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

Abstract

The present invention relates to a negative photosensitive resin composition, a pattern forming method, a hardened film forming method, an interlayer insulating film, and a surface protective film. The present invention aims to provide a negative photosensitive resin composition which is soluble in an aqueous alkali solution, can form a fine pattern and obtain a high resolution, and has good mechanical properties such as a breaking elongation and a tensile strength even when hardened at a low temperature. The means for solving the problem is a negative photosensitive resin composition characterized by containing: (A) an alkali-soluble resin containing at least one or more structures selected from the group consisting of a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamide-imide structure, and a precursor structure thereof; (B) a high molecular compound having a structural unit resulting from a cyclopolymerization; (C) a compound which generates an acid by 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 capable of being developed with an alkaline aqueous solution, a method for forming a hardened film, an interlayer insulating film, a surface protective film, and electronic components. Existing technology

[0002] With the miniaturization and increasing performance of various electronic devices such as personal computers, digital cameras, and mobile phones, the requirements for further miniaturization, thinning, and high density in 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 have long been used as protective films and insulating layers. Their insulation, mechanical properties, and adhesion to the substrate have continued to receive attention, and their development remains thriving.

[0004] Various methods have been employed to further improve the aforementioned required properties. In particular, some researchers have proposed using photosensitive resin compositions of closed-ring polyimide resins to achieve lower post-curing temperatures (Patent Document 1, Patent Document 2). However, it is difficult to simultaneously achieve satisfactory results in terms of cured film properties such as resolution, mechanical properties (elongation, tensile strength), and adhesion, leaving room for improvement.

[0005] Furthermore, regarding the improvement of the mechanical strength of the hardened film, some researchers have proposed adding (meth)acrylic resins to balance photolithography properties and the physical properties of the hardened film (Patent Documents 3, 4, and 5). However, since this is for the modification of the main resin, there is still room for improvement in the mechanical strength of the hardened film.

[0006] On the other hand, as an improvement method, research has been conducted on resins in which cyclic olefin (norbenzyl monomer, maleic anhydride, or maleimide) structural units or cyclized polymer monomer units are introduced into the main chain backbone, in addition to polyimide, its precursor, polybenzoxazole, and its precursor (Patent Document 6, Patent Document 7, Patent Document 8, Patent Document 9).

[0007] Patent documents 6 and 7 have proposed alkali-soluble resins containing N-hydroxymaleimide units and norcamphene units, and further added phenolic varnish resins and used positive photosensitive resin compositions of diazonium quinone compounds, but there is no detailed discussion on micronization, and no record of the physical properties of the hardened film.

[0008] Furthermore, Patent Document 8 has proposed the use of a negative photosensitive resin composition consisting of a copolymer of (meth)acrylate units and maleimide, a compound having more than one polymerizable group with bifunctionality, and a photopolymerization initiator, but there is no record of the resolution or mechanical strength of the fine pattern.

[0009] Furthermore, Patent Document 9 has proposed using a copolymer composed of monomers with acid groups introduced into the side chains, maleimide-based monomers, and cyclic monomers, and a negative photosensitive resin composition using an alkali-soluble resin with unsaturated double bonds introduced into the acid groups of the side chains and a photopolymerization initiator. This composition exhibits excellent mechanical properties such as elastic recovery rate and breaking strength in the hardened film. However, due to the utilization of the photosensitive properties of free radical crosslinking, there is still room for improvement in miniaturization.

[0010] Therefore, considering that in the future, with the increasing density and integration of chips, the miniaturization of patterns in the reinforcing protective film in the rewiring technology will also continue to advance, and in photosensitive resin compositions, it is strongly desired that the excellent mechanical properties of the resulting protective film will not be damaged by low-temperature heating, and that the composition can exhibit high resolution.

[0011] Existing technical documents

[0012] Patent documents

[0013] [Patent Document 1] Japanese Patent No. 4530284

[0014] [Patent Document 2] Japanese Patent Application Publication No. 2006-313237

[0015] [Patent Document 3] Japanese Patent No. 5884837

[0016] [Patent Document 4] Japanese Patent Application Publication No. 2015-129791

[0017] [Patent Document 5] Japanese Patent Application Publication No. 2015-200819

[0018] [Patent Document 6] Japanese Patent Application Publication No. 2019-045622

[0019] [Patent Document 7] Japanese Patent Application Publication No. 2020-170103

[0020] [Patent Document 8] Japanese Patent No. 6315204

[0021] [Patent Document 9] Japanese Patent No. 6694230 Summary of the Invention

[0022] The problem that the invention aims to solve

[0023] The present invention is made in view of the above facts, and aims to provide a negative photosensitive resin composition that is soluble in alkaline aqueous solution, can form fine patterns and obtain high resolution, and maintains good mechanical properties such as elongation at break and tensile strength even when hardened over a wide temperature range at low temperatures.

[0024] Methods for solving problems

[0025] To address the aforementioned issues, the present invention provides a negative photosensitive resin composition comprising:

[0026] (A) An alkali-soluble resin containing at least one structure selected from polyimide, polyamide, polybenzoxazole, polyamide-imide, and their precursor structures.

[0027] (B) Polymer compounds with structural units formed by cyclization polymerization

[0028] (C) Compounds that produce acids due to light, and

[0029] (D) Thermal crosslinking agent.

[0030] If it is such a negative photosensitive resin composition, it is soluble in alkaline aqueous solution, can form fine patterns and obtain high resolution, and even when cured over a wide temperature range at low temperatures, mechanical properties such as elongation at break and tensile strength remain good.

[0031] Furthermore, in the negative photosensitive resin composition of the present invention, the structural unit formed by the aforementioned cyclization polymerization of the aforementioned component (B) is preferably at least one of the structural units represented by the following general formula (1), general formula (2), general formula (3) and general formula (4).

[0032] [Chemistry 1]

[0033]

[0034] In the formula, R 1 R 2 R 3 R 4 R 5 and R 6 Each is an alkyl group that is independently composed of hydrogen atoms or has 1 to 5 carbon atoms and is either straight-chain or branched.

