Negative photosensitive resin composition, pattern forming method, curing coating forming method, interlayer insulating film, surface protective film

Abstract

This invention relates to negative photosensitive resin compositions, patterning methods, curing film forming methods, interlayer insulating films, and surface protective films. The objective of this invention is to provide negative photosensitive resin compositions capable of forming highly rectangular micro-patterns with high resolution, exhibiting good mechanical properties even during low-temperature curing, and whose adhesion does not deteriorate before and after high-temperature and high-humidity testing. A negative photosensitive resin composition comprises: (A) an alkali-soluble resin containing at least one structure selected from polyimide, polybenzoxazole, polyamide-imide, and their precursor structures; (B) a crosslinking polymer compound containing structural units represented by the following general formula (1) and having groups that crosslink with component (A); (C) a compound that generates acid upon light; and (D) a thermal crosslinking agent.

Description

[Technical Field]

[0001] This invention relates to a negative photosensitive resin composition, a pattern forming method using the negative photosensitive resin composition that can be developed with an alkaline aqueous solution, a method for forming a hardened film, an interlayer insulating film, a surface protective film, and electronic components. [Background Technology]

[0002] With the miniaturization and increasing performance of various electronic devices such as personal computers, digital cameras, and mobile phones, the requirements for even smaller, thinner, and higher-density semiconductor components are also rapidly increasing. Consequently, the interlayer insulating films and surface protective films of semiconductor components are required to possess superior electrical properties, heat resistance, and mechanical properties.

[0003] In high-density mounting technologies such as three-dimensional stacking, photosensitive insulating materials that can form patterns on the substrate, such as polyimide film, have been used as protective films and insulating layers since the past. Their insulation, mechanical properties, and adhesion to the substrate continue to receive attention and are now being actively developed.

[0004] Furthermore, in recent years, regarding the formation of micro-wire patterns smaller than 2μm, a wiring formation method using damascene processing has been proposed (Non-Patent Document 1). In this wiring formation method, the pattern shape formed from the photosensitive insulating film material requires a pattern with good rectangularity, considering the formation of metal wires using electrolytic plating. Also, considering the processing of CMP processes, it is necessary to have low substrate warpage and excellent mechanical strength.

[0005] Polyimide possesses excellent electrical and mechanical properties and exhibits heat resistance exceeding 300°C, making it useful as a surface protective film for semiconductor devices, an interlayer insulating film, and a wiring protective insulating film for circuit formation. Previously, as a photosensitive polyimide-based material, some proposals utilized polyamic acid, a precursor to polyimide, for example, by introducing photosensitive groups into the carboxyl groups of polyamic acid using ester bonds (Patent Document 1, Patent Document 2). However, in these proposals, after forming a patterned film, imidization treatment at temperatures exceeding 300°C is required to obtain the desired polyimide film. To withstand this high temperature, there are limitations on the substrate material or problems with copper oxidation in the wiring.

[0006] Regarding improvements, in order to lower the post-curing temperature, it has been proposed to use a photosensitive polyimide of a solvent-soluble resin that has been imidized (Patent Document 3, Patent Document 4). Although Patent Document 3 proposes a negative photosensitive composition containing a closed-ring polyimide and discusses the resolution, it only describes the adhesion and does not describe the mechanical strength.

[0007] Patent document 4 proposes a positive photosensitive resin composition consisting of an alkali-soluble closed-ring polyimide, a quinone diazide compound, and a thermal crosslinking agent with hydroxymethyl groups. It is a material with excellent resolution, but there is no record of the pattern shape. There is room for improvement in the elongation at break during low-temperature curing.

[0008] Patent document 5 proposes a negative photosensitive resin composition consisting of an alkali-soluble closed-ring polyimide, a photoradical initiator, a thermal crosslinking agent with hydroxymethyl groups, and a polymerization inhibitor. It is a material with good rectangularity and excellent pattern shape, but there is no record of the resolution of the micro-pattern or the mechanical strength.

[0009] Furthermore, regarding the improvement of the mechanical strength of the hardened film, some have proposed adding (meth)acrylic resin to balance photolithographic properties and the physical properties of the hardened film (Patent Documents 6, 7, and 8). Patent Document 6 proposes a positive photosensitive resin composition obtained by adding crosslinking acrylic resin to an alkali-soluble resin with phenolic hydroxyl groups, but the exploration of miniaturization and pattern shape is insufficient, and there is room for improvement in photosensitive properties.

[0010] Patent documents 7 and 8 propose a positive photosensitive resin composition formed by a polymer selected from polyimide, polybenzoxazole and their precursors and acrylic resin, which is a material with excellent hardened film properties and stress, but there is no record of photolithography performance.

[0011] Therefore, considering the increasing density and integration of chips in the future, the miniaturization of patterns in the rewiring technology of insulating protective films is also progressing. As far as photosensitive resin composition is concerned, there is a strong expectation for a composition that can achieve high resolution and good rectangularity of pattern shape without compromising the pattern shape obtained by heating and the excellent characteristics of the protective film such as mechanical properties and adhesion.

[0012] [Background Technical Documents]

[0013] [Patent Literature]

[0014] [Patent Document 1] Japanese Patent Application Publication No. 49-115541

[0015] [Patent Document 2] Japanese Patent Application Publication No. 55-45746

[0016] [Patent Document 3] Japanese Patent Application Publication No. 2006-133757

[0017] [Patent Document 4] Japanese Patent Application Publication No. 2006-313237

[0018] [Patent Document 5] International Publication No. 2016 / 158389

[0019] [Patent Document 6] International Publication No. 2013 / 118680

[0020] [Patent Document 7] Japanese Patent Application Publication No. 2015-129791

[0021] [Patent Document 8] Japanese Patent Application Publication No. 2015-200819

[0022] [Non-patent literature]

[0023] [Non-Patent Literature 1] Proc. ECTC, Las Vegas, USA, May 29-Jun 01, 2018, pp. 587-593 [Summary of the Invention]

[0024] [The problem that the invention aims to solve]

[0025] In view of the above facts, the present invention aims to provide a negative photosensitive resin composition that is soluble in alkaline aqueous solution, can form fine patterns with high rectangularity and obtain high resolution, and has good mechanical properties and adhesion to the substrate even when cured at low temperature.

[0026] [Methods for solving the problem]

[0027] To address the aforementioned issues, the present invention provides a negative photosensitive resin composition comprising:

[0028] (A) An alkali-soluble resin containing at least one structure selected from polyimide structure, polyamide structure, polybenzoxazole structure, polyamide-imide structure, and their precursor structures.

[0029] (B) A cross-linking polymer compound containing a structural unit represented by the following general formula (1) and having a group that can cross-link with the aforementioned component (A);

[0030] (C) Compounds that produce acids due to light; and

[0031] (D) Crosslinking agents other than those in (B) above.

[0032] [Chemistry 1]

[0033]

[0034] In the formula, R 1 R represents a hydrogen atom or a methyl group. 2It is a straight-chain, branched, or cyclic aliphatic saturated hydrocarbon group with a carbon number of 1 to 15 and a carbon number of 6 to 15, an aromatic hydrocarbon group, a benzyl group, or a naphthylmethyl group, with a carbon number of 1 to 15 and a carbon number of (n+1) valence. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups may also be replaced by oxygen atoms. n is an integer from 1 to 5. X1 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R) 3 OH)-. R 3 It consists of a divalent, linear, branched, or cyclic aliphatic saturated hydrocarbon groups with 1 to 12 carbon atoms, or aromatic hydrocarbon groups with 6 to 12 carbon atoms. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms. p is 0 or 1.

[0035] Such a negative photosensitive resin composition is soluble in alkaline aqueous solution, can form fine patterns and obtain high resolution, and even when cured at low temperature, it has good mechanical properties and good adhesion to the substrate.

[0036] Furthermore, in the negative photosensitive resin composition of the present invention, the aforementioned (B) is preferably a crosslinkable polymeric compound containing a structural unit represented by the following general formula (2), and preferably containing a structural unit represented by the following general formula (3) having a group that can crosslink with the aforementioned component (A).

[0037] [Chemistry 2]

[0038]

[0039] In the formula, R 4 Representing a hydrogen atom or a methyl group, X2 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R) 5 OH)-. R 5 It consists of a divalent, linear, branched, or cyclic aliphatic saturated hydrocarbon groups with 1 to 12 carbon atoms, or aromatic hydrocarbon groups with 6 to 12 carbon atoms. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms. p is 0 or 1.

[0040] [Chemistry 3]

[0041]

[0042] In the formula, R 6 R represents a hydrogen atom or a methyl group. 7 The group represents an oxazoline group, isocyanate group, terminal isocyanate group, oxacyclobutyl group, or epoxy group. X3 is -C(=O)-O-, or phenylene or naphthylene. p is 0 or 1.

[0043] Such a negative photosensitive resin composition can form finer patterns and achieve high resolution, and even when cured at low temperatures, it has good mechanical properties and good adhesion to the substrate.

[0044] Further, it is preferable that the component (B) is a crosslinkable polymer compound containing a structural unit represented by the following general formula (2) and containing any one or both of a structural unit represented by the following general formula (4) and a structural unit represented by the following general formula (4').

[0045] [Chemical formula 4]

[0046]

[0047] In the formula, R 8 represents a hydrogen atom or a methyl group, and each X4 is independently -C(=O)-O-, or a phenylene group or a naphthylene group. R 9 is a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may also contain a hydroxyl group, an ester group, an ether group, or an aromatic hydrocarbon, and R 10 is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or may bond with R 9 to form a ring. R 11 is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and R 12 is a hydrogen atom, or a linear alkyl group having 1 to 6 carbon atoms, and may bond with R 9 to form a ring. m is 0 or 1. p is 0 or 1. R 13’ represents a hydrogen atom or a methyl group, R 14’ represents a single bond or an alkylene group, and R 15’ is a blocked isocyanate group. 0 < b2 < 1.0, 0 ≤ b4 < 1.0, 0 ≤ b4' < 1.0, 0 < b4 + b4' < 1.0, 0 < b2 + b4 + b4' ≤ 1.0 or 0 < b2 + b4 ≤ 1.0 and 0 < b2 + b4' ≤ 1.0. R 4 represents a hydrogen atom or a methyl group, and each X2 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R 5 OH)-. R 5 is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced by an oxygen atom.

[0048] Furthermore, it is more preferable that the component (B) is a crosslinkable polymer compound containing a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (5), and containing any one or both of a structural unit represented by the following general formula (4) and a structural unit represented by the following general formula (4').

[0049] [Chemical formula 5]

[0050]

[0051] In the formula, R 13represents a hydrogen atom or a methyl group, R 14 is a linear, branched or cyclic aliphatic saturated hydrocarbon group with 1 to 12 carbon atoms and a valence of (l + 1), and the carbon atoms of the aliphatic saturated hydrocarbon group may also be replaced by oxygen atoms. Each X5 is independently -C(=O)-O-, -C(=O)-NH-, -C(=O)-N(R 15 OH)-, or a phenylene group or a naphthylene group. R 15 is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group with 1 to 12 carbon atoms, an aromatic hydrocarbon group with 6 to 12 carbon atoms, and the carbon atoms of the aliphatic saturated hydrocarbon group may also be replaced by oxygen atoms. I is 0 or 1. 0 < b2 < 1.0, 0 ≤ b4 < 1.0, 0 ≤ b4' < 1.0, 0 < b4 + b4' < 1.0, 0 ≤ b5 < 1.0, 0 < b2 + b4 + b4' + b5 ≤ 1.0 or 0 < b2 + b4 + b5 ≤ 1.0 and 0 < b2 + b4' + b5 ≤ 1.0. R 4 represents a hydrogen atom or a methyl group, and each X2 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R 5 OH)-. R 5 is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group with 1 to 12 carbon atoms, an aromatic hydrocarbon group with 6 to 12 carbon atoms, and the carbon atoms of the aliphatic saturated hydrocarbon group may also be replaced by oxygen atoms. p is 0 or 1. R 8 represents a hydrogen atom or a methyl group, and each X4 is independently -C(=O)-O-, or a phenylene group or a naphthylene group. R 9 is a linear, branched or cyclic alkylene group with 1 to 15 carbon atoms that may also contain a hydroxyl group, an ester group, an ether group, or an aromatic hydrocarbon, R 10 is a hydrogen atom, a linear, branched or cyclic alkyl group with 1 to 6 carbon atoms, or may bond with R 9 to form a ring. R 11 is a hydrogen atom, or a linear, branched or cyclic alkyl group with 1 to 6 carbon atoms, R 12 is a hydrogen atom, or a linear alkyl group with 1 to 6 carbon atoms, and may bond with R 9 to form a ring. m is 0 or 1. R​​​​​​​​When such a crosslinking polymer compound is added to (A) an alkali-soluble resin containing at least one structure selected from polyimide, polybenzoxazole, polyamide-imide, and their precursor structures, sufficient alkali solubility can be maintained, and a pattern with good rectangularity can be obtained. Furthermore, due to the presence of crosslinking groups with excellent crosslinking properties, it will undergo a crosslinking reaction with the phenolic hydroxyl groups of the alkali-soluble resin in (A), and the adhesion to the substrate after reliability testing will not deteriorate.

