diazomethane;Bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis -o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, bis-o-(camphorsulfonyl)-α-dimethylglyoxime, etc. Oxime derivatives; oxime sulfonate derivatives such as α-(benzenesulfonium oxyimino)-4-methylphenylacetonitrile; β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane; disulfone derivatives such as diphenyl disulfone and dicyclohexyl disulfone; nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate;Sulfonic acid ester derivatives such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3-tris(p-toluenesulfonyloxy)benzene; phthalimide-yl-triflate, phthalimide-yl-tosylate, 5-norbornene 2,3-dicarboximide-yl-triflate, 5-norbornene 2,3-dicarboximide-yl-tosylate, 5-norbornene 2,3-dicarboximide-yl-n-butylsulfonate, n-trifluoromethanesulfonyloxy-n-butylsulfonate, phthalimide-yl-triflate, phthalimide-yl-tosylate ... Examples of suitable photoacid generators include imidoyl sulfonate derivatives such as methylsulfonyloxynaphthylimide; iminosulfonates 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; and 2-methyl-2[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane. Among these, imidoyl sulfonates, iminosulfonates, and oxime sulfonates are preferred. The photoacid generators may be used singly or in combination.

[0190] In this case, for the same reason as above, the acid generated from the photoacid generator is preferably an organic sulfonic acid represented by the general formula (7) above.

[0191] In terms of the light absorption of the photoacid generator itself and photocurability in a thick film, the amount of the photoacid generator (B) in the negative photosensitive resin composition of the present invention is preferably 0.05 to 20 parts by mass, and more preferably 0.2 to 5 parts by mass, per 100 parts by mass of component (A).

[0192] [(C) Crosslinking Agent] The component (C) in the negative-tone photosensitive resin composition of the present invention is one or more crosslinking agents selected from the group consisting of amino condensates modified with formaldehyde or formaldehyde-alcohol, phenol compounds having an average of two or more methylol groups or alkoxymethylol groups per molecule, compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are substituted with glycidyl groups or compounds in which the hydrogen atoms of the hydroxyl groups are substituted with groups having glycidyl groups, compounds in which the hydrogen atoms of polyhydric phenols are substituted with groups represented by the following formula (C-1), compounds having a substituent (C-1) represented by the following formula (C-15), and compounds having two or more nitrogen atoms having glycidyl groups represented by the following formula (C-2). [ka] (In the formula, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, s represents 1 or 2, and u is a number satisfying 1≦u≦3.)

[0193] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include a melamine condensate modified with formaldehyde or formaldehyde-alcohol, and a urea condensate modified with formaldehyde or formaldehyde-alcohol.

[0194] The melamine condensate modified with formaldehyde or formaldehyde-alcohol can be prepared, for example, by first modifying a melamine monomer with formalin by methylolation according to a known method, or by further modifying the melamine monomer by alkoxylation with an alcohol to obtain a modified melamine represented by the following general formula (45): The alcohol is preferably a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms.

[0195] [ka] (In the formula, R 50may be the same or different and are a methylol group, an alkoxymethyl group including an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, provided that at least one is a methylol group or the above alkoxymethyl group. Above R 50 Examples of the alkyl group include alkoxymethyl groups such as a methylol group, a methoxymethyl group, and an ethoxymethyl group, and a hydrogen atom.

[0196] Specific examples of modified melamine represented by the general formula (45) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethylol melamine, etc. Next, the modified melamine represented by the general formula (45) or a polymer thereof (for example, an oligomer such as a dimer or trimer) is subjected to addition condensation polymerization with formaldehyde according to a conventional method until a desired molecular weight is reached, thereby obtaining a melamine condensate modified with formaldehyde or a formaldehyde-alcohol.

[0197] The above-mentioned urea condensate modified with formaldehyde or formaldehyde-alcohol can be prepared, for example, by methylolating a urea condensate having a desired molecular weight with formaldehyde to modify it, or by further alkoxylating it with an alcohol to modify it, according to a known method. Specific examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, and propoxymethylated urea condensate. The modified melamine condensates and modified urea condensates may be used alone or in combination of two or more.

[0198] Next, examples of phenol compounds having an average of two or more methylol groups or alkoxymethylol groups per molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and compounds represented by the following formulas (C-3) to (C-7). [ka]

[0199] The above crosslinking agents can be used alone or in combination of two or more.

[0200] On the other hand, examples of compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are substituted with glycidyl groups include compounds obtained by reacting the hydroxyl groups of bisphenol A, tris(4-hydroxyphenyl)methane, and 1,1,1-tris(4-hydroxyphenyl)ethane with epichlorohydrin in the presence of a base. Suitable examples of compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are substituted with glycidyl groups or groups having glycidyl groups include the compounds represented by the following formulas (C-8) to (C-14). [ka] (wherein t is 2≦t≦3.) One or two of these compounds in which the hydroxyl groups of polyhydric phenols are substituted with glycidoxy groups can be used as the crosslinking agent.

[0201] Examples of compounds in which the hydrogen atoms of the hydroxyl groups of a polyhydric phenol are substituted with substituents represented by the following formula (C-1) include compounds containing two or more of the substituents and represented by the following formulas C-22 to C-24. [ka]

[0202] Furthermore, examples of the compound having a substituent (C-1) represented by the following formula (C-15) include those represented by the following formula: [ka] (wherein u is a number in the range of 1≦u≦3.)

[0203] On the other hand, examples of the compound having two or more nitrogen atoms having a glycidyl group, represented by the following formula (C-2), include those represented by the following formula (C-16). [ka] (In the formula, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and s represents 1 or 2.) [ka] (In the formula, W represents a linear, branched, or cyclic alkylene group having 2 to 12 carbon atoms, or a divalent aromatic group.) Examples of the compound represented by the above formula (C-16) include compounds represented by the following formulae (C-17) to (C-20). [ka]

[0204] 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 be suitably used. [ka] One or two of these compounds containing two or more nitrogen atoms having a glycidyl group, as represented by the above formula (C-2), can be used as a crosslinking agent.