[0035] By having a ring structure in the main chain, mechanical properties such as elongation at break and tensile strength remain good even when hardened at low temperatures, and heat resistance is further improved.

[0036] Furthermore, in the negative photosensitive resin composition of the present invention, the aforementioned component (B) is preferably an alkali-soluble polymeric compound that further contains structural units represented by the following general formula (5) or (5').

[0037] [Chemistry 2]

[0038]

[0039] In the formula, R 7 Representing a hydrogen atom or a methyl group, X1 represents -C(=O)-O- or -C(=O)-OR, respectively. 8 -, -C(=O)-NH-, -C(=O)-NH-R 8 -or-C(=O)-N(R) 8 OH)-. R 8 It is a divalent aliphatic saturated hydrocarbon group with 1 to 12 carbon atoms, in the form of a straight chain, branched structure, or cyclic structure, or an aromatic hydrocarbon group with 6 to 12 carbon atoms. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon group can also be substituted with oxygen atoms. Furthermore, the hydrogen atoms of the aromatic hydrocarbon group can also be substituted with methyl groups. p is 0 or 1.

[0040] If it is such a negative photosensitive resin composition, it is soluble in alkaline aqueous solution, can form fine patterns and obtain high resolution.

[0041] Furthermore, the aforementioned component (B) should preferably be a cross-linked alkali-soluble polymer containing either or both of the structural units represented by the following general formula (6) and the structural units represented by the following general formula (α).

[0042] [Chemistry 3]

[0043]

[0044] In the formula, R 9 X represents a hydrogen atom or a methyl group, and X2 represents -C(=O)-O-, or phenylene or naphthylene, respectively. R 10 It may also contain alkylene groups of 1 to 15 carbon atoms in the form of straight-chain, branched, or cyclic groups, such as ester, ether, or aromatic hydrocarbon groups. 11 It consists of hydrogen atoms, a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or may also contain R. 10 Bonding and forming a loop. R 12 R is a hydrogen atom, or a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms. 13 It is a hydrogen atom or a straight-chain alkyl group having 1 to 6 carbon atoms, and can also be combined with R. 10 Bonding and forming a ring. m is 0 or 1. p is 0 or 1. In the formula, R1' represents a hydrogen atom or a methyl group, R2' represents a single bond or an alkylene group, and R3' is a terminal isocyanate group.

[0045] Such alkali-soluble polymers have cross-linking groups with excellent cross-linking properties, so they will undergo cross-linking reactions with the phenolic hydroxyl groups of the alkali-soluble resin of component (A). Even when hardened at low temperature, the mechanical properties such as elongation at break and tensile strength are still good, and the heat resistance is further improved.

[0046] Furthermore, the aforementioned component (B) should preferably be a cross-linked, alkali-soluble polymeric compound containing structural units represented by the following general formula (7).

[0047] [Chemistry 4]

[0048]

[0049] In the formula, R 14 R represents a hydrogen atom or a methyl group. 15 It is a straight-chain, branched, or cyclic aliphatic saturated hydrocarbon group with 1 to 13 carbon atoms, either with a single bond or (1+1) valence, and the carbon atoms of the aforementioned aliphatic saturated hydrocarbon group can also be replaced by oxygen atoms. X3 are -C(=O)-O- and -C(=O)-OR, respectively. 16 -, -C(=O)-NH-, -C(=O)-N(R 16 OH)-, or phenylene or naphthylene. R 16 It is a divalent aliphatic saturated hydrocarbon group with 1 to 12 carbon atoms, in the form of a straight chain, branched structure, or cyclic structure, or an aromatic hydrocarbon group with 6 to 12 carbon atoms, wherein the carbon atoms of the aforementioned aliphatic saturated hydrocarbon group may also be replaced by oxygen atoms. l is 0 or 1.

[0050] If it is such a polymer compound, then high-resolution patterns can be obtained because it can maintain alkali solubility while reacting with (D) thermal crosslinking agent.

[0051] In addition, the aforementioned component (B) is preferably a cross-linked alkali-soluble polymer containing any one or both of the following general formulas (3), (5), (6) or (α), and the structural unit represented by the following general formula (7).

[0052] [Chemistry 5]

[0053]

[0054] In the formula, R 4 It is a straight-chain or branched alkyl group with hydrogen atoms or 1 to 5 carbon atoms. R 7 Representing a hydrogen atom or a methyl group, X1 represents -C(=O)-O- or -C(=O)-OR, respectively. 8 -, -C(=O)-NH-, -C(=O)-NH-R 8 -or-C(=O)-N(R) 8 OH)-. R 8is 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 also be substituted with oxygen atoms. Further, the hydrogen atoms of the aromatic hydrocarbon group in the formula may also be substituted with methyl groups. R 9 represents a hydrogen atom or a methyl group, and X2 are each -C(=O)-O-, or a phenylene group or a naphthylene group. R 10 is a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may also contain an ester group, an ether group, an aromatic hydrocarbon group, R 11 is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or may also bond with R 10 to form a ring. R 12 is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, R 13 is a hydrogen atom, or a linear alkyl group having 1 to 6 carbon atoms, and may also bond with R 10 to form a ring. R1’ represents a hydrogen atom or a methyl group, R2’ represents a single bond or an alkylene group, and R3’ is a blocked isocyanate group. R 14 represents a hydrogen atom or a methyl group, R 15 is a single bond or a (l + 1)-valent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms, and the carbon atoms of the aliphatic saturated hydrocarbon group may also be substituted with oxygen atoms. X3 are each -C(=O)-O-, -C(=O)-O-R 16 -, -C(=O)-NH-, -C(=O)-N(R 16 OH)-, or a phenylene group or a naphthylene group. R 16 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 also be substituted with oxygen atoms. p is 0 or 1. m is 0 or 1. l is 0 or 1. And 0 < a1 < 1.0, 0 < a2 < 1.0, 0 ≤ a3 < 1.0, 0 ≤ b1 < 1.0, 0 < a3 + b1 < 1.0, 0 < a4 < 1.0, and satisfy any one of 0 < a1 + a2 + a3 + a4 ≤ 1.0, 0 < a1 + a2 + b1 + a4 ≤ 1.0, 0 < a1 + a2 + a3 + b1 + a4 ≤ 1.0.