[0053] Furthermore, the aforementioned component (D) preferably includes one or more crosslinking agents selected from amino condensates modified with formaldehyde or formaldehyde-alcohol, and phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups per molecule.

[0054] If it is such a (D) component, the alkali solubility of the photosensitive resin composition becomes appropriate, and sufficient cross-linking reaction is carried out at the PEB (Post Exposure Bake) temperature in patterning by photolithography, so that good patterning by photolithography can be achieved.

[0055] It is preferable to contain 10 to 100 parts by mass of the aforementioned component (B) relative to 100 parts by mass of component (A) above.

[0056] Within this range, sufficient mechanical properties of the hardened film can be obtained while maintaining photolithographic characteristics, especially elongation and tensile strength.

[0057] It should contain at least one of the following: (E) alkaline compounds, (F) hot acid generators, (G) antioxidants, and (H) silane compounds.

[0058] By including component (E), not only can the dissolution contrast during photolithographic patterning be improved, but the pattern shape can also be controlled. Component (F), through further cross-linking and curing reactions, can further improve the mechanical strength, chemical resistance, and adhesion of the obtained pattern or film. Component (G) can suppress the degradation of physical properties caused by the oxidation of the cured film during reliability tests such as high humidity tests and thermal shock tests, and can form a more ideal cured film. Component (H) can further improve the adhesion of the obtained pattern or film to the substrate.

[0059] Furthermore, the present invention provides a pattern forming method, comprising the following steps:

[0060] (1) The above negative photosensitive resin composition is coated on a substrate to form a photosensitive film;

[0061] (2) Then, after heat treatment, the aforementioned photosensitive film is exposed to high-energy rays or electron beams with wavelengths of 190–500 nm using a spacer photomask; and

[0062] (3) After irradiation, the substrate that has undergone heat treatment is developed using an alkaline aqueous solution.

[0063] If such a pattern forming method is used, by using the above-mentioned negative photosensitive resin composition, which is soluble in alkaline aqueous solution, fine patterns can be formed and high resolution can be obtained.

[0064] Furthermore, the present invention provides a method for forming a hardened film, comprising the following steps:

[0065] The patterned film obtained by the above patterning method is heated and then hardened at a temperature of 100–300°C.

[0066] Such a method of forming a hardened film can produce a hardened film (pattern) with good mechanical properties even when hardened at low temperatures.

[0067] Furthermore, the present invention provides an interlayer insulating film, which is composed of a hardened film formed by curing the above-mentioned negative photosensitive resin composition.

[0068] Furthermore, the present invention provides a surface protective film, which is composed of a hardened film formed by curing the above-mentioned negative photosensitive resin composition.

[0069] The hardened coating formed by curing the negative photosensitive resin composition of the present invention has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength and chemical resistance to alkaline stripping solutions, etc. It also has excellent reliability for semiconductor devices when used as a protective coating. Therefore, it is suitable as a protective coating (interlayer insulating film or surface protective film) for electrical and electronic parts, semiconductor devices, etc.

[0070] Furthermore, the present invention provides an electronic component having the aforementioned interlayer insulating film or surface protective film.

[0071] Such protective films (interlayer insulating films or surface protective films) are effective in insulating films for semiconductor components, including those used for rewiring, and for insulating films for multilayer printed circuit boards, due to their heat resistance, chemical resistance, and insulation properties, and can be used to manufacture electronic components with high reliability.

[0072] [The effects of the invention]

[0073] As described above, the present invention can provide a negative photosensitive resin composition that is soluble in alkaline aqueous solution, can form fine patterns with high rectangularity and obtain high resolution, and has good mechanical properties and good adhesion to the substrate even when cured at low temperature. [Attached Image Description]

[0074] [ Figure 1 [ ] is an explanatory diagram showing the method for measuring contact strength.

Detailed Implementation Methods

[0075] As mentioned above, we are seeking a photosensitive resin composition that is soluble in alkaline aqueous solutions, can form fine patterns with high rectangularity and achieve high resolution, and has good mechanical properties and adhesion to the substrate even when cured at low temperatures.

[0076] The inventors of this application have made efforts to achieve the above-mentioned objectives and have discovered a negative photosensitive resin composition containing: (A) an alkali-soluble resin containing at least one structure selected from polyimide, polyamide, polybenzoxazole, polyamide-imide, and their precursor structures; (B) a crosslinking polymer compound containing a structural unit represented by the following general formula (1) and having a group that can crosslink with component (A); (C) a compound that generates acid due to light; and (D) a crosslinking agent. The pattern obtained by using the negative photosensitive resin composition is a fine and rectangular pattern shape, and the obtained hardened film has good mechanical properties and good adhesion to the substrate.

[0077] [Chemistry 6]

[0078]

[0079] In the formula, R 1 R represents a hydrogen atom or a methyl group. 2 It is a straight-chain, branched, or cyclic aliphatic saturated hydrocarbon group with a carbon number of 1 to 15 and a carbon number of 6 to 15, an aromatic hydrocarbon group, a benzyl group, or a naphthylmethyl group, with a carbon number of 1 to 15 and a carbon number of (n+1) valence. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups may also be replaced by oxygen atoms. n is an integer from 1 to 5. X1 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R) 3 OH)-. R 3 It consists of a divalent, linear, branched, or cyclic aliphatic saturated hydrocarbon groups with 1 to 12 carbon atoms, or aromatic hydrocarbon groups with 6 to 12 carbon atoms. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms. p is 0 or 1.

[0080] Furthermore, it was discovered that the protective film obtained by pattern formation and heating using the aforementioned negative photosensitive resin composition exhibits excellent mechanical properties and superior adhesion after high temperature and humidity testing. In other words, the hardened film obtained by patterning using the aforementioned negative photosensitive resin composition is found to be excellent as a protective film for electrical and electronic components and an insulating protective film, thus completing the present invention. In addition, in this specification, electrical-electronic components are generally referred to as "electronic components".

[0081] That is, the present invention provides a negative photosensitive resin composition containing:

[0082] (A) An alkali-soluble resin containing at least one structure selected from polyimide structure, polyamide structure, polybenzoxazole structure, polyamide-imide structure, and their precursor structures.

[0083] (B) A cross-linking polymer compound containing a structural unit represented by the above general formula (1) and having a group that can cross-link with the aforementioned component (A);

[0084] (C) Compounds that produce acids due to light; and

[0085] (D) Crosslinking agents other than those in (B) above.

[0086] The present invention will now be described in detail, but the present invention is not limited thereto.

[0087] [Negative photosensitive resin composition]

[0088] The negative photosensitive resin composition of the present invention will be described.

[0089] The negative photosensitive resin composition of the present invention contains:

[0090] (A) An alkali-soluble resin containing at least one structure selected from polyimide structure, polyamide structure, polybenzoxazole structure, polyamide-imide structure, and their precursor structures.

[0091] (B) A cross-linked polymer containing a structural unit represented by the following general formula (1) and having a group that can cross-link with component (A);

[0092] (C) Compounds that produce acids due to light; and

[0093] (D)(B) Crosslinking agents other than components.

[0094] [Chemistry 7]

[0095]

[0096] In the formula, R 1 R represents a hydrogen atom or a methyl group. 2 It is a straight-chain, branched, or cyclic aliphatic saturated hydrocarbon group with a carbon number of 1 to 15 and a carbon number of 6 to 15, an aromatic hydrocarbon group, a benzyl group, or a naphthylmethyl group, with a carbon number of 1 to 15 and a carbon number of (n+1) valence. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups may also be replaced by oxygen atoms. n is an integer from 1 to 5. X1 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R) 3 OH)-. R 3It consists of a divalent, linear, branched, or cyclic aliphatic saturated hydrocarbon groups with 1 to 12 carbon atoms, or aromatic hydrocarbon groups with 6 to 12 carbon atoms. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms. p is 0 or 1.

[0097] The aforementioned negative photosensitive resin composition can be developed with alkali. Furthermore, in addition to components (A), (B), (C), and (D) mentioned above, the aforementioned negative photosensitive resin composition may also contain, as needed, (E) an alkaline compound, (F) a thermal acid generator, (G) an antioxidant, and (H) a silane compound. These components will be described in detail below.

[0098] [(A) Alkali-soluble resin]

[0099] The alkali-soluble resin (A) of the present invention contains at least one structure selected from polyimide structure, polyamide structure, polybenzoxazole structure, polyamide-imide structure, and their precursor structures. If the aforementioned resin (A) is an alkali-soluble resin containing the above-mentioned structures, there is no particular limitation, but it is preferable to contain structures represented by the following general formulas (6) and / or (7).

[0100] [Chemistry 8]

[0101]

[0102] In the formula, X6 is a tetravalent organic group, s represents 0 or 1, Z is a divalent bonding group, and when s = 0, the two aromatic rings in the formula are directly bonded without the bonding group.

[0103] [Chemistry 9]

[0104]

[0105] In the formula, X7 is a divalent organic group, and s and Z are the same as described above.

[0106] In the above general formula (6), X6 is a tetravalent organic group, and there is no limitation as long as it is a tetravalent organic group. It is preferably a tetravalent organic group of alicyclic aliphatic or aromatic group with 4 to 40 carbon atoms, and is especially preferred to be a tetravalent organic group represented by the following formula (8). Furthermore, the structure of X6 can be one type or a combination of two or more types.

[0107] [Chemistry 10]

[0108]

[0109] In the formula, the dotted line represents the bond.

[0110] In the above general formula (6), s represents 0 or 1. When s = 0, the two aromatic rings in the above general formula (6) are directly bonded without passing through the divalent bonding group Z.

[0111] On the other hand, when s = 1, the two aromatic rings in the above general formula (6) are bonded by a divalent bonding group Z. Z is not limited as long as it is a divalent group. It is preferably a divalent organic group of alicyclic aliphatic or aromatic group with 4 to 40 carbon atoms, and is especially preferred to be a divalent bonding group represented by the following formula (9). Furthermore, the structure of Z can be one type or a combination of two or more types.

[0112] [Chemistry 11]

[0113]

[0114] In the formula, q1, q2, and q3 represent integers from 1 to 6, and q4 and q5 represent integers from 1 to 10. Dotted lines represent bonds.

[0115] The divalent bonding group Z is particularly preferably a divalent group represented by the following general formula (10) or (11).

[0116] [Chemistry 12]

[0117]

[0118] In the formula, the dotted line represents the bond.

[0119] Regarding the structural unit represented by the above general formula (6), when Z in the above general formula (6) is a group represented by the above formula (10), it is preferably a structural unit represented by the following general formula (6-1). When Z in the above general formula (6) is a group represented by the above formula (11), it is preferably a structural unit represented by the following general formula (6-2).

[0120] [Chemistry 13]

[0121]

[0122] [Chemistry 14]

[0123]

[0124] In the formula, X6 is the same as described above.

[0125] As in the general formula (6-1) above, when the Z of the divalent bonding group is the hexafluoropropylene group represented by the formula (10) above, and is located at the para position of the phenolic hydroxyl group, since the hexafluoropropylene group is an electron-attracting group, the acidity of the phenolic hydroxyl group becomes higher, and the solubility of the developer in the alkaline aqueous solution is improved, which is better.

[0126] Similarly, as in the general formula (6-2) above, when the Z of the divalent bonding group is the sulfone group represented by the formula (11) above, and is located at the para position of the phenolic hydroxyl group, the sulfone group is also an electron-attracting group. Therefore, the acidity of the phenolic hydroxyl group becomes higher, and the solubility of the developer in the alkaline aqueous solution is improved, which is better.

[0127] In the above general formula (7), X7 is a divalent organic group. If it is a divalent organic group, there is no limitation. It is preferably a divalent organic group with an aliphatic long-chain structure of 4 to 40 carbon atoms, or an alicyclic aliphatic group or an aromatic group. It is especially preferred to be a divalent organic group represented by the following formula (12). Furthermore, the structure of X7 can be one type or a combination of two or more types.

[0128] [Chemistry 15]

[0129]

[0130] In the formula, R 16 R 17 Each is independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, q6 is an integer from 1 to 30, and the dotted line indicates the bond.

[0131] When X7 in the above general formula (7) is a divalent organic group with an aliphatic long chain structure, the mechanical strength, especially the elongation, of the hardened film of the negative photosensitive resin composition of the present invention becomes higher, which is better.

[0132] In the above general formula (7), s and Z are the same as before. Considering the solubility of the developer in alkaline aqueous solution, Z should preferably be the above general formula (10) or (11). In this case, similar to the cases of formulas (6-1) and (6-2) above, the acidity of the phenolic hydroxyl group becomes higher, and the solubility of the developer in alkaline aqueous solution is improved, so it is better.

[0133] Furthermore, in addition to containing the structural units represented by the above general formulas (6) and (7), the alkali-soluble resin (A) of the present invention may also contain the structural units represented by the following general formula (13) (hereinafter also referred to as structural units (13)).

[0134] [Chemistry 16]

[0135]

[0136] In the formula, X7 is the same as described above. X8 is a divalent organic group.