[0205] Component (C) is a component that undergoes a crosslinking reaction during post-curing after pattern formation of a negative-type photosensitive resin composition using a polymer containing the polyimide precursor of the present invention, thereby further increasing the strength of the cured product. From the viewpoints of photocurability and heat resistance, the weight-average molecular weight of such component (C) is preferably 150 to 10,000, and particularly preferably 200 to 3,000.

[0206] The amount of the component (C) blended is 0.5 to 50 parts by mass, preferably 1 to 30 parts by mass, and more preferably 5 to 20 parts by mass, per 100 parts by mass of the component (A).

[0207] [(E) Solvent] Component (E) in the photosensitive resin composition of the present invention is a solvent. There are no limitations on the solvent for component (E), as long as it dissolves components (A), (B), (C), and (D). Examples of the solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-amyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate (PGMEA), 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 (CyPn), propylene glycol monomethyl ether acetate, γ-butyrolactone (GBL), and mixed solvents thereof.

[0208] The amount of component (E) blended is preferably 50 to 2,000 parts by mass, and particularly preferably 100 to 1,000 parts by mass, per 100 parts by mass of component (A).

[0209] The negative-type photosensitive resin composition of the present invention may further contain components other than the components (A), (B), (C), (D), and (E). Examples of such components include an adhesion aid, a thermal crosslinking agent (F), and a surfactant (G).

[0210] Examples of the (F) thermal crosslinking agent include polymers obtained by radical polymerization of (meth)acrylate monomers represented by the following general formula (61-1) or (61-2). [ka] (In the formula, R 50 represents a hydrogen atom or a methyl group, and R 51 represents a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may contain an ester group, an ether group or an aromatic hydrocarbon group, and b represents 0 or an integer of 1 to 4.

[0211] A suitable example of the (F) thermal crosslinking agent is a polymer obtained by radical polymerization of a monomer represented by the following general formula (61-3). [ka]

[0212] As the (F) thermal crosslinking agent, a polymer obtained by radical polymerization of a (meth)acrylate monomer represented by the above general formula (61-1) or (61-2) can be preferably used, including a homopolymer obtained by polymerizing each of the (meth)acrylate monomers represented by the above general formula (61-1) or (61-2) alone, and a copolymer obtained by polymerizing the (meth)acrylate monomer represented by the above general formula (61-1) or (61-2) together with another monomer copolymerizable with the (meth)acrylate monomer.

[0213] The amount of the thermal crosslinking agent (F) that can be used in the negative photosensitive resin composition of the present invention is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 20 to 300 parts by mass, per 100 parts by mass of the component (A). Mass part From 50 Mass partis particularly preferred.

[0214] (G) The surfactant is preferably a nonionic surfactant, such as a fluorine-based surfactant, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkyl amine oxide, or fluorine-containing organosiloxane compound.

[0215] These surfactants may be commercially available, such as Fluorad "FC-4430" (manufactured by Sumitomo 3M Limited), Surflon "S-141" and "S-145" (both manufactured by Asahi Glass Co., Ltd.), Unidyne "DS-401", "DS-4031" and "DS-451" (both manufactured by Daikin Industries, Ltd.), Megafac "F-8151" (manufactured by DIC Corporation), and "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.). Of these, Fluorad "FC-4430" (manufactured by Sumitomo 3M Limited) and "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.) are preferred. The amount of the surfactant (G) that can be used in the negative-type photosensitive resin composition of the present invention is 0.01 to 1.0 part by mass, preferably 0.01 to 0.1 part by mass, and more preferably 0.01 to 0.05 part by mass, per 100 parts by mass of the component (A).

[0216] (Pattern formation method) Next, a pattern forming method using the negative photosensitive resin composition of the present invention will be described.

[0217] When a pattern is formed using the negative photosensitive resin composition of the present invention, it can be carried out by employing a known lithography technique. For example, the photosensitive resin composition is applied by spin coating to a substrate on which a pattern such as a silicon wafer, SiO2 substrate, SiN substrate, or copper wiring has been formed, and the substrate is prebaked at 80 to 130°C for about 50 to 600 seconds to form a photosensitive film having a thickness of 1 to 50 μm, preferably 1 to 30 μm, and more preferably 5 to 20 μm.

[0218] In the spin coating method, the photosensitive resin composition is applied to a silicon substrate by dispensing about 5 mL of the composition onto the substrate and then rotating the substrate. The thickness of the photosensitive film on the substrate can be easily adjusted by adjusting the rotation speed.

[0219] Next, a mask for forming a desired pattern is placed over the photosensitive film, and high-energy rays such as i-rays and g-rays with wavelengths of 190 to 500 nm or electron beams are irradiated at an exposure dose of 1 to 5,000 mJ / cm. 2 Approximately, preferably 100 to 2,000 mJ / cm 2 Expose to a level that is approximately

[0220] The negative photosensitive resin composition of the present invention can be developed with an aqueous alkaline solution.

[0221] On the other hand, a suitable alkaline aqueous solution that can be used for alkaline development is a 2.38% aqueous solution of tetramethylhydroxyammonium (TMAH). Development can be carried out by a conventional method such as a spray method or a puddle method, or by immersion in a developer. Thereafter, washing, rinsing, drying, etc. can be carried out as necessary to obtain a film of the resin composition having the desired pattern.

[0222] Furthermore, the patterned coating obtained by the above-described pattern formation method can be post-cured using an oven or hot plate at a temperature of 100 to 300°C, preferably 150 to 300°C, and more preferably 180 to 250°C, to form a cured coating. In this post-curing step, a post-curing temperature of 100 to 300°C increases the crosslink density of the photosensitive resin composition coating and removes remaining volatile components, which is preferable from the viewpoints of adhesion to the substrate, heat resistance, strength, and electrical properties. The post-curing time can be 10 minutes to 10 hours.