[0055] If it is such a crosslinkable polymer compound, sufficient alkali solubility can be maintained while obtaining a high-resolution pattern. Further, since a ring structure is introduced into the main chain skeleton and there are also crosslinkable groups with excellent crosslinkability, mechanical properties such as elongation at break and tensile strength are still good even during low-temperature curing.

[0056] 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 more than two hydroxymethyl or alkoxyhydroxymethyl groups per molecule.

[0057] If it is such a (D) component, the alkali solubility of the photosensitive resin composition is more ideal, and the cross-linking reaction can be fully carried out at the PEB (Post Exposure Bake) temperature during photolithographic patterning, and good photolithographic patterning can be achieved.

[0058] Furthermore, relative to 100 parts by mass of the aforementioned component (A), it is preferable to contain 10 to 100 parts by mass of the aforementioned component (B).

[0059] Within this range, sufficient mechanical properties of the hardened film can be obtained while maintaining photolithographic characteristics, especially elongation and tensile strength.

[0060] It should contain at least one of the following: (E) alkaline compounds, (F) hot acid generators, (G) antioxidants, and (H) silane compounds.

[0061] The alkaline compound containing component (E) not only improves the dissolution contrast during photolithographic patterning but also allows for control over the pattern shape. Furthermore, the hot acid generator in component (F) further enhances the crosslinking and curing reactions, thereby improving the mechanical strength, chemical resistance, and adhesion of the resulting pattern or film. Additionally, the antioxidant in component (G) suppresses the degradation of physical properties caused by oxidative deterioration of the cured film during reliability tests such as high humidity and thermal shock, and forms a more ideal cured film. Finally, the silane compound in component (H) further improves the adhesion of the resulting pattern or film to the substrate.

[0062] Furthermore, the present invention provides a pattern forming method, comprising the following steps:

[0063] (1) The above-mentioned negative photosensitive resin composition is coated on a substrate to form a photosensitive film.

[0064] (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

[0065] (3) After irradiation, the substrate that has undergone heat treatment is developed using an alkaline aqueous solution.

[0066] If such a pattern-forming method is used, then 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.

[0067] Furthermore, the present invention provides a method for forming a hardened film, comprising the following steps:

[0068] The patterned film obtained by the above patterning method is heated and then hardened at a temperature of 100–300°C.

[0069] If such a method of forming a hardened film is used, a hardened film (pattern) with good mechanical properties can still be formed even when hardening at low temperatures.

[0070] 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.

[0071] 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.

[0072] 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., and the reliability of semiconductor elements using it as a protective coating is also excellent. Therefore, it is suitable as a protective coating (interlayer insulating film or surface protective film) for electrical and electronic parts, semiconductor elements, etc.

[0073] Furthermore, the present invention provides an electronic component having the above-mentioned interlayer insulating film or the above-mentioned surface protective film.

[0074] Such protective films (interlayer insulating films or surface protective films) are effective in applications such as insulating films for semiconductor components used in rewiring and insulating films for multilayer printed circuit boards, taking into account their heat resistance, chemical resistance, and insulation properties, and can be used to manufacture electronic components with high reliability.

[0075] The effects of the invention

[0076] As described above, the present invention can provide a negative photosensitive resin composition that is soluble in alkaline aqueous solutions, can form fine patterns and achieve high resolution, and maintains high elongation, high strength and good mechanical properties and excellent adhesion even when cured over a wide temperature range with low temperatures. Attached Figure Description

[0077] [ Figure 1 [ ] is an explanatory diagram showing the method for measuring contact strength. Detailed Implementation

[0078] As described above, a photosensitive resin composition is required that is soluble in alkaline aqueous solutions, can form fine patterns and achieve high resolution, and retains good mechanical properties even when cured at low temperatures.

[0079] Through in-depth research to achieve the above-mentioned objectives, the inventors discovered that patterns obtained using a negative photosensitive resin composition can form fine patterns, and the resulting cured film exhibits excellent mechanical properties; this negative photosensitive resin composition is characterized by containing:

[0080] (A) An alkali-soluble resin containing at least one structure selected from polyimide, polyamide, polybenzoxazole, polyamide-imide, and their precursor structures.

[0081] (B) Polymer compounds with structural units formed by cyclization polymerization

[0082] (C) Compounds that produce acids due to light, and

[0083] (D) Thermal crosslinking agent.

[0084] Furthermore, it was found that the protective film obtained by using the above-mentioned negative photosensitive resin composition and through pattern formation and heating exhibits excellent adhesion after high temperature and high humidity testing. In other words, it was found that a hardened film obtained by using a pattern formed from the above-mentioned negative photosensitive resin composition is excellent as a protective film for electrical-electronic components, an insulating protective film, and thus completes the present invention. In addition, electrical-electronic components are collectively referred to as "electronic components" in this specification.

[0085] That is, the present invention is a negative photosensitive resin composition, characterized by containing:

[0086] (A) An alkali-soluble resin containing at least one structure selected from polyimide, polyamide, polybenzoxazole, polyamide-imide, and their precursor structures.

[0087] (B) Polymer compounds with structural units formed by cyclization polymerization

[0088] (C) Compounds that produce acids due to light, and

[0089] (D) Thermal crosslinking agent.

[0090] The present invention will now be described in detail, but it is not limited thereto.

[0091] [Negative photosensitive resin composition]

[0092] The negative photosensitive resin composition of the present invention will be described.

[0093] The negative photosensitive resin composition of the present invention contains:

[0094] (A) An alkali-soluble resin containing at least one structure selected from polyimide, polyamide, polybenzoxazole, polyamide-imide, and their precursor structures.

[0095] (B) Polymer compounds with structural units formed by cyclization polymerization

[0096] (C) Compounds that produce acids due to light, and

[0097] (D) Thermal crosslinking agent.

[0098] The aforementioned negative photosensitive resin composition is alkaline-developable. 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 will be explained in detail below.