[0137] In the above general formula (13), X8 is a divalent organic group. If it is a divalent organic group, there is no limitation. It is preferably a divalent organic group with 6 to 40 carbon atoms, and it is more preferably a cyclic organic group containing 1 to 4 aromatic or aliphatic rings with substituents, or an aliphatic group or siloxane without a cyclic structure. As a more ideal X8, the structure represented by the following formula (14) or (15) can be listed. In addition, the structure of X8 can be one type or a combination of two or more types.

[0138] [Chemistry 17]

[0139]

[0140] In the formula, the dotted line represents the bond with the amino group.

[0141] [Chemistry 18]

[0142]

[0143] In the formula, the dotted line represents the bond with the amino group, R 15 Each can independently represent methyl, ethyl, propyl, n-butyl, or trifluoromethyl, and q7 represents a positive number from 2 to 20.

[0144] Furthermore, in addition to containing the structural units represented by the above general formulas (6) and (7), the alkali-soluble resin (A) of the present invention preferably contains the structural units represented by the following general formula (16) (hereinafter also referred to as structural units (16)).

[0145] [Chemistry 19]

[0146]

[0147] In the formula, X9 is a tetravalent organic group that is the same as or different from X6 mentioned above, X 10 The group represented by the following general formula (17) is a group.

[0148] [Chemistry 20]

[0149]

[0150] In the formula, R 16 ~R 19 Each is an independent linear or branched alkylene group having 2 to 10 carbon atoms, m1 is an integer from 1 to 40, and m2 and m3 are independent integers from 0 to 40.

[0151] In formula (16), X9 can be any of the tetravalent organic groups listed for X6, such as the tetravalent organic group represented by formula (8) above. Also, X 10 Organic groups that can be ideally used in (the groups represented by the general formula (17) above) are specifically listed below. However, they are not limited to these.

[0152] [Chemistry 21]

[0153]

[0154] By using an alkali-soluble resin (A) containing such structural units (16), flexibility is achieved, resulting in a hardened film with high elongation and low warpage.

[0155] In addition, the alkali-soluble resin (A) of the present invention may contain structural units represented by the following general formula (18) or (19) (hereinafter referred to as structural unit (18) and structural unit (19)).

[0156] [Chemistry 22]

[0157]

[0158] [Chemistry 23]

[0159]

[0160] In the formula, X 11 It is a tetravalent organic group that is the same as or different from the aforementioned X6, X 12 It is a divalent organic group that is the same as or different from X8; s and Z are the same as described above. R 23 and R 24 Each is independently a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group represented by the following general formula (20), R 23 and R 24 At least one of them is an organic group represented by the following general formula (20).

[0161] [Chemistry 24]

[0162]

[0163] In the formula, the dotted line represents the bond. R 25 R is a hydrogen atom or an organic group having 1 to 3 carbon atoms. 26 and R 27 Each is an independent hydrogen atom or an organic group having 1 to 3 carbon atoms, and o is an integer from 2 to 10.

[0164] X in the above structural units (18) and (19) 11 It is a tetravalent organic group, which may be the same as or different from X6 above. If it is a tetravalent organic group, there is no limitation. It is preferably a tetravalent organic group of alicyclic aliphatic or aromatic group with 4 to 40 carbon atoms, and is especially preferred to be a tetravalent organic group represented by formula (8) above. Also, X 11 The structure can be one type or a combination of two or more types.

[0165] On the other hand, X in the above structural unit (19) 12 It is a divalent organic group, which may be the same as or different from X8 above. If it is a divalent organic group, there is no limitation. It is preferably a divalent organic group with 6 to 40 carbon atoms, and more preferably a cyclic organic group containing 1 to 4 aromatic or aliphatic rings with substituents, or an aliphatic group or siloxane group without a cyclic structure. As a more ideal X... 12 The structures represented by equations (14) or (15) above can be listed. Also, X 12 The structure can be one type or a combination of two or more types.

[0166] R in the above structures (18) and (19) 23 and R 24 Each is independently a hydrogen atom or a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group represented by the above general formula (20), R 23 and R 24 At least one of them is an organic group represented by the above general formula (20).

[0167] R in the above general formula (20) 25 There are no restrictions as long as it is a hydrogen atom or a monovalent organic group with 1 to 3 carbon atoms. However, considering the photosensitivity of negative photosensitive resin components, it is preferable to use a hydrogen atom or a methyl group.

[0168] R in the above general formula (20) 26 and R 27 There are no restrictions as long as each component is an independent hydrogen atom or a monovalent organic group with 1 to 3 carbon atoms. However, considering the photosensitivity of negative photosensitive resin components, hydrogen atoms are preferable.

[0169] In the above general formula (20), o is an integer from 2 to 10. Considering the photosensitivity, it is preferable to be an integer from 2 to 4. o is especially preferred to be 2.

[0170] [(B) Cross-linked polymers]

[0171] The cross-linked polymer (B) used in this invention is not particularly limited as long as it contains a structural unit represented by the following general formula (1) and contains a group that can cross-link with component (A).

[0172] [Chemistry 25]

[0173]

[0174] Here, in general formula (1), R 1 R represents a hydrogen atom or a methyl group. 2The carbon atoms of the aliphatic saturated hydrocarbon group (n+1) with 1 to 15 carbon atoms can be linear, branched, or cyclic, or have an aromatic hydrocarbon group with 6 to 15 carbon atoms, benzyl, or naphthylmethyl. The carbon atoms of these aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms. Furthermore, n is an integer from 1 to 5, and X1 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R) 3 OH)-. R 3 It consists of aliphatic saturated hydrocarbon groups with a carbon number of 1 to 12 and a carbon number of 6 to 12, in a divalent form. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms, and p is 0 or 1.

[0175] Furthermore, regarding the monomers used to obtain the structure represented by general formula (1), as an example of an ideal user, the following can be specifically exemplified.

[0176] [Chemistry 26]

[0177]

[0178] In the formula, R 1 As mentioned above.

[0179] [Chemistry 27]

[0180]

[0181] In the formula, R 1 As mentioned above.

[0182] [Chemistry 28]

[0183]

[0184] In the formula, R 1 As mentioned above.

[0185] Furthermore, there are no particular limitations on the groups that can crosslink with the alkali-soluble resin of component (A), but examples include oxazolinyl, isocyanate, terminal isocyanate, oxetyl, and epoxy groups, which are described later.

[0186] In addition, regarding component (B), in order to maintain alkali solubility and improve crosslinking density, it is better to contain structural units represented by the following general formula (2) and the following general formula (3).

[0187] [Chemistry 29]

[0188]

[0189] Here, in general formula (2), R 4 Representing a hydrogen atom or a methyl group, X2 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R)5 OH)-. R 5 It consists of a divalent, linear, branched, or cyclic aliphatic saturated hydrocarbon groups with 1 to 12 carbon atoms, or aromatic hydrocarbon groups with 6 to 12 carbon atoms. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms. p is 0 or 1.

[0190] [Chemistry 30]

[0191]

[0192] Here, in general formula (3), R 6 R represents a hydrogen atom or a methyl group. 7 The group represents an oxazoline group, isocyanate group, terminal isocyanate group, oxacyclobutyl group, or epoxy group. X3 is -C(=O)-O-, or phenylene or naphthylene. p is 0 or 1.

[0193] In particular, the structure represented by general formula (2) has an electron-attracting carbonyl or amide group at the para position of the phenolic hydroxyl group, which increases the acidity of the phenolic hydroxyl group and improves its solubility in alkaline aqueous solutions. Examples of monomers that can ideally be used to form structural units of general formula (2) are shown below. However, they are not limited to these examples.

[0194] [Chemistry 31]

[0195]

[0196] In the formula, R 4 As mentioned above.

[0197] As for general formula (2), in addition to improving alkali solubility, it is effective as a unit to promote cross-linking, and can further improve hardening properties by using it in combination with cross-linking groups.

[0198] In addition, in order to improve the crosslinking density, it is advisable to copolymerize monomers having epoxy or oxetane groups represented by the following general formula (4) or monomers having terminal isocyanate groups represented by the following general formula (4′).

[0199] [Chemistry 32]

[0200]

[0201] Here, in general formula (4), R 8 Representing a hydrogen atom or a methyl group, X4 is independently -C(=O)-O-, or phenylene or naphthylene. R 9 It may also contain ester groups, ether groups, or aromatic hydrocarbons in the form of straight-chain, branched, or cyclic alkylene groups having 1 to 15 carbon atoms. 10 It is a straight-chain, branched, or cyclic alkyl group with hydrogen atoms and 1 to 6 carbon atoms, or it can be combined with R.9 A ring is formed by bonding. R 11 R is a hydrogen atom, or a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms. 12 It is a hydrogen atom or a straight-chain alkyl group having 1 to 6 carbon atoms. m is 0 or 1. p is 0 or 1. Examples of units of formula (4) are listed below.

[0202] [Chemistry 33]

[0203]

[0204] In the formula, R 8 As mentioned above.

[0205] [Chemistry 34]

[0206]

[0207] In the formula, R 8 As mentioned above.

[0208] [Chemistry 35]

[0209]

[0210] In the formula, R 8 As mentioned above.

[0211] Furthermore, a subset of monomers used to obtain repeating units having epoxy groups and oxetyl groups are disclosed in Japanese Patent Application Publication Nos. 2003-55362, 2005-8847, and 2005-18012.

[0212] Here, in general formula (4′), R 13’ R represents a hydrogen atom or a methyl group. 14’ Indicates a single bond or alkylene group, R 15’ It is a capped isocyanate group.

[0213] The terminated isocyanate group mentioned above refers to an organic group in which the isocyanate group (-N=C=O) is capped with an appropriate protecting group. The terminated isocyanate group can be formed by reacting the isocyanate group with a capping agent.

[0214] End-capped isocyanates are stable at room temperature, but above a certain temperature, the end-capping agent decapsulates (decapsulates), and the hydroxyl or carboxyl groups in component (A) react with the isocyanate groups to form a cross-linked structure. The end-capping agent is a compound containing active hydrogen that can react with isocyanates, such as alcohols, phenols, polycyclic phenols, amides, imides, imines, thiols, oximes, lactams, heterocycles containing active hydrogen, and compounds containing active methylene groups.

[0215] Furthermore, the ideal capped isocyanate group is described in paragraphs

[0015] to

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

[0216] Considering the good polymerizability and the availability of commercially available products, the monomer units shown below are preferred. Furthermore, these monomers can be used alone or in combination with more than one type.

[0217] [Chemistry 36]

[0218]

[0219] In the formula, R 13’ As mentioned above.

[0220] In addition, it is preferable that the end capping is not removed by heat treatment (pre-baking) after spin coating of the photosensitive composition and heat treatment (post-exposure baking (PEB)), but is removed by post-curing using heat treatment after development, and cross-linked with alkali-soluble resin.

[0221] Therefore, the following monomer units are preferred for desealing in the range of 140°C to 200°C.

[0222] [Chemistry 37]

[0223]

[0224] In the formula, R 13’ As mentioned above.

[0225] Specific examples that can be used as commercially available products include the Karenz MOI series and the AOI series (manufactured by Showa Denko, Inc., product name).

[0226] Furthermore, the structural unit represented by general formula (2) has excellent solvent and alkali solubility, but lacks crosslinking properties, and therefore must be copolymerized with structural units represented by general formula (4) or general formula (4') that have crosslinking properties. Polymers composed only of epoxy groups and oxetyl groups represented by general formula (4) that have crosslinking properties and terminal isocyanate groups represented by general formula (4') have excellent crosslinking properties, but lack alkali solubility, and therefore must be copolymerized with structural units represented by general formula (2).

[0227] Therefore, when repeating units are copolymerized in this way, it is preferable to have repeating units of the following formula (1a). However, structural units having crosslinkable epoxy groups, oxetyl groups and terminal isocyanate groups may be both or only one of them.

[0228] [Chemistry 38]

[0229]

[0230] In the formula, R4 and R 8 to R 12 and R 13’ to R 15’ 、X2, X4, m and p are the same as above, 0 < b2 < 1.0, 0 ≤ b4 < 1.0, 0 ≤ b4’ < 1.0, 0 < b4 + b4’ < 1.0, 0 < b2 + b4 + b4’ ≤ 1.0 or 0 < b2 + b4 ≤ 1.0 and 0 < b2 + b4’ ≤ 1.0.

[0231] In addition, from the viewpoint of further improving the crosslinking reactivity during lithographic patterning and improving the dissolution contrast between the unexposed / exposed portions with respect to an alkaline developer, a crosslinkable polymer compound containing structural units represented by the following general formula (2), general formula (4), general formula (4′) and general formula (5) is more preferable. However, it may be both or only one of the structural units represented by general formula (4) and general formula (4′).