[0223] (Protective coating and interlayer insulating film that covers electronic components such as wiring, circuits, and boards) The patterns formed as described above are used as protective coatings and interlayer insulating films that cover electronic components such as wiring, circuits, and substrates. These formed patterns and protective coatings have excellent insulating properties and also exhibit excellent adhesion to the metal layers of the wiring or circuit, such as Cu, that they cover, the metal electrodes that exist on the substrate, or the insulating substrate, such as SiN, that they cover. They also have mechanical strength suitable for protective coatings and interlayer insulating films, while enabling significant improvements in resolution performance to enable the formation of even finer patterns.

[0224] The cured coating thus obtained has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance to alkaline stripping solutions, and is also highly reliable for semiconductor elements that use it as a protective coating, particularly in preventing cracking during temperature cycle tests. Therefore, it is suitable for use as a protective coating or interlayer insulating film for electrical and electronic components, semiconductor elements, etc.

[0225] The above protective coatings and interlayer insulating films are effective for applications such as insulating films for semiconductor devices including rewiring, insulating films for multilayer printed circuit boards, solder masks, and coverlay films due to their heat resistance, chemical resistance, and insulating properties. 。 [Example]

[0226] EXAMPLES The present invention will be specifically explained below using examples and comparative examples, but the present invention is not limited to these.

[0227] The present invention will be specifically explained below by showing synthesis examples, comparative synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

[0228] I. Resin synthesis The chemical structures and names of the compounds used in the synthesis examples are shown below. [ka]

[0229] 6FAP 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane BPS Bis(3-amino-4-hydroxyphenyl) sulfone s-ODPA 3,3',4,4'-oxydiphthalic dianhydride s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride DC-1 Sebacic acid dichloride PAP 4-aminophenol Rf-1 4,4,5,5,5-pentafluoropentanol

[0230] [Synthesis Example 1] Synthesis of polyimide resin (A-1) In a 1 L flask equipped with a stirrer and thermometer, 30 g (81.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 170 g of N-methyl-2-pyrrolidone were added and stirred at room temperature to dissolve. Next, a solution of 12.7 g (41.0 mmol) of 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA) and 18.8 g (41.0 mmol) of tetracarboxylic dianhydride (AN-1) in 320 g of N-methyl-2-pyrrolidone was added dropwise at room temperature and stirred for 3 hours at room temperature. After the addition, 40 g of xylene was added to the reaction mixture and heated to reflux at 170 °C for 3 hours while removing the water generated. After cooling to room temperature, the reaction solution was added dropwise to 2 L of ultrapure water under stirring, and the precipitate was filtered off, washed appropriately with water, and then dried under reduced pressure at 40°C for 48 hours to obtain polyimide resin (A-1). The molecular weight of this polymer was measured by GPC and found to be 35,000 in terms of polystyrene.

[0231] [Synthesis Example 2] Synthesis of polyimide resin (A-2) Polyimide resin (A-2) was obtained in the same manner as in Synthesis Example 1, except that 18.8 g of tetracarboxylic dianhydride (AN-1) was replaced with 26.3 g of tetracarboxylic dianhydride (AN-2) having the weight shown in Table 1 below. polymer The molecular weight of the polymer was measured by GPC and was found to be 34,000 in terms of polystyrene.

[0232] [Synthesis Example 3] Synthesis of polyimide resin (A-3) Polyimide resin (A-3) was obtained using the same procedure as in Synthesis Example 1, except that 30.0 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) was replaced with 23.0 g of bis(3-amino-4-hydroxyphenyl)sulfone (BPS). The molecular weight of this polymer was measured by GPC, and as shown in Table 1, the weight average molecular weight was 33,000 in terms of polystyrene.

[0233] [Synthesis Example 4] Synthesis of tetracarboxylic acid diester dichloride (X-1) In a 3 L flask equipped with a stirrer and thermometer, 100 g (322 mmol) of 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA), 65.2 g (644 mmol) of triethylamine, 39.3 g (322 mmol) of N,N-dimethyl-4-aminopyridine, and 400 g of γ-butyrolactone were added and stirred at room temperature. 114.7 g (644 mmol) of 4,4,5,5,5-pentafluoropentanol (Rf-1) was added dropwise and the mixture was stirred at room temperature for 24 hours. The reaction was then quenched by adding 370 g of 10% aqueous hydrochloric acid solution dropwise under ice cooling. 800 g of 4-methyl-2-pentanone was added to the reaction mixture, and the organic layer was separated and washed six times with 600 g of ultrapure water. The solvent in the resulting organic layer was evaporated, yielding 193 g of tetracarboxylic acid diester compound (X-1). To the resulting tetracarboxylic acid diester compound, 772 g of N-methyl-2-pyrrolidone was added and the mixture was stirred at room temperature to dissolve. Next, under ice cooling, 75.8 g (637 mmol) of thionyl chloride was added dropwise while maintaining the reaction solution temperature at 10°C or less. After the dropwise addition, the mixture was stirred under ice cooling for 2 hours to obtain an N-methyl-2-pyrrolidone solution of tetracarboxylic acid diester dichloride (X-1).