[0099] [(A) Alkali-soluble resin]

[0100] The alkali-soluble resin (A) used in this invention contains at least one structure selected from polyimide, polyamide, polybenzoxazole, polyamide-imide, and their precursor structures. There are no particular limitations on the resin (A) containing the above-mentioned structures; it is preferable to contain structures represented by the following general formulas (8) and / or (9).

[0101] [Chemistry 6]

[0102]

[0103] In the formula, X4 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 being separated by bonding groups.

[0104] [Chemistry 7]

[0105]

[0106] In the formula, X5 is a divalent organic group, and s and Z are the same as above.

[0107] In the above general formula (8), X4 is a tetravalent organic group, but there is no limitation on whether it is a tetravalent organic group. It is preferable to be a tetravalent organic group of alicyclic aliphatic or aromatic group with 4 to 40 carbon atoms, and it is more preferably a tetravalent organic group represented by the following formula (10). Furthermore,

[0108] The structure of X4 can be one type or a combination of two or more types.

[0109] [Chemistry 8]

[0110]

[0111] In the formula, the dotted line represents the bond.

[0112] In the above general formula (8), s represents 0 or 1. When s = 0, the two aromatic rings in the above general formula (8) are directly bonded without being separated by a divalent bonding group Z.

[0113] On the other hand, when s = 1, the two aromatic rings in the above general formula (8) are bonded together by a divalent bonding group Z. There is no limitation on whether Z is a divalent group. It is preferable to be a divalent organic group of alicyclic aliphatic or aromatic group with 4 to 40 carbon atoms, and it is more preferably a divalent bonding group represented by the following formula (11). Furthermore, the structure of Z can be one type or a combination of two or more types.

[0114] [Chemistry 9]

[0115]

[0116] 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.

[0117] It is particularly preferred that the divalent bonding group Z is represented by the following formula (12) or (13).

[0118] [Chemistry 10]

[0119]

[0120] In the formula, the dotted line represents the bond.

[0121] Regarding the structural unit represented by the above general formula (8), when Z in the above general formula (8) is a group represented by the above formula (12), it is preferable to be a structural unit represented by the following general formula (8-1), and when Z in the above general formula (8) is a group represented by the above formula (13), it is preferable to be a structural unit represented by the following general formula (8-2).

[0122] [Chemistry 11]

[0123]

[0124] [Chemistry 12]

[0125]

[0126] In the formula, X4 is the same as above.

[0127] As shown in the general formula (8-1) above, when Z, which is a divalent bonding group, is the hexafluoropropylene group represented by the formula (12) above, and is located at the para position of the phenolic hydroxyl group, the acidity of the phenolic hydroxyl group will increase because the hexafluoropropylene group is an electron-withdrawing group, and the solubility of the developer in the alkaline aqueous solution will be improved, which is more ideal.

[0128] Similarly, as shown in the above general formula (8-2), when Z, which is a divalent bonding group, is a sulfone group represented by the above formula (13) and is located at the para position of the phenolic hydroxyl group, since the sulfone group is also an electron-withdrawing group, the acidity of the above phenolic hydroxyl group will also increase, and the solubility of the developer in the alkaline aqueous solution will be improved, which is more ideal.

[0129] In the above general formula (9), X5 is a divalent organic group, and there is no limitation on whether it is a divalent organic group. It is preferable to be 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 more preferable to be a divalent organic group represented by the following formula (14). Furthermore, the structure of X5 can be one type or a combination of two or more types.

[0130] [Chemistry 13]

[0131]

[0132] In the formula, R 17 R 18 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 represents the bond.

[0133] When X5 in the above general formula (9) 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 will be higher, which is more ideal.

[0134] In the above general formula (9), s and Z are the same as above. Considering the solubility of the developer in alkaline aqueous solution, Z should preferably be the above formula (12) or (13). In this case, as in the above general formulas (8-1) and (8-2), the acidity of the phenolic hydroxyl group will increase, and the solubility of the developer in alkaline aqueous solution will be improved, which is more ideal.

[0135] Furthermore, the alkali-soluble resin (A) used in this invention may contain structural units represented by the above general formulas (8) and (9), as well as structural units represented by the following general formula (15) (hereinafter also referred to as structural unit (15)).

[0136] [Chemistry 14]

[0137]

[0138] In the formula, X6 and X5 are the same. X7 is a divalent organic group.

[0139] In the above general formula (15), X7 is a divalent organic group. There is no limitation on the divalent organic group, but it is preferably a divalent organic group with 6 to 40 carbon atoms. It is 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. For a more ideal X7, the structures represented by the following formula (16) or the following general formula (17) can be listed. Furthermore, the structure of X7 can be one or a combination of two or more.

[0140] [Chemistry 15]

[0141]

[0142] In the formula, the dotted line represents the bond with amino groups.

[0143] [Chemistry 16]

[0144]

[0145] In the formula, the dotted line represents the bond with the amino group, R 19 Each can be independently represented as methyl, ethyl, propyl, n-butyl, or trifluoromethyl, and q7 represents an integer from 2 to 20.

[0146] Furthermore, the alkali-soluble resin (A) used in this invention, in addition to containing the structural units represented by the above general formulas (8) and (9), preferably contains the structural units represented by the following general formula (18) (hereinafter also referred to as structural units (18)).

[0147] [Chemistry 17]

[0148]

[0149] In the formula, X8 is a tetravalent organic group that is the same as or different from X4 above, and X9 is a group represented by the following general formula (19).

[0150] [Chemistry 18]

[0151]

[0152] In the formula, R 20 ~R 23 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.

[0153] In the above general formula (18), X8 can be a tetravalent organic group listed in relation to X4, such as the tetravalent organic group represented by formula (10) above. Furthermore, the organic groups that can ideally be used in X9 (the group represented by the above general formula (19)) are listed below. However, it is not limited to these.

[0154] [Chemistry 19]

[0155]

[0156] Alkali-soluble resin (A) can produce a hardened film with flexibility, high elongation and low warpage by containing such structural units (19).