[0232] [Chemical formula 39]

[0233]

[0234] Here, in general formula (5), R 13 represents a hydrogen atom or a methyl group, R<00001**09>is a linear, branched or cyclic aliphatic saturated hydrocarbon group having a valence of (l + 1) and 1 to 12 carbon atoms, and the carbon atoms of the above aliphatic saturated hydrocarbon group may be replaced by oxygen atoms. X5 are each independently -C(=O)-O-, -C(=O)-NH-, -C(=O)-N(R 15 OH)-, or a phenylene group or a naphthylene group. R 15 is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and the carbon atoms of the above aliphatic saturated hydrocarbon group may be replaced by oxygen atoms. I is 0 or 1. 0 < b2 < 1.0, 0 ≤ b4 < 1.0, 0 ≤ b4’ < 1.0, 0 < b4 + b4’ < 1.0, 0 ≤ b5 < 1.0, 0 < b2 + b4 + b4’ + b5 ≤ 1.0 or 0 < b2 + b4 + b5 ≤ 1.0 and 0 < b2 + b4’ + b5 ≤ 1.0. In general formula (2), (4), (4’), R 4 、R 8 to R<** 12 、R 13’ to R 15’ 、X2, X4, m and p are the same as above.

[0235] It should be noted that there seems to be a small error in the original text where "R 14 " is repeated with different numbering in the translation. Also, "R 12 " has an asterisk added in the translation to mark the potential error in the original numbering. These are minor issues in the original text that are carried over as accurately as possible in the translation.The crosslinkable polymer of the present invention is based on repeating units formed by monomers having repeating units with hydroxyl groups as represented by the above general formula (1) (hereinafter referred to as b1) and monomers having repeating units composed of either or both of the repeating units formed by the above general formula (4) and general formula (4′) having repeating groups that can crosslink with the alkali-soluble resin of component (A) (hereinafter referred to as b4 and b4'). In order to improve adhesion to the substrate, flexibility of the hardened film, and further improve mechanical properties and thermal shock resistance, monomers having repeating units represented by the following general formula (21) can also be copolymerized.

[0236] [Chemistry 40]

[0237]

[0238] Here, in general formula (21), R 28 R represents a hydrogen atom or a methyl group. 29 It is a monovalent organic group having a primary, secondary, or tertiary amino group, and may also have an alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alicyclic group having 6 to 10 carbon atoms. X 13 It should be -C(=O)-O- or -C(=O)-NH-. b6 is 0≤b6<1.

[0239] Monomers that obtain the repeating unit represented by the above general formula (21) can be exemplified by the following specific examples: (meth)acrylate aminoethyl ester, (meth)acrylate N-methylaminoethyl ester, (meth)acrylate N,N-dimethylaminoethyl ester, (meth)acrylate N-ethylaminoethyl ester, (meth)acrylate N,N-diethylaminoethyl ester, (meth)acrylate aminopropyl ester, (meth)acrylate N-methylaminopropyl ester, (meth)acrylate N,N-dimethylaminopropyl ester, (meth)acrylate N-ethylaminopropyl ester, (meth)acrylate N,N-diethylaminopropyl ester, aminoethyl(meth)acrylamide, N-methylaminoethyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N-ethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, aminopropyl(meth)acrylamide, N-methylaminopropyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, aminopropyl(meth)acrylamide, N-methylaminopropyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide N-ethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, piperidine-4-ester (meth)acrylate, 1-methylpiperidine-4-ester (meth)acrylate, 2,2,6,6-tetramethylpiperidine-4-ester (meth)acrylate, 1,2,2,6,6-pentamethylpiperidine-4-ester (meth)acrylate, (piperidine-4-yl)methyl methacrylate, 2-(piperidine-4-yl)ethyl methacrylate, (meth)acrylate, 1-methylpiperidine-4-ester (meth)acrylate, 2,2,6,6-tetramethylpiperidine-4-ester (meth)acrylate, 1,2,2,6,6-pentamethylpiperidine-4-ester (meth)acrylate, (piperidine-4-yl)methyl methacrylate, 2-(piperidine-4-yl)ethyl methacrylate, etc.

[0240] In addition, monomers that obtain the repeating unit represented by the above general formula (21) can be alkyl methacrylates, such as: butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecanyl methacrylate, octadecyl methacrylate, nonadecanyl methacrylate, eicosyl methacrylate, etc.

[0241] In addition, to improve the mechanical strength of the hardened film, it is also possible to copolymerize olefins with aromatic groups such as styrene, vinylnaphthalene, vinylanthracene, vinylcarbazole, vinylnaphthalene, and indene, as well as alicyclic olefins such as camphene and camphenediene.

[0242] Among the above repeating units b2, b4, b4', b5, b6, b7, and b8, the ratios of the repeating units are 0 < b2 < 1.0, 0 ≤ b4 < 1.0, 0 ≤ b4' < 1.0, 0 < b4 + b4' < 1.0, 0 ≤ b5 < 1.0, 0 ≤ b6 ≤ 0.8, 0 ≤ b7 ≤ 0.8, 0 ≤ b8 ≤ 0.8, 0 < b2 + b4 + b4' ≤ 1.0, and 0 < b2 + b4 ≤ 1.0 or 0 < b2 + b4' ≤ 1.0. It is preferably 0 < b2 ≤ 0.5, 0 ≤ b4 ≤ 0.9, 0 ≤ b4' ≤ 0.9, 0 ≤ b5 ≤ 0.6, more preferably in the range of 0.2 ≤ b2 ≤ 0.4, 0.2 ≤ b4 ≤ 0.8, 0 ≤ b4' ≤ 0.5, 0 ≤ b5 ≤ 0.5, 0.1 ≤ b2 + b4 ≤ 1.0, 0.1 ≤ b2 + b4' ≤ 1.0, 0.1 ≤ b2 + b4 + b4' ≤ 1.0, 0 ≤ b6 ≤ 0.5, 0 ≤ b7 ≤ 0.5, and 0 ≤ b8 ≤ 0.5. In addition, the sum of these repeating units is 100 mol% of the total amount of all repeating units.

[0243] The crosslinkable polymer compound (B) used in the present invention has a polystyrene-reduced weight average molecular weight of 1,000 to 500,000 obtained by gel permeation chromatography (GPC), and is particularly preferably 2,000 to 30,000. If the weight average molecular weight is greater than the lower limit of these, the glass transition temperature is high enough, and the pattern will not deform during the thermal crosslinking after development of the negative-type photosensitive resin composition. If it is smaller than the upper limit, there is no risk of pinhole defects occurring during coating.

[0244] In addition, two or more polymers having different composition ratios, molecular weight distributions, and molecular weights can also be blended.

[0245] Also, at this time, the addition amount of the crosslinkable polymer compound (B) is preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A). If the addition amount is 10 parts by mass or more, the toughness of the cured film of the alkali-soluble resin (A) as described above is high. If it is 100 parts by mass or less, the tensile strength of the cured film will not decrease. Therefore, the addition amount of the crosslinkable polymer compound (B) is preferably in the above range. The addition amount of the component (B) is more preferably 10 parts by mass or more and 70 parts by mass or less, and even more preferably 30 parts by mass or more and 50 parts by mass or less. By being in this range, the balance between the lithographic patterning performance and the physical properties of the cured film becomes good.

[0246] [(C) Compound that generates acid upon light]

[0247] The photosensitive acid-generating compound (C) of this invention is suitable for any compound that generates acid upon exposure to high-energy radiation. Ideal compounds include: sulfonium salts, sulfonyl diazomethanes, N-sulfonyloxyimide type, benzoin sulfonate type, gallophenol trisulfonate type, nitrobenzene sulfonate type, sulfone type, and glyoxime derivative type acid generators. These will be described in detail below; they can be used alone or in combination of two or more.

[0248] Sulfonium salts are salts of sulfonium cations and sulfonate groups. Examples of sulfonium cations include: triphenylsulfonium, (4-tert-butoxyphenyl)diphenylsulfonium, bis(4-tert-butoxyphenyl)phenylsulfonium, tris(4-tert-butoxyphenyl)sulfonium, (3-tert-butoxyphenyl)diphenylsulfonium, bis(3-tert-butoxyphenyl)phenylsulfonium, tris(3-tert-butoxyphenyl)sulfonium, (3,4-di-tert-butoxyphenyl)diphenylsulfonium, bis(3,4-di-tert-butoxyphenyl)phenylsulfonium, tris(3,4-di-tert-butoxyphenyl)sulfonium, diphenyl(4-thiophenoxyphenyl)sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl)diphenylsulfonium, tris(4-tert-butoxycarbonylmethyloxyphenyl)sulfonium, (4- Tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium, tris(4-dimethylaminophenyl)sulfonium, 2-naphthyldiphenylsulfonium, dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium, etc. Sulfonates include: trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, 4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate, camphorsulfonate. Sulfonate, octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, methane sulfonate, etc., are examples of combinations of these sulfonates.

[0249] A ferric salt is a salt of a ferric cation and a sulfonate ion. Examples of ferric cations include: diphenylferric, bis(4-tert-butylphenyl)ferric, 4-tert-butoxyphenylphenylferric, 4-methoxyphenylphenylferric, etc., which are aryl ferric cations. Examples of sulfonates include: trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, 4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, etc., and combinations of these ferric salts can also be listed.

[0250] Examples of sulfonyl diazonium methanes include: bis(ethylsulfonyl)diazomethane, bis(1-methylpropylsulfonyl)diazomethane, bis(2-methylpropylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(perfluoroisopropylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(4-methylphenylsulfonyl)diazomethane, and bis(2,4-dimethylphenylsulfonyl)diazomethane. Acyl)diazomethane, bis(2-naphthylsulfonyl)diazomethane, 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl-2-naphthylbenzoyldiazomethane, methylsulfonylbenzoyldiazomethane, tert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane, etc., are all bissulfonyldiazomethanes and sulfonylcarbonyldiazomethanes.

[0251] Examples of N-sulfonyloxyimide type photoacid generators include: compounds consisting of succinimide, naphthyldicarboxyimide, phthalimide, cyclohexyldicarboxyimide, 5-norcampene-2,3-dicarboxyimide, 7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboxyimide, etc., with an imide skeleton combined with trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, methane sulfonate, etc.

[0252] Examples of photoacid generators of benzoin sulfonate type include benzoin toluene sulfonate, benzoin methane sulfonate, and benzoin butane sulfonate.

[0253] Gallamol trisulfonate type photoacid generators can include compounds obtained by replacing all the hydroxyl groups of gallamol, fluoroglycine, catechol, resorcinol, and hydroquinone with trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, methane sulfonate, etc.

[0254] Nitrobenzyl sulfonate type photoacid generators include 2,4-dinitrobenzyl sulfonate, 2-nitrobenzyl sulfonate, and 2,6-dinitrobenzyl sulfonate. Specific examples of sulfonates include trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, and methane sulfonate. Furthermore, compounds can also be obtained by replacing the nitro group on the benzyl side with a trifluoromethyl group.

[0255] Examples of sulfone-type photoacid generators include: bis(phenylsulfonyl)methane, bis(4-methylphenylsulfonyl)methane, bis(2-naphthylsulfonyl)methane, 2,2-bis(phenylsulfonyl)propane, 2,2-bis(4-methylphenylsulfonyl)propane, 2,2-bis(2-naphthylsulfonyl)propane, 2-methyl-2-(p-toluenesulfonyl)phenylacetone, 2-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, 2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one, etc.

[0256] Examples of glyoxime derivatives of photoacid generators include: bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonic acid)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, and bis-o-(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 Diketoxime, 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- (cyclohexylsulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, bis-o-(camphorsulfonyl)-α-dimethylglyoxime, etc.

[0257] Among them, the ideal photoacid generators are bis(sulfonyl)diazomethane and N-sulfonyloxyimide.

[0258] Alternatively, an oxime-type acid generator as shown in WO2004 / 074242A2 may be added.

[0259] Furthermore, the aforementioned acid generators can be used alone or in combination of two or more. Onium salts exhibit excellent rectangularity improvement, while diazomethane derivatives and glyoxime derivatives demonstrate excellent standing wave reduction; therefore, by combining these two, fine-tuning of the profile can be achieved.

[0260] The amount of photoacid generator in the negative photosensitive resin composition of the present invention is preferably 0.05 to 20 parts by mass relative to 100 parts by mass of component (A), and particularly preferably 1 to 10 parts by mass. A dosing amount of 0.05 parts by mass or more provides sufficient contrast (the difference in dissolution rate of the exposed and unexposed areas to the developer), while a dosing amount of 20 parts by mass or less avoids the risk of resolution degradation due to light absorption by the acid generator itself.

[0261] [Crossing agents other than components (D)(B)]

[0262] The crosslinking agent (D) of the present invention is a crosslinking agent other than the component (B) described above. It is acceptable as long as it is a compound having a group that can crosslink with component (A). Specific examples of crosslinking agents that can be used here include: melamine compounds, guanidine compounds, urea compounds or urea compounds substituted with at least one group selected from hydroxymethyl, alkoxymethyl, and acyloxymethyl groups, epoxy compounds, oxadiazonium compounds, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, compounds containing benzyl alcohol, etc., and oxazoline-based crosslinking agents disclosed in Japanese Patent Application Publication Nos. 2-60941, 2-99537, and 2-115238.

[0263] Among the specific examples of the aforementioned crosslinking agents, further examples of epoxy compounds include: tris(2,3-epoxypropyl)isocyanurate, trimethylolpropane triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, triethylolethane triepoxypropyl ether, etc.