[0234] [Synthesis Example 5] Synthesis of polyamideimide resin (A-4) In a 500 ml flask equipped with a stirrer and thermometer, 30.0 g (81.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 170 g of N-methyl-2-pyrrolidone were added and stirred at room temperature to dissolve. Next, a solution of 12.7 g (41.0 mmol) of 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA) and 5.6 g (12.3 mmol) of tetracarboxylic dianhydride (AN-1) in 185 g of N-methyl-2-pyrrolidone was added dropwise at room temperature and stirred for 3 hours at room temperature. After the addition, 40 g of xylene was added to the reaction mixture and heated to reflux at 170 °C for 3 hours while removing the water generated. After cooling to room temperature, 1.4 g (18.0 mmol) of pyridine was added, and a mixture of 14.7 g (4.1 mmol as tetracarboxylic acid diester dichloride) of a separately prepared N-methyl-2-pyrrolidone solution (X-1) and 5.9 g (24.6 mmol) of sebacic acid dichloride (DC-1) was added dropwise to maintain the temperature below 5°C. After the addition was completed, the mixture was returned to room temperature, and the reaction solution was added dropwise to 2 L of ultrapure water with stirring. The precipitate was filtered, washed appropriately with water, and dried under reduced pressure at 40°C for 48 hours to obtain polyamideimide resin (A-4). The molecular weight of this polymer was measured by GPC, and found to be 38,000 weight average molecular weight in terms of polystyrene.

[0235] [Synthesis Example 6] Synthesis of polyamideimide resin (A-5) Polyimide resin (A-5) was obtained in the same manner as in Synthesis Example 5, except that 5.6 g of tetracarboxylic dianhydride (AN-1) was replaced with 7.9 g of tetracarboxylic dianhydride (AN-2). The molecular weight of this polymer was measured by GPC, and as shown in Table 1, the weight average molecular weight was 39,000 in terms of polystyrene.

[0236] [Synthesis Example 7] Synthesis of polyamideimide resin (A-6) Polyimide resin (A-6) was obtained using the same procedure as in Synthesis Example 5, except that 30 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) was replaced with 23.0 g of bis(3-amino-4-hydroxyphenyl)sulfone (BPS). The molecular weight of this polymer was measured by GPC, and as shown in Table 1, the weight average molecular weight was 35,000 in terms of polystyrene.

[0237] [Synthesis Example 8] Synthesis of polyamideimide resin (A-7) A 500 ml flask equipped with a stirrer and thermometer was charged with 27.0 g (73.7 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 108 g of N-methyl-2-pyrrolidone, which were stirred at room temperature until dissolved. Next, a solution of 12.7 g (41.0 mmol) of 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA) and 5.6 g (12.3 mmol) of tetracarboxylic dianhydride (AN-1) in 185 g of N-methyl-2-pyrrolidone was added dropwise at room temperature. The mixture was stirred at room temperature for 3 hours. 40 g of xylene was then added to the reaction mixture, which was then heated to reflux at 170 °C for 3 hours, while removing the water generated. After cooling to room temperature, 0.9 g (8.2 mmol) of 4-aminophenol (PAP) and 1.4 g (18.0 mmol) of pyridine were added, and a mixture of 14.7 g (4.1 mmol of tetracarboxylic acid diester dichloride) of a separately prepared N-methyl-2-pyrrolidone solution (X-1) and 5.9 g (24.6 mmol) of sebacic acid dichloride (DC-1) was added dropwise to maintain the temperature below 5°C. After the addition, the mixture was returned to room temperature, and the reaction solution was added dropwise to 2 L of ultrapure water with stirring. The precipitate was filtered, washed appropriately, and dried at 40°C for 48 hours under reduced pressure to obtain polyamideimide resin (A-7). The molecular weight of this polymer was measured by GPC and found to be 30,000 in terms of polystyrene equivalent, as shown in Table 1.

[0238] [Synthesis Example 9] Synthesis of polyamideimide resin (A-8) Polyimide resin (A-8) was obtained using the same procedure as in Synthesis Example 8, except that 12.7 g (41.0 mmol) of 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA) was changed to 14.0 g (45.1 mmol) and the N-methyl-2-pyrrolidone solution of tetracarboxylic acid diester dichloride (X-1) was omitted. The molecular weight of this polymer was measured by GPC, and as shown in Table 1, the weight average molecular weight was 31,000 in terms of polystyrene.

[0239] [Synthesis Example 10] Synthesis of polyamideimide resin (A-9) Polyimide resin (A-9) was obtained using the same procedure as in Synthesis Example 8, except that 12.7 g (41.0 mmol) of 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA) was replaced with 11.4 g (36.9 mmol) and 1.2 g (4.1 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) was added. The molecular weight of this polymer was measured by GPC and found to be 30,000 in polystyrene equivalents, as shown in Table 1.

[0240] [Synthesis Example 11] Synthesis of polyamideimide resin (A-10) Polyimide resin (A-10) was obtained using the same procedure as in Synthesis Example 10, except that 11.4 g (36.9 mmol) of 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA) was replaced with 12.6 g (40.6 mmol), and 1.2 g (4.1 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) was replaced with 1.35 g (4.6 mmol), and the N-methyl-2-pyrrolidone solution of tetracarboxylic acid diester dichloride (X-1) was omitted. The molecular weight of this polymer was measured by GPC, and the weight average molecular weight (Mw) was 30,000 in terms of polystyrene, as shown in Table 1.

[0241] [Table 1]

[0242] II. Preparation of Photosensitive Resin Composition Using the polyimide resins (A-1) to (A-3) synthesized in Synthesis Examples 1 to 3 above and the polyamideimide resins (A-4) to (A-10) synthesized in Synthesis Examples 5 to 11 above as base resins, resin compositions were prepared at 20 mass% resin equivalent with the formulations and blending amounts shown in Tables 2 and 3. The mixture was then stirred, mixed, and dissolved, followed by microfiltration through a 0.5 μm Teflon (registered trademark) filter to obtain photosensitive resin compositions. In the tables, the solvent PGMEA stands for propylene glycol monomethyl ether acetate, and CyPn stands for cyclopentanone.