[0157] Furthermore, the alkali-soluble resin (A) used in this invention may contain structural units represented by the following general formula (20) or (21) (hereinafter referred to as structural unit (20) and structural unit (21)).

[0158] [Chemistry 20]

[0159]

[0160] [Chemistry 21]

[0161]

[0162] In the formula, X 10 X is a tetravalent organic group that is the same as or different from X4 mentioned above. 11 For divalent organic groups that are the same as or different from X7, s and Z are the same as above. R 24 and R 25 R 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 (22). 24 and R 25 At least one of them is an organic group represented by the following general formula (22).

[0163] [Chemistry 22]

[0164]

[0165] In the formula, the dotted line represents the bond. R 26 R is a hydrogen atom or an organic group having 1 to 3 carbon atoms. 27 and R 28 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.

[0166] X in the above structural units (20) and (21) 10The organic group is tetravalent. If it is the same as or different from X4 above and is tetravalent, there is no limitation. It is preferably a tetravalent organic group of alicyclic aliphatic or aromatic groups having 4 to 40 carbon atoms, and more preferably a tetravalent organic group represented by formula (10) above. Also, X 10 The structure can be one type or a combination of two or more types.

[0167] On the other hand, X in the above structural unit (21) 11 It is a divalent organic group; if it is the same as or different from X7 above and is divalent, there is no limitation. It is preferably a divalent organic group with 6 to 40 carbon atoms, and more preferably a cyclic organic group with substituents containing 1 to 4 aromatic or aliphatic rings, or an aliphatic group or siloxane group without a cyclic structure. For a more ideal X... 11 In this regard, structures represented by the above formula (16) or general formula (17) can be listed. Also, X 11 The structure can be one type or a combination of two or more types.

[0168] R in the above structures (20) and (21) 24 and R 25 R 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 (22). 24 and R 25 At least one of them is an organic group represented by the above general formula (22).

[0169] R in the above general formula (22) 26 There are no restrictions if it is a hydrogen atom or a monovalent organic group with 1 to 3 carbon atoms. However, considering the photosensitivity of negative photosensitive resin compositions, it is preferable to use a hydrogen atom or a methyl group.

[0170] R in the above general formula (22) 27 and R 28 There are no restrictions if they are either hydrogen atoms or monovalent organic groups with 1 to 3 carbon atoms, but considering the photosensitivity of negative photosensitive resin compositions, hydrogen atoms are preferable.

[0171] In the above general formula (22), o is an integer from 2 to 10. Considering the photosensitive characteristics, it is better to use an integer from 2 to 4. O being 2 is even better.

[0172] [(B) Polymers with structural units formed by cyclization polymerization]

[0173] There are no particular limitations on the polymer compound (B) used in this invention if it has a structural unit formed by cyclization polymerization.

[0174] Examples of monomers that can be ideally used to obtain structural units formed by cyclization polymerization include diallyl quaternary ammonium salts, ether-type perfluoro1,6-dienes, and α-(allyloxymethyl)acrylates.

[0175] Furthermore, in order to improve the adhesion to the substrate, it is preferable that the structural unit formed by the cyclization polymerization of the above-mentioned component (B) is at least one of the structural units represented by the following general formula (1), the following general formula (2), the following general formula (3) and the following general formula (4).

[0176] [Chemistry 23]

[0177]

[0178] Here, R 1 R 2 R 3 R 4 R 5 and R 6 Each is an alkyl group that is independently composed of hydrogen atoms or has 1 to 5 carbon atoms and is either straight-chain or branched.

[0179] For the monomer units used to form the structural units formed by cyclization polymerization, the monomer units listed in the following general formulas (23) and (24) are particularly preferred. These monomers can be used alone or in more than two types.

[0180] [Chemistry 24]

[0181]

[0182] In the formula, R 4 R 5 and R 6 As mentioned above.

[0183] In particular, specific examples available for commercial use include: ACRYCURE RD series and ACRYCURE RE series (manufactured by Nippon Shokubai Co., Ltd., product name).

[0184] In particular, considering the aspects of polymerizability and stability, the structural unit of the above general formula (3) and the above monomer unit (23) are preferred.

[0185] In addition, in order to impart alkali solubility and improve crosslinking density, it is preferable that the polymer of component (B) contains structural units represented by the following general formula (5) or (5').

[0186] [Chemistry 25]

[0187]

[0188] Here, R 7Representing a hydrogen atom or a methyl group, X1 represents -C(=O)-O- or -C(=O)-OR, respectively. 8 -, -C(=O)-NH-, -C(=O)-NH-R 8 -or-C(=O)-N(R) 8 OH)-. R 8 It is a divalent aliphatic saturated hydrocarbon group with 1 to 12 carbon atoms, in the form of a straight chain, branched structure, or cyclic structure, or an aromatic hydrocarbon group with 6 to 12 carbon atoms. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon group can also be substituted with oxygen atoms. Furthermore, the hydrogen atoms of the aromatic hydrocarbon group can also be substituted with methyl groups. p is 0 or 1.

[0189] Furthermore, in the structure represented by general formula (5), it is preferable to have an ester group or an amide group, which is an electron-withdrawing group, at the para position of the phenolic hydroxyl group. In this case, the acidity of the phenolic hydroxyl group will increase, and the solubility in the developer of the alkaline aqueous solution will be improved. Examples of monomers that can be ideally used as structural units to form the above general formulas (5) and (5') are specifically illustrated below. However, this is not a limitation.

[0190] [Chemistry 26]

[0191]

[0192] In the formula, R 7 As stated above.

[0193] [Chemistry 27]

[0194]

[0195] In the formula, R 7 As stated above.

[0196] The structures represented by general formulas (5) and (5') are effective not only as units that promote alkali solubility but also as units that promote crosslinking. By combining them with structural units formed by cyclization polymerization, the mechanical properties of the hardened film can be further improved.

[0197] In addition, in order to improve the crosslinking density, in the polymer of component (B), it is advisable to copolymerize monomers having epoxy or oxetane groups represented by the following general formula (6), or monomers having terminal isocyanate groups represented by the following general formula (α).