[0264] Or, examples could include: phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,5-diphenylphenol, 2-naphthylphenol, 3-naphthylphenol, 4-naphthylphenol, 4-triphenylmethylphenol. Phenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, catechol, 4-tert-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, gallnutol, thymol, isothymol, 4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'-dimethyl-4,4'-(9H-fluorene) -9-yl)bisphenol, 2,2'-diallyl-4,4'-(9H-fluorene-9-yl)bisphenol, 2,2'-difluoro-4,4'-(9H-fluorene-9-yl)bisphenol, 2,2'-diphenyl-4,4'-(9H-fluorene-9-yl)bisphenol, 2,2'-dimethoxy-4,4'-(9H-fluorene-9-yl)bisphenol, 2,3,2',3'-tetrahydro-(1,1')-spiroindene-6,6'-diol, 3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spiroindene The hydroxyl groups of -6,6'-diol, 3,3,3',3',4,4'-hexamethyl-2,3,2',3'-tetrahydro-(1,1')-spiroindene-6,6'-diol, 2,3,2',3'-tetrahydro-(1,1')-spiroindene-5,5'-diol, and 5,5'-dimethyl-3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spiroindene-6,6'-diol are obtained by epoxy propylene etherification, or the hydroxyl groups of the aforementioned phenolic varnish resins of phenolic compounds are obtained by epoxy propylene etherification.

[0265] Specific examples of melamine compounds include: hexamethylolmelamine, hexamethoxymethylmelamine, compounds obtained by methoxymethylation of 1-6 hydroxymethyl groups in hexamethylolmelamine, or mixtures thereof; hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds obtained by acyloxymethylation of 1-6 hydroxymethyl groups in hexamethylolmelamine, or mixtures thereof. Examples of guanidine compounds include: tetramethylolguanidine, tetramethoxymethylguanidine, compounds obtained by methoxymethylation of 1-4 hydroxymethyl groups in tetramethylolguanidine, or mixtures thereof; tetramethoxyethylguanidine, tetraacyloxyguanidine, compounds obtained by acyloxymethylation of 1-4 hydroxymethyl groups in tetramethylolguanidine, or mixtures thereof. Examples of urea compounds include: tetrahydroxymethylurea, tetramethoxyurea, tetramethoxymethylurea, compounds obtained by methoxymethylation of 1-4 hydroxymethyl groups in tetrahydroxymethylurea, or mixtures thereof; compounds obtained by acylmethylation of 1-4 hydroxymethyl groups in tetrahydroxymethylurea, or mixtures thereof. Examples of urea compounds include: tetrahydroxymethylurea, tetramethoxymethylurea, compounds obtained by methoxymethylation of 1-4 hydroxymethyl groups in tetrahydroxymethylurea, or mixtures thereof; tetramethoxyethylurea, etc.

[0266] Examples of isocyanate compounds include: toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, etc. Examples of azide compounds include: 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylene bisazide, 4,4'-oxy bisazide.

[0267] Compounds containing alkenyl ether groups include: ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, neopentyl tetraethylene glycol trivinyl ether, neopentyl tetraethylene glycol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, etc.

[0268] Additionally, examples include: Japanese Patent Application Publication No. 11-100378, Japanese Patent Application Publication No. 2003-231860, Japanese Patent Application Publication No. 2005-146038, Japanese Patent Application Publication No. 2006-290052, Japanese Patent Application Publication No. 2006-199790, and Japanese Patent Application Publication No. 2006-273748, cyclic epoxy compounds described in Japanese Patent Application Publication No. 2006-348252, crosslinking agents having oxocyclopropane rings bonded to the ring, epoxy crosslinking agents based on dendritic polymers and hyperbranched polymers as shown in Japanese Patent Application Publication No. 2008-24920, crosslinking agents having both hydroxyl and oxocyclobutane groups described in Japanese Patent Application Publication No. 2001-310937, and crosslinking agents having both hydroxyl and epoxy groups described in Japanese Patent Publication No. 3824286.

[0269] Regarding epoxy groups, the rings are highly deformable and reactive, while oxetanes are highly basic and readily bond with acids. It has been reported that combining oxetanes with epoxy groups significantly improves the reactivity of cationic polymerization.

[0270] Furthermore, component (D) in the negative photosensitive resin composition of the present invention is preferably one or more crosslinking agents selected from amino condensates modified with formaldehyde or formaldehyde-alcohol, or phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups per molecule.

[0271] The aforementioned amino condensates modified with formaldehyde or formaldehyde-alcohol include, for example, melamine condensates modified with formaldehyde or formaldehyde-alcohol, or urea condensates modified with formaldehyde or formaldehyde-alcohol.

[0272] The preparation of the above-mentioned melamine condensate modified with formaldehyde or formaldehyde-alcohol involves, for example, first modifying the melamine monomer by hydroxymethylation with formalin using a known method, or further modifying it by alkoxylation with an alcohol, to prepare the modified melamine represented by the following general formula (22). Furthermore, the alcohol is preferably a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms.

[0273] [Chemistry 41]

[0274]

[0275] In the formula, R 30 They may be the same or different, and can be hydroxymethyl, alkoxymethyl containing alkoxy groups with 1 to 4 carbon atoms, or hydrogen atoms, with at least one being hydroxymethyl or the above-mentioned alkoxymethyl.

[0276] As mentioned above, R 30 Examples include hydroxymethyl, methoxymethyl, ethoxymethyl, and other alkoxymethyl groups, as well as hydrogen atoms.

[0277] The modified melamine represented by the above general formula (22) can specifically include: trimethoxymethyl monohydroxymethyl melamine, dimethoxymethyl monohydroxymethyl melamine, trihydroxymethyl melamine, hexahydroxymethyl melamine, hexamethoxymethyl melamine, etc. Then, the modified melamine represented by the above general formula (22) or its polymers (e.g., dimers, trimers, etc. oligomers) are subjected to addition condensation polymerization with formaldehyde using conventional methods until the desired molecular weight is achieved, thereby obtaining a melamine condensate modified with formaldehyde or formaldehyde-alcohol.

[0278] Furthermore, the preparation of the above-mentioned urea condensate modified with formaldehyde or formaldehyde-alcohol can be achieved, for example, by following known methods, modifying the urea condensate of the desired molecular weight by hydroxymethylation with formaldehyde, or by further modifying it by alkoxylation with an alcohol.

[0279] Specific examples of the urea condensates modified with formaldehyde or formaldehyde-alcohols mentioned above include, for example, methoxymethylated urea condensates, ethoxymethylated urea condensates, propoxymethylated urea condensates, etc.

[0280] Furthermore, these modified melamine condensates and modified urea condensates can be used in combination, either one or two or more.

[0281] Then, phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups per molecule, such as (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and compounds represented by formulas (D-3) to (D-7).

[0282] [Chemistry 42]

[0283]

[0284] In addition, one or more of the above-mentioned crosslinking agents may be used.

[0285] Regarding component (D), in the PEB step of the negative photosensitive resin composition of the present invention, the acid generated from (C) acts as a catalyst to undergo a crosslinking reaction with (A) and (B). Furthermore, it is a component that undergoes a crosslinking reaction during subsequent post-curing, further enhancing the strength of the cured product. Considering photocurability and heat resistance, the weight-average molecular weight of such component (D) is preferably 150 to 10,000, and particularly preferably 200 to 3,000.

[0286] Furthermore, regarding the amount of component (D), in the negative photosensitive resin composition of the present invention, it is preferably 0.5 to 50 parts by mass relative to 100 parts by mass of component (A), and more preferably 1 to 30 parts by mass.

[0287] [(E) Basic compounds]

[0288] The negative photosensitive resin composition of the present invention, in addition to containing the aforementioned essential components (A), (B), (C), and (D), may further contain a basic compound (E). Ideally, the basic compound (E) should be one that can suppress the diffusion rate of acid generated by the photoacid generator in the resist film. By incorporating such a basic compound, the diffusion rate of acid in the resist film is suppressed, thereby improving resolution, suppressing sensitivity changes after exposure, reducing substrate and environmental dependence, and improving exposure margin, pattern outline, etc.

[0289] The above-mentioned basic compounds can be listed as follows: primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds with carboxyl groups, nitrogen-containing compounds with sulfonyl groups, nitrogen-containing compounds with hydroxyl groups, nitrogen-containing compounds with hydroxyphenyl groups, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, etc.

[0290] Specifically, examples of primary aliphatic amines include: ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. Examples of secondary aliphatic amines include: dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, disec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, di(dodecyl)amine, etc. Dicerylamine, N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, N,N-dimethyltetraethylenepentamine, etc., and tertiary aliphatic amines can be exemplified as: trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trinonylamine, tridecylamine, tri(dodecyl)amine, tricerylamine, N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyltetraethylenepentamine, etc.

[0291] Furthermore, examples of mixed amines include: dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, etc. Specific examples of aromatic amines and heterocyclic amines include: aniline derivatives (e.g., aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, etc.), diphenyl(p-toluyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., Pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (e.g., oxazole, isoxazole, etc.), thiazole derivatives (e.g., thiazole, isothiazole, etc.), imidazole derivatives (e.g., imidazole, 4-methylimidazolium, 4-methyl-2-phenylimidazolium, etc.), pyrazole derivatives, furazane derivatives, pyrrolidone derivatives (e.g., pyrrolidone, 2-methyl-1-pyrrolidone, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidone, N-methylpyrrolidone, etc.), imidazoline. Derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives Pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoleline derivatives, quinoline derivatives (e.g., quinoline, 3-quinoline carboxynitrile), isoquinoline derivatives, cyclophosphamide derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroxaloline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, ureoside derivatives, etc.

[0292] In addition, nitrogen-containing compounds with carboxyl groups include, for example, aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (e.g., nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.), nitrogen-containing compounds with sulfonyl groups include, for example, 3-pyridinesulfonic acid, p-toluenesulfonic acid pyridine, etc., nitrogen-containing compounds with hydroxyl groups, nitrogen-containing compounds with hydroxyphenyl groups, and alcoholic nitrogen-containing compounds include, for example, 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, and 2,2'-imine. 4-aminoethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidine ethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidone, 3-piperidinyl-1,2-propanediol, 3-pyrrolyl-1,2-propanediol, 8-hydroxy-julolidine, 3-quinuclidinol, 3-tropine alcohol, 1-methyl-2-pyrrolidine ethanol, 1-aziridinyl ethanol, N-(2-hydroxyethyl)phthalimide, N-(2-hydroxyethyl)isonicotinamide, etc. Examples of amide derivatives include: formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzo[a]amide, etc. Examples of imide derivatives include: phthalimide, succinimide, maleimide, etc.

[0293] Furthermore, one alkaline compound can be used alone or in combination of two or more. The amount of the compound is 0 to 2 parts by mass relative to 100 parts by mass of the alkali-soluble resin of component (A). It is preferable to mix 0.01 to 2 parts by mass, especially 0.01 to 1 part by mass. If the amount of the compound is less than 2 parts by mass, the sensitivity can be adequately ensured.

[0294] [(F) Thermal acid generating agent]

[0295] The negative photosensitive resin composition of the present invention may further contain (F) a compound that generates acid upon heating (a heat-generating agent). The heat-generating compound (F) may be added to promote the crosslinking reaction of components (A), (B), and (D) during the heating and post-curing steps performed at a temperature of 100–300°C after the above-mentioned pattern formation.

[0296] Regarding component (F), it is particularly preferable that it does not promote film curing until pattern formation is achieved through development, and does not hinder pattern formation. To achieve this, component (F) is preferably one that does not generate acid at the temperature of the solvent removal and drying step after coating the photosensitive resin composition, but generates acid for the first time through heat treatment after pattern formation, and promotes the curing of the pattern or film of the negative photosensitive resin composition. Specifically, it is preferable that it is a compound that decomposes and generates acid through heat treatment at 100°C to 300°C, preferably 150°C to 300°C. By containing such component (F), the step of heating and curing the pattern or film of the negative photosensitive resin composition at a temperature of 100°C to 300°C after pattern formation can be transformed into a pattern or film in which cross-linking and curing reactions further occur. Through further cross-linking and curing reactions, component (F) can further improve the mechanical strength, chemical resistance, adhesion, etc. of the obtained pattern or film.

[0297] Ideally, a compound that produces an acid upon heating can be used, and the compound described in paragraphs

[0061] to

[0085] of Japanese Patent Application Publication No. 2007-199653 can be used.

[0298] The amount of the compound that produces acid upon heating is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and more preferably 30 parts by mass or less, more preferably 5 parts by mass or less, relative to 100 parts by mass of component (A) in the negative photosensitive resin composition of the present invention. A content of 0.1 parts by mass or more promotes the cross-linking reaction. Furthermore, a content of 30 parts by mass or less prevents degradation of the alkaline developability of the composition and avoids the formation of developing residues.

[0299] (G) Antioxidants

[0300] The negative photosensitive resin composition of the present invention may further contain an antioxidant (G). The antioxidant containing component (G) can inhibit the oxidative degradation of the aliphatic groups and phenolic hydroxyl groups of component (A). Furthermore, through its rust-preventive effect on metallic materials, it can inhibit metal oxidation caused by external moisture, photoacid generators, thermal acid generators, etc., and the associated reduction in adhesion and peeling.