[0243] [Table 2]

[0244] [Table 3]

[0245] In Table 2, the acid generator (B-1), crosslinking agent (CL-1), (CL-2), (CL-3), (CL-4), Ammonium salts and sulfonium salts (D-1) to (D-7), Basic compounds (Amine-1), (Amine-2), and (Amine-3) used in the comparative photosensitive resin compositions The details are as follows:

[0246] Acid generator (B-1) [ka]

[0247] Crosslinker (CL-1) [ka]

[0248] Crosslinker (CL-2) [ka]

[0249] Crosslinker (CL-3) [ka] (n=0.9~1) Epoxy resin: ADEKA Corporation EP4000L

[0250] Crosslinker (CL-4) [ka] (n=1-3) Toagosei Co., Ltd. OXT-121

[0251] Onium salt (D-1) [ka]

[0252] Onium salt (D-2) [ka]

[0253] Onium salt (D-3) [ka]

[0254] Onium salt (D-4) [ka]

[0255] Onium salt (D-5) [ka]

[0256] Onium salt (D-6) [ka]

[0257] Onium salt (D-7) [ka]

[0258] Basic Compound (Amine-1) [ka]

[0259] Basic Compound (Amine-2) [ka]

[0260] Basic compounds (Amine-3) [ka]

[0261] III.Storage stability The above photosensitive resin compositions 1 to 18 and comparative photosensitive resin compositions 1 to 3 were stirred, mixed, and dissolved as described above, and then microfiltered using a 0.5 μm Teflon (registered trademark) filter. Immediately thereafter, 5 mL of the solution was dispensed onto a silicon wafer, and the wafer was then rotated to form a film by spin coating. Next, the film was prebaked on a hot plate at 100°C for 2 minutes. The film thickness after prebaking was 6. μ The rotation speed was adjusted so that the film thickness was 1 / 3 m. The film thickness was measured and recorded as the initial film thickness.

[0262] The filtered solutions of the above photosensitive resin compositions 1 to 18 and comparative photosensitive resin compositions 1 to 3 were stored at room temperature for 3 weeks, and the film thickness after pre-baking in the same manner as above was 600 nm. μ The film was formed at a rotation speed of 100 m. Then, the film was pre-baked on a hot plate at 100°C for 2 minutes. The film thickness was measured after 3 weeks, and the amount of change was evaluated using the following formula. The results are summarized in Table 4 below. Change (%) = Thickness after 3 weeks - Initial thickness ×100 Initial film thickness

[0263] IV. Pattern Formation 5 mL of each of the above photosensitive resin compositions 1 to 18 and comparative photosensitive resin compositions 1 to 3 was dispensed onto a silicon wafer, and then the substrate was rotated, i.e., by spin coating, to coat the film so that the film would have a thickness of 6 μm after heating for post-curing, which is performed after pattern formation. That is, considering in advance that the film thickness would decrease after the post-curing step, the rotation speed during coating was adjusted so that the finished film thickness after post-curing would be 5 μm.

[0264] Next, the substrate was prebaked on a hot plate at 100°C for 2 minutes. Then, an i-line exposure machine AP-300E manufactured by Veeco Japan was used to perform pattern formation. A negative pattern mask was used for pattern formation. The mask had a pattern that allowed for the formation of holes in a 1:1 vertical / horizontal arrangement, with 10 μm intervals from 50 μm to 20 μm, 5 μm intervals from 20 μm to 10 μm, and 1 μm intervals from 10 μm to 1 μm.

[0265] In the development process, an alkaline aqueous solution was used as the developer, and a 2.38% aqueous tetramethylammonium hydroxide solution was used as the developer. After one-minute puddle development with a 2.38% aqueous tetramethylammonium hydroxide (TMAH) solution was performed the appropriate number of times shown in Table 4, the film was rinsed with ultrapure water.

[0266] The resulting pattern on the wafer was then post-cured in an oven at 180° C. for 2 hours while purging with nitrogen.

[0267] Next, each substrate was cut out so that the shape of the resulting hole pattern could be observed, and the hole pattern shape was observed using a scanning electron microscope (SEM). The diameter of the smallest opening hole at a film thickness of 5 μm after post-curing was determined, and the pattern shape was evaluated. These results, along with the sensitivity at which the smallest pattern could be formed, are shown in Table 4.

[0268] The hole pattern shape was evaluated according to the following criteria, and the evaluation results are shown in Table 4. Good: Holes that are rectangular or tapered (the dimensions of the top of the hole are larger than the dimensions of the bottom) Poor: Reverse tapered shape (the dimensions of the top of the hole are smaller than the dimensions of the bottom), overhang shape (the top of the hole protrudes), significant film loss, or residue at the bottom of the hole

[0269] V. Breaking elongation, breaking strength The above-mentioned photosensitive resin compositions 1 to 18 and comparative photosensitive resin compositions 1 to 3 were spin-coated onto aluminum substrates so that the final film thickness after curing would be 10 μm, and then pre-baked on a hot plate at 110°C for 4 minutes to obtain photosensitive resin films.

[0270] The wafer was then cured in an oven at 200°C for 2 hours while purging with nitrogen, yielding a cured photosensitive resin film. The wafer with the cured film was then cleaved into strips measuring 10 mm wide and 60 mm long, and the cured film was peeled off from the substrate by immersing in 20% by mass hydrochloric acid. The resulting cured film was measured for breaking elongation and breaking strength using an autograph AGX-1KN manufactured by Shimadzu Corporation. Ten measurements were performed per sample, and the average values ​​are shown in Table 4. A high breaking elongation is preferred, more preferably 20% or higher. A high breaking strength is preferred, more preferably 100 MPa or higher.

[0271] [Table 4]

[0272] As shown in Table 4, the negative-type photosensitive resin composition of the present invention exhibited a good pattern shape in alkaline solvent development, and it was found that it was possible to open a minimum hole dimension of 5 μm or less in a finished film thickness of 5 μm, and to achieve an aspect ratio of 1.

[0273] The above results demonstrate that the present invention is comparable to a comparative photosensitive resin composition containing a basic compound, which is capable of providing high resolution.