[0198] [Chemistry 28]

[0199]

[0200] Here, R 9 X represents a hydrogen atom or a methyl group, and X2 represents -C(=O)-O-, or phenylene or naphthylene, respectively. R 10It may also contain alkylene groups of 1 to 15 carbon atoms in the form of straight-chain, branched, or cyclic groups, such as ester, ether, or aromatic hydrocarbon groups. 11 It consists of hydrogen atoms, a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or may also contain R. 10 Bonding and forming a loop. R 12 R is a hydrogen atom, or a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms. 13 It is a hydrogen atom or a straight-chain alkyl group having 1 to 6 carbon atoms, and can also be combined with R. 10 Bonding and forming a ring. m is 0 or 1. p is 0 or 1. Also, R1' represents a hydrogen atom or a methyl group, R2' represents a single bond or an alkylene group, and R3' is a capped isocyanate group.

[0201] Examples of monomers used to form the structural unit of the above general formula (6) can be listed below.

[0202] [Chemistry 29]

[0203]

[0204] In the formula, R 9 As stated above.

[0205] [Chemistry 30]

[0206]

[0207] In the formula, R 9 As stated above.

[0208] [Chemistry 31]

[0209]

[0210] In the formula, R 9 As stated above.

[0211] In addition, a portion of the monomers used to obtain repeating units having epoxy groups and oxetyl groups have been disclosed in Japanese Patent Application Publication Nos. 2003-55362, 2005-8847, and 2005-18012.

[0212] In this general formula (α), R1' represents a hydrogen atom or a methyl group, R2' represents a single bond or an alkylene group, and R3' is a capped isocyanate group.

[0213] The aforementioned terminated isocyanate group refers to an organic group formed by end-capping an isocyanate group (-N=C=O) with a suitable protecting group. The terminated isocyanate group can be formed by reacting the isocyanate group with a terminating agent.

[0214] The isocyanate-capped groups are stable at room temperature, but above a certain temperature, the capping agent will decapsulate (uncapping), and the hydroxyl or carboxyl groups in component (A) will react with the isocyanate groups to form a cross-linked structure. The 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] In addition, the ideal end-capped isocyanate group is described in paragraphs

[0015] to

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

[0216] In particular, from the viewpoint of good polymerizability and commercial availability, the monomer units shown below are preferred. Furthermore, these monomers can be used alone or in combination of two or more.

[0217] [Chemistry 32]

[0218]

[0219] In the formula, R1' is as described above.

[0220] Furthermore, the photosensitive component does not deseal during heat treatment (pre-baking) after spin coating and heat treatment (post-exposure baking (PEB)) after exposure, but it does deseal during post-curing (post-development heat treatment) and undergoes a cross-linking reaction with alkali-soluble resin more effectively.

[0221] Therefore, the following monomer unit is preferred for unsealing in the range of 140°C to 200°C.

[0222] [Chemistry 33]

[0223]

[0224] In the formula, R1' is as described above.

[0225] In particular, specific examples that are commercially available include the KARENZ MOI series and the AOI series (manufactured by Showa Denko, Inc., product name).

[0226] In addition, considering the need to improve the crosslinking reactivity during photolithography patterning and to improve the dissolution contrast of the unexposed / exposed parts of the alkaline developer, it is advisable to copolymerize the structural units of the following general formula (7) in the polymer of component (B).

[0227] [Chemistry 34]

[0228]

[0229] Here, R 14R represents a hydrogen atom or a methyl group. 15 It is a straight-chain, branched, or cyclic aliphatic saturated hydrocarbon group with 1 to 13 carbon atoms, either with a single bond or (1+1) valence, and the carbon atoms of the aforementioned aliphatic saturated hydrocarbon group can also be replaced by oxygen atoms. X3 are -C(=O)-O- and -C(=O)-OR, respectively. 16 -, -C(=O)-NH-, -C(=O)-N(R 16 OH)-, or phenylene or naphthylene. R 16 It is a divalent aliphatic saturated hydrocarbon group with 1 to 12 carbon atoms, in the form of a straight chain, branched structure, or cyclic structure, or an aromatic hydrocarbon group with 6 to 12 carbon atoms, wherein the carbon atoms of the aforementioned aliphatic saturated hydrocarbon group may also be replaced by oxygen atoms. l is 0 or 1.

[0230] Examples of monomers used to form the structural unit of the above general formula (7) can be listed below.

[0231] [Chemistry 35]

[0232]

[0233] In the formula, R 14 As stated above.

[0234] [Chemistry 36]

[0235]

[0236] In the formula, R 14 As stated above.

[0237] [Chemistry 37]

[0238]

[0239] In the formula, R 14 As stated above.

[0240] Here, since the structural units formed by cyclization polymerization represented by the above general formulas (1) to (4) have excellent mechanical strength and heat resistance, but lack crosslinking and alkali solubility, it is advisable to copolymerize the structural units represented by the above general formulas (5), (5'), and (7) which have excellent alkali solubility, and the structural units represented by the above general formula (6) which have crosslinking properties, such as epoxy groups, oxetyl groups, and terminal isocyanate groups represented by the above general formula (α), in the polymer of component (B). If this is done, it is easier to take into account all the mechanical properties, alkali solubility, and crosslinking properties compared to polymers composed only of structural units represented by each of the above general formulas (1) to (4).

[0241] Therefore, when repeating units are copolymerized in this way, repeating units with the following formula (1a) are preferred.

[0242] [Chemical formula 38]

[0243]

[0244] In the formula, 0 < a1 < 1.0, 0 < a2 < 1.0, 0 ≤ a3 < 1.0, 0 ≤ b1 < 1.0, 0 < a3 + b1 < 1.0, 0 < a4 < 1.0, and it satisfies any one of 0 < a1 + a2 + a3 + a4 ≤ 1.0, 0 < a1 + a2 + b1 + a4 ≤ 1.0, 0 < a1 + a2 + a3 + b1 + a4 ≤ 1.0. R 4 、R 7 、R 9 ~R 13 、R 14 、R 15 、R1’ to R3’, X1, X2, X3, m, p and l are the same as described above.