[0301] Specific examples of antioxidants that can be used here include hindered phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. However, they are not limited to these. Furthermore, these antioxidants can be used alone or in combination of two or more.

[0302] Among the specific examples of the antioxidants mentioned above, hindered phenolic antioxidants can be further exemplified as follows: neopentyl tetroxide tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan, IRGANOX 1010), thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan, IRGANOX 1035), octadecyl[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan, IRGANOX 1076), octyl 1-3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamic acid (BASF Japan, IRGANOX 1135), 4,6-bis(octylthiomethyl-o-cresol) (BASF Japan, IRGANOX 1520L), Sumilizer GA80 (manufactured by Sumitomo Chemical Co., Ltd., trade name), ADEKASTAB AO-20 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-30 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-40 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-50 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-60 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-80 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-330 (manufactured by ADEKA Co., Ltd., trade name), and hindered phenolic antioxidants as described in Japanese Patent Application Publication No. WO2017 / 188153A1, etc.

[0303] Among the specific examples of the antioxidants mentioned above, phosphorus-based antioxidants can be further exemplified as follows: triphenyl phosphite, tri(methylphenyl) phosphite, triisooctyl phosphite, tridecanyl phosphite, tri(2-ethylhexyl) phosphite, tri(nonylphenyl) phosphite, tri(octylphenyl) phosphite, tri[decyl poly(oxyethylene) phosphite, tri(cyclohexylphenyl) phosphite, tricyclohexyl phosphite, tri(decyl) thiophosphite, triisodecyl thiophosphite, and phosphorus... Phenyl bis(2-ethylhexyl) ester, phenyl diisodecyl phosphite, tetradecyl poly(oxyethylidene)-bis(ethylphenyl) ester, phenyl dicyclohexyl phosphite, phenyl diisooctyl phosphite, phenyl di(tetrazyl) ester, diphenyl cyclohexyl phosphite, diphenyl isooctyl phosphite, diphenyl-2-ethylhexyl phosphite, diphenyl isodecyl phosphite, diphenyl cyclohexyl phenyl phosphite, diphenyl thiophosphite, di(tetrazyl) ester, etc.

[0304] Among the specific examples of antioxidants mentioned above, sulfur-based antioxidants can be further exemplified by ADEKASTAB AO-412S (manufactured by ADEKA Corporation, trade name), AO-503S (manufactured by ADEKA Corporation, trade name), and Sumilizer TP-D (manufactured by Sumitomo Chemical Corporation, trade name), etc.

[0305] For sulfur-based and phosphorus-based antioxidants, the effect of decomposing peroxides can be expected.

[0306] Furthermore, the antioxidant content of (G) is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass, relative to 100 parts by mass of the alkali-soluble resin of component (A). A content of 0.1 parts by mass or more improves adhesion to metallic materials and inhibits peeling. Furthermore, a content of 10 parts by mass or less does not deteriorate the alkali developability of the composition or the toughness of the hardened film.

[0307] [(H)silane compounds]

[0308] The negative photosensitive resin composition of the present invention may contain more silane compounds containing (H). By using silane compounds containing (H), not only can the adhesion to metallic materials be improved, but the peeling of the hardened film in reliability tests such as thermal shock tests and high temperature and humidity tests can also be suppressed.

[0309] Any silane compound used here that has an alkoxysilane group is acceptable. Ideal examples are listed below: γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, etc. Silanes containing phenyltriethoxysilanes, triethoxysilylpropylethylaminocarbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, silane compounds containing amide groups as described in Japanese Patent 6414060, silane compounds containing thiourea groups as described in Japanese Patent Application Publication WO2016 / 140024 and Japanese Patent 5987984, and silane compounds containing thiol groups as described in Japanese Patent 2017-044964, etc. However, they are not limited to these. Furthermore, these silane compounds can be used alone or in combination of two or more.

[0310] Furthermore, the content of the silane compound in (H) relative to 100 parts by weight of the alkali-soluble resin in component (A) is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, and even more preferably 3 to 6 parts by weight. A content of 0.1 parts by weight or more imparts more sufficient adhesion to the substrate, while a content of 20 parts by weight or less further suppresses problems such as viscosity increase during storage at room temperature. Also, by having a content of less than 10 parts by weight, the alkali developability of the composition will not deteriorate, and no developing residue will be generated.

[0311] [Other ingredients]

[0312] Furthermore, the negative photosensitive resin composition of the present invention may also contain components other than (A), (B), (C), (D), (E), (F), (G), and (H). Examples of other components include (I) dissolution inhibitors, (J) surfactants, and (K) solvents. The compounds exemplified below are ideally used. However, the invention is not limited to these.

[0313] Regarding (I) dissolution inhibitors, examples include: compounds with a weight-average molecular weight of 100 to 1,000, preferably 150 to 800, and having two or more phenolic hydroxyl groups in the molecule, wherein the hydrogen atoms of the phenolic hydroxyl groups in the compound are replaced by acid-labile groups in an average of 0 to 100 mol%; or compounds having a carboxyl group in the molecule, wherein the hydrogen atoms of the carboxyl group in the compound are replaced by acid-labile groups in an average of 50 to 100 mol%.

[0314] Furthermore, the substitution rate of the hydrogen atoms of the phenolic hydroxyl group by acid-labile groups is on average 0 mol% or more of the total phenolic hydroxyl group, preferably 30 mol% or more, with an upper limit of 100 mol%, and more preferably 80 mol%. The substitution rate of the hydrogen atoms of the carboxyl group by acid-labile groups is on average 50 mol% or more of the total carboxyl group, preferably 70 mol% or more, with an upper limit of 100 mol%.

[0315] At this time, compounds having two or more phenolic hydroxyl groups or compounds having carboxyl groups are preferably represented by the following formulas (I1) to (I14).

[0316] [Chemistry 43]

[0317]

[0318] However, in the above formula, R 201 R 202 Each can independently represent a hydrogen atom, or a straight-chain or branched alkyl or alkenyl group having 1 to 8 carbon atoms. R 203Represents a hydrogen atom, or a straight-chain or branched alkyl or alkenyl group having 1 to 8 carbon atoms. R 204 It represents -(CH2) i -(i=2~10), arylene, carbonyl, sulfonyl, oxygen or sulfur atoms with 6~10 carbon atoms. R 205 R represents an alkylene group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom, or a sulfur atom. 206 Represents a hydrogen atom, a straight-chain or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or a phenyl or naphthyl group, respectively substituted with a hydroxyl group. R 208 Represents a hydrogen atom or a hydroxyl group. j is an integer from 0 to 5. u and h are 0 or 1. s, t, s', t', s”, and t” each independently satisfy s+t=8, s'+t'=5, s”+t”=4, and are numbers such as having at least one hydroxyl group in each phenyl skeleton. A is a number that makes the molecular weight of the compounds of formulas (I8) and (I9) between 100 and 1,000.

[0319] The amount of dissolution inhibitor incorporated is 0 to 50 parts by weight, preferably 5 to 50 parts by weight, and more preferably 5 to 20 parts by weight, relative to 100 parts by weight of the alkali-soluble resin of component (A). It can be used alone or in combination with two or more components. If the amount of incorporation is sufficient, the resolution is improved; if it is less than 50 parts by weight, no pattern loss will occur, and high resolution can be obtained.

[0320] (J) Surfactants should preferably be nonionic, such as fluorinated surfactants, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkyl amine oxides, fluorinated organosiloxane compounds, and nonfluorinated organosiloxane compounds.

[0321] These surfactants can be commercially available products, such as: Fluorad FC-4430 (manufactured by Sumitomo 3M Co., Ltd., trade name), PF-6320 (manufactured by OMNOVA Co., Ltd., trade name), PF-636 (manufactured by OMNOVA Co., Ltd., trade name), Surflon S-141 and S-145 (manufactured by Asahi Glass Co., Ltd., trade names), Unidyne DS-401, DS-4031 and DS-451 (manufactured by Daikin Industries, Ltd., trade names), Megafac F-8151 (manufactured by DIC Co., Ltd., trade name), X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), etc. Among these, Fluorad FC-4430 (manufactured by Sumitomo 3M Co., Ltd., product name), PF-6320 (manufactured by OMNOVA Co., Ltd., product name), PF-636 (manufactured by OMNOVA Co., Ltd., product name), and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd., product name) are recommended.

[0322] The amount of surfactant incorporated relative to 100 parts by weight of alkali-soluble resin of component (A) should preferably be 0.01 to 5 parts by weight, and more preferably 0.01 to 3 parts by weight.

[0323] (K) The solvent is not limited to any solvent that can dissolve components (A), (B), (C), and (D). Examples of solvents include: ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone, etc. One or more of these solvents may be used. Especially suitable solvents include ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, or mixtures thereof.

[0324] The amount of component (K) is preferably 50 to 2,000 parts by mass relative to the total amount of components (A), (B), (C) and (D) of 100 parts by mass, and more preferably 100 to 1,000 parts by mass.

[0325] (Pattern Formation Method)

[0326] The present invention provides a pattern forming method, comprising the following steps.

[0327] (1) The above negative photosensitive resin composition is coated on a substrate to form a photosensitive film;

[0328] (2) After heat treatment, the photomask exposes the photosensitive film using high-energy rays or electron beams with wavelengths of 190–500 nm; and

[0329] (3) After irradiation, the substrate that has undergone heat treatment is developed using an alkaline aqueous solution.

[0330] The following describes a pattern forming method using the negative photosensitive resin composition of the present invention.

[0331] In the negative photosensitive resin composition of the present invention, in order to form a pattern, a known photolithography technique can be used, for example, on a silicon wafer or SiO2 substrate, SiN substrate, or substrate with a pattern formed of copper wiring, the negative photosensitive resin composition is coated by spin coating and pre-baked at 80 to 130°C for about 50 to 600 seconds to form a photosensitive film with a thickness of 1 to 50 μm, preferably 1 to 30 μm, and more preferably 1 to 20 μm.

[0332] In spin coating, approximately 5 mL of a negative photosensitive resin composition is dispensed onto a silicon substrate, and then the substrate is rotated to coat the substrate with the negative photosensitive resin composition. The thickness of the photosensitive film on the substrate can be easily adjusted by changing the rotation speed.

[0333] Then, a mask for forming the desired pattern is placed over the aforementioned photosensitive film, with an exposure dose of approximately 1 to 5,000 mJ / cm. 2 The preferred value is approximately 100–2,000 mJ / cm³. 2 Irradiation with high-energy rays or electron beams with wavelengths of 190–500 nm, such as i-rays and g-rays.

[0334] Then, the product is subjected to post-exposure heating treatment (PEB) on a heating plate at 60–150°C for 50–600 seconds, preferably 80–120°C for 60–300 seconds.

[0335] Then, development is performed. In the negative photosensitive resin composition of the present invention described above, alkaline development can be performed using an alkaline aqueous solution.

[0336] On the other hand, an ideal alkaline aqueous solution for alkaline development is a 2.38% tetramethylhydroxyammonium (TMAH) aqueous solution. Development can be performed using conventional methods such as spraying, immersion, or soaking in the developing solution. Afterward, washing, rinsing, and drying are performed as needed to obtain a resist film with the desired pattern.

[0337] (Method for forming a hardened coating)

[0338] Furthermore, the patterned film obtained using the above-described patterning method is heated and post-cured using an oven and a heating plate at a temperature of 100–300°C, preferably 150–300°C, and most preferably 180–250°C, thereby forming a cured film. A post-curing temperature of 100–300°C can increase the cross-linking density of the negative photosensitive resin composition film and remove residual volatile components, which is beneficial for the substrate's adhesion, heat resistance, strength, and consequently, electrical properties. The post-curing time can be set to 10 minutes to 10 hours.

[0339] The patterns formed above are used for the purpose of covering protective films for wiring, circuits, and substrates. These patterns and protective films have excellent insulation properties and exhibit excellent adhesion to metal layers such as Cu in the covered wiring and circuits, metal electrodes on the substrate, or insulating substrates such as SiN in the covered wiring and circuits. They also have mechanical strength suitable for use as protective films and can significantly improve the resolution performance that can be used to form fine patterns.

[0340] (hardened membrane)

[0341] The hardened coating obtained in this way has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance to alkaline stripping solutions. The reliability of semiconductor devices using it as a protective coating is also excellent. In particular, it can prevent cracking during temperature cycling tests. It can be ideally used as a protective coating (interlayer insulating film or surface protective film) for electrical and electronic parts, semiconductor devices, etc.

[0342] That is, the present invention provides an interlayer insulating film or surface protective film composed of a hardened film formed by curing the above-mentioned negative photosensitive resin composition.

[0343] The aforementioned protective films are effective in applications such as insulating films for semiconductor components, insulating films for multilayer printed circuit boards, solder mask, and surface coating films due to their heat resistance, chemical resistance, and insulation properties.

[0344] Furthermore, the present invention provides an electronic component having the aforementioned interlayer insulating film or surface protective film. Such an electronic component exhibits excellent reliability due to the protective coating (interlayer insulating film or surface protective film) possessing heat resistance, chemical resistance, and insulation properties.