[0274] That is, in a negative-tone photosensitive resin composition using the polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, or polybenzoxazole precursor-containing polymer of the present invention as a base resin, when an onium salt capable of improving resolution performance is used, the composition exhibits resolution performance equivalent to that when a basic compound is used, and it has also been shown that the use of the onium salt of the present invention can eliminate the poor storage stability that occurs when a basic compound is used in combination with a base resin of polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, or polybenzoxazole precursor-containing polymer.

[0275] Furthermore, since the base resin of the negative-type photosensitive resin composition of the present invention is polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, or a polymer containing a polybenzoxazole precursor, it has been shown that the composition exhibits good mechanical strength and is suitable for use as an interlayer insulating film or a surface protective film.

[0276] Furthermore, it has been shown that the polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor-containing polymer, which are the base resins of the negative-type photosensitive resin composition of the present invention, are easily soluble in commonly used and safe organic solvents.

[0277] The present specification includes the following aspects. [1]: A negative photosensitive resin composition, (A) an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof; (B) a photoacid generator; (C) one or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having two or more methylol groups or alkoxymethylol groups on average per molecule, a compound in which the hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which the hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), a compound having a substituent (C-1) represented by the following formula (C-15), and a compound having two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2), [ka] (In the formula, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, s represents 1 or 2, and u is a number satisfying 1≦u≦3.) (D) an onium salt represented by the following general formula (1), [ka] (In the formula, A represents iodine, sulfur, phosphorus, or nitrogen; Q may be the same or different, and each may be linked or substituted, and each may represent a monovalent hydrocarbon group having 1 to 100 carbon atoms, optionally interrupted by a heteroatom; E - represents the anion of an organic or inorganic acid salt, and m represents 2 when A is iodine, 3 when A is sulfur, and 4 when A is phosphorus or nitrogen. (E) a solvent; A negative photosensitive resin composition comprising: [2]: The negative photosensitive resin composition according to the above [1], wherein the component (D) is a quaternary ammonium salt represented by the following general formula (1-1), in which A in the general formula (1) is nitrogen. [ka] (In the formula, Q1, Q2, Q3, and Q4 may be the same or different, may be linked to each other, may be substituted, and may be a monovalent hydrocarbon group having 1 to 100 carbon atoms, optionally interrupted by a heteroatom; E - represents the anion of the same organic acid salt or inorganic acid salt as above. [3]: E in the general formula (1) in the component (D) - The negative photosensitive resin composition according to the above [1] or [2], wherein is an anion of an organic carboxylic acid represented by the following general formula (6): [ka] (In the formula, R E represents a hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. [4]: The component (A) is a negative photosensitive resin composition according to the above [1], [2] or [3], which is an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, which is a reaction product of a diamine containing at least one diamine represented by the following general formula (2) or the following general formula (3) with at least one tetracarboxylic dianhydride represented by the following general formula (4) or a dicarboxylic acid or dicarboxylic acid halide represented by the following general formula (5): [ka] [ka] [ka] [ka] (In the formula, L1 represents a tetravalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. L2 represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. T represents a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, -OCOR T , -OSO2R T , -OSO3R T However, R T is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. [5]: The negative photosensitive resin composition according to the above [1], [2], [3] or [4], wherein the acid generated from the photoacid generator in the component (B) is an organic sulfonic acid represented by the following general formula (7): [ka] (In the formula, R U represents a hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. [6]: The negative photosensitive resin composition according to [1], [2], [3], [4] or [5] above, wherein the component (A) is an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, which are reaction products of one or more of tetracarboxylic dianhydrides represented by the following general formula (8), or dicarboxylic acids or dicarboxylic acid halides represented by the following general formula (9): [ka] [ka] (wherein Z is an alicyclic structure having 3 to 20 carbon atoms, an alicyclic structure in which aromatic rings are linked, or an alicyclic structure containing or interposed with a heteroatom) structureor an alicyclic structure formed by linking aromatic rings. T is a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, -OCO2R T , -OSO2R T , -OSO3R T wherein j represents 0 or 1, and when j is 0, the phthalic anhydride structure in the general formula (8) and the cyclic structure Z, and the benzoic acid structure in the general formula (9) and the cyclic structure Z are directly bonded, and when j is 1, X1 and X2 represent a divalent linking group. [7]: The negative photosensitive resin composition according to [6] above, wherein the alicyclic structure Z in the general formulae (8) and (9) is a structure represented by the following general formula (10) or (11): [ka] (In the formula, the dotted line represents a bond, and k represents an integer of 0 or 1 or more. When k=0, Y2 represents a divalent group selected from any one of the following general formulae (13), (14), (15) and (16). When k=1, Y1 represents a divalent group selected from any one of the following general formulae (17), (18), and (19), and Y2 represents a divalent group selected from any one of the following general formulae (13), (14), (15), and (16). When k is 2 or more, Y1 represents the following general formula (17), and Y2 represents a divalent group selected from the following general formulas (13), (14), (15) and (16). R 1 , R 2 , R 3 , R 4 and R in the following formula (16) 5 , R 6 represents the same or different substituents, and may be a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 12 carbon atoms, Condition or a cyclic alkyl group or R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are bonded to form an alicyclic or aromatic ring.) [ka] (wherein the dotted line represents a bond, R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 represents the same or different substituents, and may be a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 12 carbon atoms, Condition Or it represents a cyclic alkyl group. m and p each represent an integer of 0 or 1 to 9; n represents 0 or 1; Y3 represents a divalent group selected from any one of the following general formulae (12), (13), (14), (15), (16), (17), (18), and (19). [ka] (wherein the dotted line represents a bond, R 5 , R 6 is the same as above. R 7 is a methyl group, an ethyl group, a linear or branched chain with 3 to 12 carbon atoms Condition or a cyclic alkyl group. [8]: The negative photosensitive resin composition according to the above [6] or [7], wherein the divalent linking groups X1 and X2 in the general formula (8) and the general formula (9) have a structure represented by any one of the following general formulas (20), (21), (22), (23), (24) and (25): [ka] (In the formula, the dotted line represents a bond.) [9]: The negative photosensitive resin composition according to [4], [5], [6], [7] or [8] above, wherein the diamine represented by the general formula (2) is a diamine represented by the following general formula (26): [ka]

[10] : The negative photosensitive resin composition according to [1], [2], [3], [4], [5], [6], [7], [8] or [9] above, wherein the component (A) is an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, which is a reaction product further containing a tetracarboxylic acid diester compound represented by the following general formula (27): [ka] (Wherein W1 is a tetravalent organic group, R 16 is represented by the following general formula (28): [ka] (In the formula, the dotted line represents a bond, V1 represents an (r+1)-valent organic group, Rf represents a linear, branched or cyclic alkyl group or aromatic group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms, r represents 1, 2 or 3, and q represents 0 or 1.)