[0245] In the high molecular compound of component (B) used in the present invention, the monomers that can form the structural units obtained by cyclization polymerization represented by the above general formulas (1) to (4) (hereinafter labeled as a), the monomers that obtain the repeating units with hydroxyl groups represented by the above general formulas (5) and (7) (hereinafter labeled as b and c), and the monomers that obtain the repeating units with groups that can crosslink with the alkali-soluble resin of component (A) represented by the general formulas (6) and (α) (hereinafter labeled as d) are used as the basis. However, in order to improve the adhesion to the substrate, the flexibility of the cured film, and further improve the mechanical properties and heat shock resistance, the monomer that obtains the repeating unit represented by the following general formula (25) (hereinafter labeled as e) can also be copolymerized.

[0246] [Chemical formula 39]

[0247]

[0248] Here, in the general formula (25), R 29 represents a hydrogen atom or a methyl group, R 30 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 12 is preferably -C(=O)-O- or -C(=O)-NH-. 0 ≤ e < 1.

[0249] Regarding monomers that obtain the repeating unit represented by the above general formula (25), the following specific examples can be listed. Examples include: aminoethyl methacrylate, N-methylaminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, N-ethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, aminopropyl methacrylate, N-methylaminopropyl methacrylate, N,N-dimethylaminopropyl methacrylate, N-ethylaminopropyl methacrylate, N,N-diethylaminopropyl methacrylate, 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-dimethyl ...propyl(meth)acrylamide, N-methylaminopropyl(meth)acrylamide, N-methylaminopropyl(meth)acrylamide, N-methylaminopropyl(meth)acrylamide, N-methylamino Propyl (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)acrylate Methyl ester, 2-(piperidin-4-yl)ethyl acrylate, piperidine-4-ester (meth)acrylate, 1-methylpiperidin-4-ester (meth)acrylate, 2,2,6,6-tetramethylpiperidin-4-ester (meth)acrylate, 1,2,2,6,6-pentamethylpiperidin-4-ester (meth)acrylate, (piperidin-4-yl)methyl acrylate, 2-(piperidin-4-yl)ethyl acrylate, etc.

[0250] Furthermore, for the monomers that obtain the repeating unit represented by the above general formula (25), alkyl methacrylates can be used, and specific examples include: 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.

[0251] In addition, in order to improve the mechanical strength of the cured film, olefins f having an aromatic group such as styrenes, vinylnaphthalenes, vinylanthracenes, vinylcarbazoles, acenaphthenes, indenes, etc., or alicyclic olefins g such as norbornenes, norbornadienes, etc. may be copolymerized.

[0252] Among the above repeating units a1, a2, a3, a4, b1, e, f, g, the ratio of the repeating units is preferably 0 < a1 < 0.8, 0 < a2 ≤ 0.8, 0 ≤ a3 ≤ 0.8, 0 < a4 ≤ 0.8, 0 ≤ b1 ≤ 0.6, 0 ≤ e ≤ 0.8, 0 ≤ f ≤ 0.8, 0 ≤ g ≤ 0.8. It is more preferable that 0 < a1 ≤ 0.5, 0.1 ≤ a2 ≤ 0.6, 0.1 ≤ a3 ≤ 0.6, 0.1 ≤ a4 ≤ 0.7, 0 ≤ b1 ≤ 0.4, 0 ≤ e ≤ 0.4, 0 ≤ f ≤ 0.4, 0 ≤ g ≤ 0.4. It is even more preferable that the range is 0 < a1 ≤ 0.4, 0.1 ≤ a2 ≤ 0.4, 0.1 ≤ a3 ≤ 0.4, 0.2 ≤ a4 ≤ 0.7, 0 ≤ b1 ≤ 0.2, 0 ≤ e ≤ 0.4, 0 ≤ f ≤ 0.4, 0 ≤ g ≤ 0.4. In addition, it is preferably in accordance with any one of a1 + a2 + a3 + a4 = 1, a1 + a2 + b1 + a4 = 1, a1 + a2 + a3 + b1 + a4 = 1, a1 + a2 + a3 + b1 + a4 + e + f + g = 1, and the sum of these repeating units is preferably 100 mol% of the total amount of all repeating units.

[0253] The polystyrene equivalent weight average molecular weight of the (crosslinkable) high molecular compound (B) used in the negative photosensitive composition of the present invention by gel permeation chromatography (GPC) is 1,000 to 500,000, and it is particularly preferably 2,000 to 30,000. If the weight average molecular weight is 1,000 or more, the glass transition temperature is high enough, and in the thermal crosslinking after development of the negative photosensitive resin composition, the pattern will not deform. If it is 500,000 or less, there are no pinhole defects during coating, or there is no concern about layer separation between the pattern formed by photolithographic patterning and the alkali-soluble resin. In addition, two or more polymers with different composition ratios, molecular weight distributions, and molecular weights may be blended.

[0254] Furthermore, at this time, the addition amount of the (crosslinkable) high molecular 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 is high in the cured film with the alkali-soluble resin (A) as described above. 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) high molecular compound (B) is preferably set within the above range. It is more preferable that the addition amount of component (B) is 10 parts by mass or more and 70 parts by mass or less, and it is even more preferable that it is 30 parts by mass or more and 50 parts by mass or less. By setting within this range, the balance between the photolithographic patterning performance and the physical properties of the cured film can be good.

[0255] [(C) Compounds that produce acids due to light]

[0256] The photoacid-generating compound (C) used in this invention can be any compound that generates acid due to high-energy radiation. Ideal compounds include: sulfonium salts, sulfonyl diazomethanes, N-sulfonyloxyimide type, benzoin sulfonate type, gallophenol trisulfonate type, sulfonic acid nitrobenzyl ester type, sulfone type, glyoxime derivative type acid generators, etc. These will be described in detail below, but two or more of them can be used alone or in combination.