[0345] [Example]

[0346] The present invention will be specifically described below with examples of synthesis, embodiments, and comparative examples, but the present invention is not limited to the following examples. Furthermore, the weight-average molecular weight (Mw) represents the weight-average molecular weight of polystyrene obtained using GPC.

[0347] I. Synthesis of Alkali-Soluble Resin (A)

[0348] The chemical structural formulas and names of the compounds used in the following synthesis examples are shown below.

[0349] [Chemistry 44]

[0350]

[0351] [Synthesis Example 1] Synthesis of polyimide resin (A1)

[0352] In a 1L flask equipped with a stirrer and thermometer, 30g (81.9mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.9g (8.6mmol) of 4-aminophenol (PAP), and 125g of N-methyl-2-pyrrolidone were added and stirred at room temperature until dissolved. Then, at room temperature, a solution obtained by dissolving 26.7g (86.2mmol) of 3,3',4,4'-oxyphthalic dianhydride (s-ODPA) in 270g of N-methyl-2-pyrrolidone was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 3 hours. Subsequently, 40g of xylene was added to the reaction solution, and the mixture was heated under reflux for 3 hours at 170°C to remove the generated water from the system. After cooling to room temperature, 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 polyimide resin (A1). The molecular weight of this polymer, when determined by GPC, is 35,000 (converted to polystyrene).

[0353] [Synthesis Example 2] Synthesis of polyimide resin (A2)

[0354] In Synthesis Example 1, 30 g (81.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) was replaced with 21.2 g (81.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), and the same formulation was used to obtain polyimide resin (A2). The molecular weight of this polymer, determined by GPC, was 34,000 (weight average) converted to polystyrene.

[0355] [Synthesis Example 3] Synthesis of Polyamide-Imide Resin (A3)

[0356] In a 500 mL flask equipped with a stirrer and thermometer, 28.5 g (77.8 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.9 g (8.2 mmol) of 4-aminophenol (PAP), and 118 g of N-methyl-2-pyrrolidone were added and stirred at room temperature until dissolved. Then, at room temperature, a solution obtained by dissolving 19.0 g (61.4 mmol) of 3,3',4,4'-oxyphthalic dianhydride (s-ODPA) in 192 g of N-methyl-2-pyrrolidone was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 3 hours. Subsequently, 40 g of xylene was added to the reaction solution, and the mixture was heated under reflux at 170 °C for 3 hours to remove the generated water from the system. After cooling to room temperature, 3.2 g (41.0 mmol) of pyridine was added, followed by the dropwise addition of 4.9 g (20.5 mmol) of sebacyl chloride (DC-1) while maintaining the temperature below 5°C. After the addition was complete, the mixture was allowed to return to room temperature. The reaction solution was then 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 polyamide-imide resin (A3). The molecular weight of this polymer, determined by GPC, was 35,000 (converted to polystyrene weight average).

[0357] [Synthesis Example 4] Synthesis of Polyamide Resin (A4)

[0358] In a 500 mL flask equipped with a stirrer and thermometer, 28.5 g (77.8 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.9 g (8.2 mmol) of 4-aminophenol (PAP), and 118 g of N-methyl-2-pyrrolidone were added and stirred at room temperature until dissolved. Then, 13.0 g (163.8 mmol) of pyridine was added, followed by dropwise addition of 19.6 g (81.9 mmol) of sebacate chloride (DC-1) while maintaining the temperature below 5 °C. After the addition was complete, the temperature 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 polyamide resin (A4). The molecular weight of this polymer, determined by GPC, was 38,000 (converted to polystyrene).

[0359] [Synthetic Example 5] Synthesis of tetracarboxylic acid diester compound (X-1)

[0360] In a 3L flask equipped with a stirrer and thermometer, 100 g (322 mmol) of 3,3',4,4'-oxyphthalic 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. The mixture was stirred at room temperature, and 83.8 g (644 mmol) of hydroxyethyl methacrylate (HEMA) was added dropwise. The mixture was stirred at room temperature for 24 hours. Then, 370 g of 10% hydrochloric acid aqueous solution was added dropwise under ice-cold conditions to stop the reaction. 800 g of 4-methyl-2-pentanone was added to the reaction solution, and the organic layer was separated and washed six times with 600 g of water. The solvent of the obtained organic layer was distilled off to obtain 180 g of tetracarboxylic acid diester compound (X-1).

[0361] [Synthetic Example 6] Synthesis of polyimide precursor (A5)

[0362] In a 1L flask equipped with a stirrer and thermometer, 57.1g (100mmol) of (X-1) and 228g of N-methyl-2-pyrrolidone were added and stirred at room temperature to dissolve. Then, 24.4g (205mmol) of thionyl chloride was added dropwise under ice-cold conditions to maintain the temperature of the reaction solution below 10°C. After the addition was completed, the mixture was stirred under ice-cold conditions for 2 hours. Then, under ice-cold conditions to maintain the temperature of the reaction solution below 10°C, a solution obtained by dissolving 34.8g (95mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 1.1g (10mmol) of 4-aminophenol (PAP), and 32.4g (410mmol) of pyridine in 144g of N-methyl-2-pyrrolidone was added dropwise. After the addition was complete, the mixture was brought back to room temperature. The reaction solution was then added dropwise to 3 L of water with stirring. The precipitate was filtered, washed appropriately with water, and dried under reduced pressure at 40 °C for 48 hours to obtain the polyimide precursor (A5). The molecular weight of this polymer, when determined by GPC, was 36,000 (converted to polystyrene).

[0363] II. Synthesis of cross-linked polymers (B)

[0364] [Synthesis example]

[0365] For cross-linked polymeric compounds (polymeric additives), the monomers were copolymerized in tetrahydrofuran solvent, followed by crystallization and drying in hexane to obtain polymeric compounds with the compositions shown below (polymers B1-B22, comparative polymers C1 and C2). The composition of the obtained polymeric compounds was confirmed by 1H-NMR, and the molecular weight was confirmed by gel permeation chromatography.

[0366] [Synthesis Example 7] Polymer B1

[0367] Molecular weight (Mw) = 11,600

[0368] [Chemistry 45]

[0369]

[0370] [Synthesis Example 8] Polymer B2

[0371] Molecular weight (Mw) = 11,800

[0372] [Chemistry 46]

[0373]

[0374] [Synthesis Example 9] Polymer B3

[0375] Molecular weight (Mw) = 11,000

[0376] [Chemistry 47]

[0377]

[0378] [Synthetic Example 10] Polymer B4 molecular weight (Mw) = 10,800

[0379] [Chemistry 48]

[0380]

[0381] [Synthesis Example 11] Polymer B5

[0382] Molecular weight (Mw) = 11,300

[0383] [Chemistry 49]

[0384]

[0385] [Synthesis Example 12] Polymer B6

[0386] Molecular weight (Mw) = 9,800

[0387] [Transformation 50]

[0388]

[0389] [Synthesis Example 13] Polymer B7

[0390] Molecular weight (Mw) = 9,500

[0391] [Chemistry 51]

[0392]

[0393] [Synthesis Example 14] Polymer B8

[0394] Molecular weight (Mw) = 10,200

[0395] [Chemistry 52]

[0396]

[0397] [Synthesis Example 15] Polymer B9

[0398] Molecular weight (Mw) = 12,300

[0399] [Chemistry 53]

[0400]

[0401] [Synthesis Example 16] Polymer B10

[0402] Molecular weight (Mw) = 11,800

[0403] [Chemistry 54]

[0404]

[0405] [Synthesis Example 17] Polymer B11

[0406] Molecular weight (Mw) = 9,000

[0407] [Chemistry 55]

[0408]

[0409] [Synthesis Example 18] Polymer B12

[0410] Molecular weight (Mw) = 9,300

[0411] [Chemistry 56]

[0412]

[0413] [Synthesis Example 19] Polymer B13

[0414] Molecular weight (Mw) = 9,500

[0415] [Chemistry 57]

[0416]

[0417] [Synthesis Example 20] Polymer B14

[0418] Molecular weight (Mw) = 10,400

[0419] [Chem.58]

[0420]

[0421] [Synthesis Example 21] Polymer B15

[0422] Molecular weight (Mw) = 12,300

[0423] [Chemistry 59]

[0424]

[0425] [Synthesis Example 22] Polymer B16

[0426] Molecular weight (Mw) = 12,300

[0427] [Transformation 60]

[0428]

[0429] [Synthesis Example 23] Polymer B17

[0430] Molecular weight (Mw) = 11,300

[0431] [Chemistry 61]

[0432]

[0433] [Synthesis Example 24] Polymer B18

[0434] Molecular weight (Mw) = 11,700

[0435] [Chemistry 62]

[0436]

[0437] [Synthesis Example 25] Polymer B19

[0438] Molecular weight (Mw) = 11,300

[0439] [Chemistry 63]

[0440]

[0441] [Synthesis Example 26] Polymer B20

[0442] Molecular weight (Mw) = 12,300

[0443] [Chemistry 64]

[0444]

[0445] [Synthesis Example 27] Polymer B21

[0446] Molecular weight (Mw) = 11,300

[0447] [Chemistry 65]

[0448]

[0449] [Synthesis Example 28] Polymer B22

[0450] Molecular weight (Mw) = 10,300

[0451] [Chemistry 66]

[0452]

[0453] [Synthetic Example 29] Comparative polymer C1

[0454] Molecular weight (Mw) = 11,900

[0455] [Chemistry 67]

[0456]

[0457] [Synthetic Example 30] Comparison of polymer C2

[0458] Molecular weight (Mw) = 10,600

[0459] [Chemistry 68]

[0460]

[0461] III. Preparation of Negative Photosensitive Resin Compositions

[0462] Using 70 parts by mass of the alkali-soluble resins (A1) to (A5) synthesized in Synthetic Examples 1 to 6, the crosslinking polymers (B1) to (B22), (C1), and (C2) synthesized in Synthetic Examples 7 to 30, and the following comparative polymer (C3) in 30 parts by mass as the base resin, a resin composition of 20% by mass was prepared according to the composition and blending amount listed in Table 1. After stirring, mixing, and dissolving, the mixture was precisely filtered using a 1.0 μm filter made with Teflon (registered trademark) to obtain a negative photosensitive resin composition. In the table, PGMEA represents propylene glycol monomethyl ether acetate, and GBL represents γ-butyrolactone.

[0463] [Table 1]

[0464]

[0465] In addition, Table 1 lists the following as detailed information: photoacid generator of oxime sulfonate compound (PAG-1), photosensitive agent of quinone diazide compound (PAC-1), crosslinking agent (CL-1)(CL-2)(CL-3)(CL-4), basic compound (E-1), thermal acid generator (F-1), (F-2), antioxidant (G-1), silane compound (H-1), dissolution inhibitor (I-1), surfactant (J-1), and phenolic varnish resin (C3).

[0466] Photoacid generator (PAG-1)

[0467] [Chemistry 69]

[0468]

[0469] Photosensitive agent (PAC-1)

[0470] [Chemistry 70]

[0471]

[0472] In the formula, Q represents the 1,2-naphthoquinone diazidosulfonyl group or hydrogen atom represented by the following formula (23), and 90% of Q is substituted by the 1,2-naphthoquinone diazidosulfonyl group represented by the following formula (23).

[0473] [Chemistry 71]

[0474]

[0475] Crosslinking agent (CL-1)

[0476] [Chemistry 72]

[0477]

[0478] Crosslinking agent (CL-2)

[0479] [Chemistry 73]

[0480]

[0481] Crosslinking agent (CL-3)

[0482] Oxycyclic butane resin: OXT-121 manufactured by Toa Synthetic Co., Ltd.

[0483] Crosslinking agent (CL-4)

[0484] Epoxy resin: EP4000L manufactured by ADEKA (stock).

[0485] Basic compounds (E-1)

[0486] [Chemistry 74]

[0487]

[0488] Hot acid generator (F-1)

[0489] [Chemistry 75]

[0490]

[0491] Hot acid generator (F-2)

[0492] [Chemistry 76]

[0493]

[0494] Antioxidant (G-1)

[0495] Hindered phenolic antioxidants: Sumitomo Chemical Co., Ltd.'s Sumilizer GA-80

[0496] Silane compounds (H-1)

[0497] Aminosilane coupling agent: KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.

[0498] Dissolution inhibitor (I-1)

[0499] [Chemistry 77]

[0500]

[0501] Surfactant (J-1)

[0502] Fluorinated surfactant: PF-6320 manufactured by OMNOVA

[0503] Comparison using polymer C3

[0504] Phenolic varnish resin: Asahi Organic Materials Industry Co., Ltd. EP6030G

[0505] IV. Pattern Formation

[0506] By applying 5 mL of the aforementioned photosensitive resin compositions 1-28 and comparative photosensitive resin compositions 1-4 to a silicon substrate treated with hexamethylsilazane, and then rotating the substrate (i.e., spin coating), the post-cured film thickness after pattern formation was 3 μm. Specifically, considering that the film thickness would decrease after the post-curing step, the coating speed was adjusted to achieve a final post-cured film thickness of 2 μm.