[11] : R in the general formula (27) 16 is an organic group selected from the group represented by the following general formulae (29), (30), (31) and (32): [ka] [ka] [ka] [ka] (In the formula, the dotted line represents a bond. Rf is the same as defined above. Ra and Rb represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. V2 and V3 represent a linear or branched alkylene group having 1 to 6 carbon atoms. n1 represents an integer of 0 to 6, n2 represents an integer of 1 to 6, n3 represents an integer of 0 to 6, n4 represents an integer of 1 to 6, n5 represents an integer of 0 to 6, and n6 represents 0 or 1.)

[12] : R in the general formula (27) 16 is a group represented by the following general formula (28-1): [ka] (In the formula, the dotted line represents a bond. Rf is the same as above.)

[13] : The component (A) is the negative photosensitive resin composition according to the above [6], [7], [8], [9],

[10] ,

[11] or

[12] , which is an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, wherein the alicyclic structure Z of the above general formula (8) is a reaction product with one or more of a tetracarboxylic dianhydride of the following general formula (33) or (34) and / or a dicarboxylic acid or a dicarboxylic acid halide selected from structures represented by the following formulas (35), (36), (37), (38), (39) and (40): [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (wherein the dotted line represents a bond, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 represents the same or different substituents, and may be a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 12 carbon atoms, Condition or a cyclic alkyl group or R 1 , R 2 , R 3 , R 4 , R 5 , R 6 R represents an alicyclic or aromatic ring. 7 is a methyl group, an ethyl group, a linear or branched chain with 3 to 12 carbon atoms Condition or a cyclic alkyl group. 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 represents the same or different substituents, and may be a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 12 carbon atoms, Condition or a cyclic alkyl group.

[14] : (1) A step of applying the negative photosensitive resin composition of [1], [2], [3], [4], [5], [6], [7], [8], [9],

[10] ,

[11] ,

[12] or

[13] above onto a substrate to form a photosensitive film; (2) a step of exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask after heat-treating the photosensitive film; (3) developing the exposed photosensitive film using an alkaline aqueous developer; A pattern forming method comprising:

[15] : In the pattern forming method, (4) A step of post-curing the developed photosensitive film by heating at a temperature of 100 to 300°C. The pattern forming method according to

[14] above, comprising:

[16] : An interlayer insulating film comprising a cured product of the negative photosensitive resin composition according to [1], [2], [3], [4], [5], [6], [7], [8], [9],

[10] ,

[11] ,

[12] or

[13] above.

[17] : A surface protective film comprising a cured product of the negative photosensitive resin composition according to [1], [2], [3], [4], [5], [6], [7], [8], [9],

[10] ,

[11] ,

[12] or

[13] above.

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

[16] above.

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

[17] above.

[0278] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. A negative photosensitive resin composition, (A) an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof; (B) a photoacid generator; (C) one or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or a formaldehyde-alcohol, a phenol compound having two or more methylol groups or alkoxymethylol groups on average per molecule, a compound in which the hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group or a group having a glycidyl group, a compound in which the hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), a compound having a substituent (C-1) represented by the following formula (C-15), and a compound having two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2); 【Chemistry 1】 (In the formula, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, s represents 1 or 2, and u is a number satisfying 1≦u≦3.) (D) an onium salt represented by the following general formula (1), 【Chemistry 2】 (wherein A represents iodine, sulfur, phosphorus, or nitrogen; Q may be the same or different, and each may be linked or substituted, and may be a monovalent hydrocarbon group having 1 to 100 carbon atoms, optionally interrupted by a heteroatom; E － represents an anion of an organic carboxylic acid represented by the following general formula (6), and m represents 2 when A is iodine, 3 when A is sulfur, and 4 when A is phosphorus or nitrogen. 【Transformation 3】 (In the formula, R Ｅ represents a hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. (E) a solvent; and A negative photosensitive resin composition, wherein the acid generated from the photoacid generator in the component (B) is an organic sulfonic acid represented by the following general formula (7): 【Chemistry 4】 (In the formula, R U represents a hydrocarbon group having 1 to 100 carbon atoms which may be substituted with or may be interrupted by a heteroatom.)

2. The negative photosensitive resin composition according to claim 1, wherein the component (D) is a quaternary ammonium salt represented by the following general formula (1-1), in which A in the general formula (1) is nitrogen: 【Transformation 5】 (In the formula, Q １ , Q ２ , Q ３ , Q ４ may be the same or different, may be linked to each other, may be substituted, and may be a monovalent hydrocarbon group having 1 to 100 carbon atoms, optionally interrupted by a heteroatom; E － represents the anion of the same organic carboxylic acid as above.

3. 2. The negative photosensitive resin composition according to claim 1, wherein the component (A) is an alkali-soluble resin containing at least one structure selected from the group consisting of a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, which are reaction products of a diamine containing at least one diamine represented by the following general formula (2) or the following general formula (3) with at least one tetracarboxylic dianhydride represented by the following general formula (4) or a dicarboxylic acid or dicarboxylic acid halide represented by the following general formula (5): 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 (In the formula, L １ represents a tetravalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. ２ represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may be substituted with or may be interrupted by a heteroatom; T represents a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, —OCO ２ R Ｔ , -OSO ２ R Ｔ , -OSO ３ R Ｔ However, R Ｔ is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with or interrupted by a heteroatom.

4. 2. The negative photosensitive resin composition according to claim 1, wherein the component (A) is an alkali-soluble resin containing at least one structure selected from the group consisting of a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, which are reaction products of one or more of a tetracarboxylic dianhydride represented by the following general formula (8), or a dicarboxylic acid or a dicarboxylic acid halide represented by the following general formula (9): 【Chemistry 10】 【Chemistry 11】 (In the formula, Z represents an alicyclic structure having 3 to 20 carbon atoms, an alicyclic structure in which aromatic rings are linked, or an alicyclic structure containing or having a heteroatom interposed therebetween, or an alicyclic structure in which aromatic rings are linked. T represents a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, —OCO ２ R Ｔ , -OSO ２ R Ｔ , -OSO ３ R Ｔ j represents 0 or 1, and when j is 0, the phthalic anhydride structure and the cyclic structure Z in the general formula (8) are directly bonded, and when j is 1, X １ , X ２ represents a divalent linking group.

5. 5. The negative photosensitive resin composition according to claim 4, wherein the alicyclic structure Z in the general formulas (8) and (9) is a structure represented by the following general formula (10) or (11): 【Chemistry 12】 (In the formula, the dotted line represents a bond, and k represents an integer of 0 or 1 or more. When k=0, Y ２ represents a divalent group selected from the following general formulae (13), (14), (15) and (16). When k=1, Y １ represents a divalent group selected from the following general formulas (17), (18), and (19), and Y ２ represents a divalent group selected from the following general formulae (13), (14), (15) and (16). When k is 2 or more, Y １ represents the following general formula (17), and Y ２ represents a divalent group selected from the following general formulae (13), (14), (15) and (16). R １ , R ２ , R ３ , R ４ and R in the following formula (16) ５ , R ６ represent the same or different substituents, and R １ , R ２ , R ３ , R ４ , R ５ , R ６ are bonded to form an alicyclic or aromatic ring.) 【Chemistry 13】 (wherein the dotted line represents a bond, R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , R １５ represents the same or different substituents, which are a hydrogen atom, a methyl group, an ethyl group, or a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms. m and p each represent an integer of 0 or 1 to 9; n represents 0 or 1; Y ３ represents a divalent group selected from any one of the following general formulas (12), (13), (14), (15), (16), (17), (18), and (19). 【Chemistry 14】 (wherein the dotted line represents a bond, R ５ , R ６ is the same as above. ７ represents a methyl group, an ethyl group, or a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms.

6. The divalent linking group X of the general formula (8) and the general formula (9) １ , X ２ The negative photosensitive resin composition according to claim 4, wherein the compound (I) has a structure represented by any one of the following general formulas (20), (21), (22), (23), (24), and (25): 【Chemistry 15】 (In the formula, the dotted line represents a bond.)

7. 4. The negative photosensitive resin composition according to claim 3, wherein the diamine represented by the general formula (2) is a diamine represented by the following general formula (26): 【Chemistry 16】

8. 2. The negative photosensitive resin composition according to claim 1, wherein the component (A) is an alkali-soluble resin containing at least one structure selected from the group consisting of a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, which is a reaction product further containing a tetracarboxylic acid diester compound represented by the following general formula (27): 【Chemistry 17】 (Wherein W1 is a tetravalent organic group, R １６ is represented by the following general formula (28): [Chemistry 18] (wherein the dotted line represents a bond, V １ is an (r+1)-valent organic group, Rf is a linear, branched or cyclic alkyl group or aromatic group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms, r is 1, 2 or 3, and q is 0 or 1.

9. R in the general formula (27) １６ 9. The negative photosensitive resin composition according to claim 8, wherein is an organic group selected from the groups represented by the following general formulas (29), (30), (31) and (32): 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 (In the formula, the dotted line represents a bond. Rf is the same as above, Ra and Rb are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and V ２ and V ３ represents a linear or branched alkylene group having 1 to 6 carbon atoms, n1 represents an integer of 0 to 6, n2 represents an integer of 1 to 6, n3 represents an integer of 0 to 6, n4 represents an integer of 1 to 6, n5 represents an integer of 0 to 6, and n6 represents 0 or 1.

10. R in the general formula (27) １６ is a group represented by the following general formula (28-1): 【Chemistry 23】 (In the formula, the dotted line represents a bond. Rf is the same as above.)

11. The negative photosensitive resin composition according to claim 4, wherein the component (A) is an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and a precursor structure thereof, wherein the alicyclic structure Z of the general formula (8) is a reaction product with a tetracarboxylic dianhydride of the following general formula (33) or (34) and / or a dicarboxylic acid or dicarboxylic acid halide selected from structures represented by the following formulas (35), (36), (37), (38), (39), and (40): 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 【Chemistry 27】 【Chemistry 28】 【Chemistry 29】 【Transformation 30】 【Chemistry 31】 (wherein the dotted line represents a bond, R １ , R ２ , R ３ , R ４ , R ５ , R ６ represent the same or different substituents, and R １ , R ２ , R ３ , R ４ , R ５ , R ６ R represents a ring formed by bonding with each other to form an alicyclic or aromatic ring. ７ represents a methyl group, an ethyl group, or a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms. ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , R １５ represent the same or different substituents, which are a hydrogen atom, a methyl group, an ethyl group, or a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms.

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

13. In the pattern forming method, (4) A step of heating the developed photosensitive film at a temperature of 100 to 300°C to post-cure it. The pattern forming method according to claim 12, further comprising:

14. An interlayer insulating film comprising a cured product of the negative photosensitive resin composition according to any one of claims 1 to 11.

15. A surface protection film comprising a cured product of the negative photosensitive resin composition according to any one of claims 1 to 11.

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

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

Images