[0507] Then, pre-baking was performed at 100°C for 2 minutes on a heated plate. Next, i-ray exposure was performed using a Veeco AP300E i-ray stepper. After irradiation, post-exposure baking (PEB) was performed at 110°C for 2 minutes, followed by cooling. A mask for negative patterning was used in pattern formation. This mask has the capability to form a 1:1 line-to-space pattern (hereinafter referred to as LS pattern) with 2μm spacing, and can form LS patterns in 1μm increments within a range of 10μm to 2μm.

[0508] Then, a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution was used as the developer, and the film was immersed for 1 minute until the unexposed parts of the coating were dissolved. Then, the film was rinsed with ultrapure water.

[0509] Then, the patterned substrate is post-cured by blowing nitrogen into an oven at 180°C for 2 hours.

[0510] Then, each substrate was cut out in such a way that the shape of the observable LS pattern was obtained, and the shape of the line pattern was observed using a scanning electron microscope (SEM). The shape of the 2μm LS line pattern after curing was evaluated. Furthermore, these results, along with the sensitivity and number of development cycles required to form a 2μm pattern, are shown in Table 2.

[0511] Furthermore, the shape of the LS pattern was evaluated based on the following criteria, and the evaluation results are shown in Table 2. The pattern cross-section of the smallest LS line was observed, and the widths of the uppermost and lowermost parts of the cross-section were compared. Patterns with a difference of 0 μm or more but less than 0.2 μm were rated A; those with a difference of more than 0.2 μm but less than 0.5 μm were rated B; those with a difference of more than 0.5 μm but less than 1.0 μm were rated C; and those with a difference of more than 1.0 μm were rated D.

[0512] V. Elongation at break and tensile strength

[0513] The above-mentioned photosensitive resin compositions 1 to 28 and comparative photosensitive resin compositions 1 to 4 were spin-coated onto an aluminum substrate to achieve a final film thickness of 10 μm after curing. Then, the film was pre-baked at 100°C for 4 minutes on a heating plate to obtain a photosensitive resin film.

[0514] Subsequently, a Quintel UL-7000 contact aligner was used with a wideband wavelength and a setting of 500 mJ / cm². 2The substrate was exposed to a certain amount of light through contact exposure. After irradiation, a PEB treatment was performed at 110°C for 4 minutes, followed by cooling. Then, curing was carried out in an oven at 180°C with nitrogen blowing for 2 hours to obtain a photosensitive resin curing film. The wafer with the curing film was then cut into strips 10 mm wide and 60 mm long, and immersed in 20% hydrochloric acid to peel the curing film off the substrate. The elongation at break and tensile strength of the obtained curing film were measured using an Autograph AGX-1KN device manufactured by Shimadzu Corporation. Ten measurements were performed for each sample, and the average values ​​are shown in Table 2.

[0515] [Table 2]

[0516]

[0517] VI. Close Contact

[0518] Using the same procedure as described above for pattern formation, and employing photosensitive resin compositions 1-28 and comparative photosensitive resin compositions 3-4, a 1 cm square pattern was exposed to I-rays on a SiN substrate to achieve a final film thickness of 5 μm after curing. This resulted in a grid-like pattern across the entire substrate. The exposure amount was determined based on the LS pattern evaluation to achieve the minimum pattern size. Pre-baking was performed at 100°C for 4 minutes, and PEB was performed at 110°C for 4 minutes. Development involved immersion development for 1 minute until the coating film in the unexposed areas dissolved, repeated a predetermined number of times.

[0519] Next, nitrogen gas was blown in at 180°C for 2 hours to perform post-curing of the patterned substrate. Then, the cured substrate was monolithically processed according to a 1cm square pattern to obtain a wafer with a cured film. Epoxy resin-coated aluminum pins were attached to the obtained wafer, and the wafer was heated at 150°C for 1 hour to bond the aluminum pins to the wafer, thus preparing a test sample. After cooling, the sample was analyzed using a ROMULUS instrument manufactured by QuadGroup. Figure 1 The method shown (hereinafter referred to as the Stud-pull method) was used to determine the contact strength. The measurement was performed at a speed of 20 N / sec. Figure 1 This is an explanatory diagram showing the method for measuring contact strength. In addition, Figure 1 In the diagram, 1 represents the SiN substrate (substrate), 2 represents the hardened film, 3 represents the aluminum pin with adhesive, 4 represents the support platform, 5 represents the gripping part, and 6 represents the stretching direction. The obtained values ​​are the average of 10 measurements; the higher the value, the stronger the adhesion of the hardened film to the copper-plated substrate. Furthermore, regarding the peel interface, the adhesion at the peel interface of the hardened film / adhesive is higher than that at the substrate / hardened film peel interface. Adhesion is evaluated by comparing the obtained values ​​and peel interfaces.

[0520] In addition, for the high temperature and high humidity test, the obtained wafers were placed in a pressure cooker at 2 atmospheres saturation, 120°C, and 100% RH for 168 hours. Afterwards, the adhesion strength after the test was evaluated using the Stud-pull method, and the results, together with the results before the test, are shown in Table 3 as the adhesion strength to the substrate.

[0521] [Table 3]

[0522]

[0523] As shown in Table 2, compared to the negative photosensitive resin compositions 1-2 (which contain polymeric compounds consisting only of crosslinking groups) and 4 (which contain a thermal crosslinking agent), the negative photosensitive resin composition of the present invention exhibits good rectangularity and can resolve LS patterns as small as 2 μm. Furthermore, the film of the comparative photosensitive resin composition 3 is more brittle, and its elongation at break and tensile strength cannot be measured.

[0524] Furthermore, as shown in Table 3, the negative photosensitive resin composition of the present invention can produce a cured film with good mechanical properties and high temperature and humidity resistance even when cured at low temperatures below 200°C. On the other hand, the cured films obtained using comparative photosensitive resin compositions 3 and 4 show deterioration in adhesion after high temperature and humidity compared to the cured films obtained using the composition of the present invention.

[0525] The results above show that the compositions of Examples 1 to 28 achieved the following results: good rectangularity, excellent resolution of fine patterns with a resolution of 2 μm, sufficient characteristics as a photosensitive material, and their hardened film has good substrate adhesion and good high temperature and high humidity resistance, making them useful as protective films for circuits and electronic components.

[0526] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any embodiments having substantially the same structure as the technical concept described in the claims of the present invention and achieving the same effect are included within the technical scope of the present invention.

[0527] [Symbol Explanation]

[0528] 1:SiN substrate (substrate)

[0529] 2: Hardened membrane

[0530] 3: Aluminum pins with adhesive

[0531] 4: Support Taiwan

[0532] 5: Grasping section

[0533] 6: Tension direction

Claims

1. A negative photosensitive resin composition, comprising: (A) An alkali-soluble resin containing at least one structure selected from polyimide structure, polyamide structure, polybenzoxazole structure, polyamide-imide structure, and their precursor structures, wherein component (A) contains a structure represented by the following general formula (6), general formula (7) or general formula (18); (B) A cross-linked polymeric compound, wherein (B) is a cross-linked polymeric compound containing structural units represented by the following general formula (2) and containing structural units represented by any one or both of the following general formulas (4) and (4′); (C) Compounds that produce acids due to light; and (D) A crosslinking agent other than component (B); component (D) contains one or more crosslinking agents selected from amino condensates modified with formaldehyde or formaldehyde-alcohol, and phenolic compounds having an average of more than two hydroxymethyl or alkoxyhydroxymethyl groups in one molecule; In the formula, R 14’ , 9 , 13’ , 11 , 12 , 10 , 9 , 5 , 15’ , 4 represents a hydrogen atom or a methyl group, and X4s are each independently -C(=O)-O-, or a phenylene group or a naphthylene group; R 9 is a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may also contain a hydroxyl group, an ester group, an ether group, or an aromatic hydrocarbon, R 10 is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or may bond with R 9 to form a ring; R 11 is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, R 12 is a hydrogen atom, or a linear alkyl group having 1 to 6 carbon atoms, and may bond with R 9 to form a ring; m is 1; p is 0 or 1; R 13’ represents a hydrogen atom or a methyl group, R 14’ represents a single bond or an alkylene group, R 15’ is a blocked isocyanate group; 0 < b2 < 1.0, 0 ≤ b4 < 1.0, 0 ≤ b4' < 1.0, 0 < b4 + b4' < 1.0, 0 < b2 + b4 + b4' ≤ 1.0 or 0 < b2 + b4 ≤ 1.0 and 0 < b2 + b4' ≤ 1.0; R 4 represents a hydrogen atom or a methyl group, and X2s are each independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R 5 OH)-; R 5 is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and the carbon atoms of the aliphatic saturated hydrocarbon group may be replaced by oxygen atoms; In formula (6), X6 is a tetravalent organic group, s represents 0 or 1, Z is a divalent bonding group, and when s = 0, the two aromatic rings in the formula are directly bonded without the bonding group; In formula (7), X7 is a divalent organic group, and s and Z are the same as described above; In equation (18), X 11 It is a tetravalent organic group that is the same as or different from X6 mentioned above; s and Z are the same as those mentioned above; R 23 and R 24 Each is independently a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group represented by the following general formula (20), R 23 and R 24 At least one of them is an organic group represented by the following general formula (20); In equation (20), the dotted line represents the bond, R 25 R is a hydrogen atom or an organic group having 1 to 3 carbon atoms. 26 and R 27 Each is an independent hydrogen atom or an organic group having 1 to 3 carbon atoms, and o is an integer from 2 to 10.

2. The negative photosensitive resin composition according to claim 1, wherein, The (B) component contains structural units represented by the following general formula (2), structural units represented by the following general formula (5), and cross-linked polymeric compounds containing any one of the following general formulas (4) and (4′) or both; In the formula, R 13 represents a hydrogen atom or a methyl group, R 14 is a linear, branched or cyclic aliphatic saturated hydrocarbon group with 1 to 12 carbon atoms and a valence of (l + 1), and the carbon atoms of the aliphatic saturated hydrocarbon group can also be replaced by oxygen atoms; X5 are each independently -C(=O)-O-, -C(=O)-NH-, -C(=O)-N(R 15 OH)-, or a phenylene group or a naphthylene group; R 15 is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group with 1 to 12 carbon atoms, an aromatic hydrocarbon group with 6 to 12 carbon atoms, and the carbon atoms of the aliphatic saturated hydrocarbon group can also be replaced by oxygen atoms; l is 0 or 1; 0 < b2 < 1.0, 0 ≤ b4 < 1.0, 0 ≤ b4' < 1.0, 0 < b4 + b4' < 1.0, 0 ≤ b5 < 1.0, 0 < b2 + b4 + b4' + b5 ≤ 1.0 or 0 < b2 + b4 + b5 ≤ 1.0 and 0 < b2 + b4' + b5 ≤ 1.0; R 4 represents a hydrogen atom or a methyl group, X2 are each independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R 5 OH)-; R 5 is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group with 1 to 12 carbon atoms, an aromatic hydrocarbon group with 6 to 12 carbon atoms, and the carbon atoms of the aliphatic saturated hydrocarbon group can also be replaced by oxygen atoms; p is 0 or 1; R 8 represents a hydrogen atom or a methyl group, X4 are each independently -C(=O)-O-, or a phenylene group or a naphthylene group; R 9 is a linear, branched or cyclic alkylene group with 1 to 15 carbon atoms that may also contain a hydroxyl group, an ester group, an ether group, or an aromatic hydrocarbon, R 10 is a hydrogen atom, a linear, branched or cyclic alkyl group with 1 to 6 carbon atoms, or may bond with R 9 to form a ring; R 11 is a hydrogen atom, or a linear, branched or cyclic alkyl group with 1 to 6 carbon atoms, R 12 is a hydrogen atom, or a linear alkyl group with 1 to 6 carbon atoms, and may bond with R 9 to form a ring; m is 1; R 13’ represents a hydrogen atom or a methyl group, R 14’ represents a single bond or an alkylene group, R 15’ is a blocked isocyanate group.

3. The negative photosensitive resin composition according to claim 1 or claim 2, wherein, The content of component (B) is 10 to 100 parts by mass relative to 100 parts by mass of component (A).

4. The negative photosensitive resin composition according to claim 1 or claim 2 further contains one or more of (E) an alkaline compound, (F) a thermal acid generator, (G) an antioxidant, and (H) a silane compound.

5. A method for forming a pattern, comprising the following steps: (1) The negative photosensitive resin composition according to any one of claims 1 to 4 is coated on a substrate to form a photosensitive film; (2) After heat treatment, the photosensitive film is exposed to high-energy rays or electron beams with wavelengths of 190–500 nm using a spacer photomask; and (3) After irradiation, the substrate that has undergone heat treatment is developed using an alkaline aqueous solution.

6. A method for forming a hardened film, comprising the following steps: The patterned film obtained by the patterning method according to claim 5 is heated and then hardened at a temperature of 100 to 300°C.

7. An interlayer insulating film comprising a hardened film formed by curing a negative photosensitive resin composition according to any one of claims 1 to 4.

8. A surface protective film comprising a hardened film formed by curing a negative photosensitive resin composition according to any one of claims 1 to 4.

9. An electronic component having an interlayer insulating film according to claim 7 or a surface protective film according to claim 8.

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