[0257] 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, tri(4-tert-butoxyphenyl)sulfonium, (3-tert-butoxyphenyl)diphenylsulfonium, bis(3-tert-butoxyphenyl)phenylsulfonium, tri(3-tert-butoxyphenyl)sulfonium, (3,4-di(tert-butoxy)phenyl)diphenylsulfonium, bis(3,4-di(tert-butoxy)phenyl)phenylsulfonium, tri(3,4-di(tert-butoxy)phenyl)sulfonium, diphenyl(4-thiophenoxyphenyl)sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl)diphenylsulfonium, tri(4-tert-butoxycarbonylmethyloxyphenyl)sulfonium, (4-tert-butoxyphenyl)bis(4-thiophenoxyphenyl)sulfonium. Sulfonates include (-dimethylaminophenyl)sulfonium, tris(4-dimethylaminophenyl)sulfonium, 2-naphthyldiphenylsulfonium, dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-side-oxycyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium, etc. Sulfonates can be listed as follows: trifluoromethanesulfonate, nonafluorobutyrate, heptadecafluorooctylsulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, 4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octylsulfonate, dodecylbenzenesulfonate, butyrate, methanesulfonate, etc. Sulfonate salts of these combinations can also be listed.

[0258] 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, nonafluorobutyrate, heptadecafluorooctanoate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, 4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanoic acid sulfonate, dodecylbenzenesulfonate, butyrate, methanesulfonate, etc., and combinations of these ferric salts can also be listed.

[0259] Examples of sulfonyl diazonium methanes include: bis(ethylsulfonyl)diazonium methane, bis(1-methylpropylsulfonyl)diazonium methane, bis(2-methylpropylsulfonyl)diazonium methane, bis(1,1-dimethylethylsulfonyl)diazonium methane, bis(cyclohexylsulfonyl)diazonium methane, bis(perfluoroisopropylsulfonyl)diazonium methane, bis(phenylsulfonyl)diazonium methane, bis(4-methylphenylsulfonyl)diazonium methane, and bis(2,4-dimethylphenylsulfonyl)diazonium methane. Di(2-naphthylsulfonyl)diazomethane, bis(2-naphthylsulfonyl)diazomethane, 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl-2-naphthyldiazomethane, methylsulfonylbenzoyldiazomethane, tert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane, etc., are bissulfonyldiazomethanes and sulfonylcarbonyldiazomethanes.

[0260] Examples of N-sulfonyloxyimide type photoacid generators include: compounds composed of imide skeletons such as succinic imide, naphthalene dicarboximide, phthalene dicarboximide, cyclohexyl dicarboximide, 5-norcamphen-2,3-dicarboximide, and 7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboximide, combined with trifluoromethanesulfonate, nonafluorobutyrate, heptadecafluorooctylsulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octylsulfonate, dodecylbenzenesulfonate, butyrate, and methanesulfonate.

[0261] Examples of photoacid generators of the benzoin sulfonate type include: benzoin toluene sulfonate, benzoin methane sulfonate, benzoin butyrate sulfonate, etc.

[0262] Examples of gallnut trisulfonate-type photoacid generators include compounds in which all the hydroxyl groups of gallnut, fluoroglycine, catechol, resorcinol, and hydroquinone are replaced by trifluoromethanesulfonate, nonafluorobutyrate, heptadecanofluorooctyl sulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octylsulfonate, dodecylbenzenesulfonate, butyrate, methanesulfonate, etc.

[0263] Examples of photoacid generators of the nitrobenzyl sulfonate type include: 2,4-disulfonic acid nitrobenzyl ester, 2-sulfonic acid nitrobenzyl ester, and 2,6-disulfonic acid nitrobenzyl ester. Specific examples of sulfonate groups include: trifluoromethanesulfonate, nonafluorobutyrate, heptadecafluorooctanoate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octylsulfonate, dodecylbenzenesulfonate, butyrate, and methanesulfonate. Furthermore, compounds formed by replacing the nitro group on the benzyl side with a trifluoromethyl group can also be used.

[0264] 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.

[0265] Examples of photoacid generators of the glyoxime derivative type include: bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-O-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-O-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-O-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, and bis-O-(p-toluenesulfonyl)-2-methylglyoxime. -3,4-Pentanedione glyoxime, bis-O-(n-butanesulfonyl)-α-dimethylglyoxime, bis-O-(n-butanesulfonyl)-α-diphenylglyoxime, bis-O-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-O-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-O-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime 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.

[0266] Among them, the photoacid generators that can be ideally used are bis(sulfonyl)diazomethane and N-sulfonyloxyimide.

[0267] In addition, an oxime-type acid generator, represented by WO2004 / 074242A2, may also be added.

[0268] In addition, the aforementioned acid generating agents can be used alone or in combination of two or more. Onium salts have excellent effects on improving rectangularity, while diazomethane derivatives and glyoxime derivatives have excellent effects on reducing standing waves; therefore, by combining the two, fine adjustments to the profile can be made.

[0269] The amount of photoacid generator in the negative photosensitive resin composition of the present invention is preferably 0.05 to 20 parts by mass, or 1 to 10 parts by mass, relative to 100 parts by mass of component (A). If the amount of photoacid generator is 0.05 parts by mass or more, sufficient contrast (difference in the dissolution rate of the developer between the exposed and unexposed areas) can be obtained, and if it is 20 parts by mass or less, there is no concern that the resolution will be degraded due to the light absorption of the photoacid generator itself.

[0270] [(D) Thermal crosslinking agent]

[0271] If the thermal crosslinking agent (D) used in this invention is a compound having a group that crosslinks with component (A) other than component (B) mentioned above, then any of them are acceptable. Specific examples of crosslinking agents that can be used herein include: melamine compounds, guanidine compounds, urea compounds or urea compounds, epoxy compounds, oxadiazonane compounds, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, compounds containing benzyl alcohol, etc., which are formed by replacing at least one group selected from hydroxymethyl, alkoxymethyl, and acyloxymethyl groups; oxazoline-based crosslinking agents as described in Japanese Patent Application Publication Nos. 2-60941, 2-99537, and 2-115238.

[0272] 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.

[0273] Alternatively, 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, and 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-enoxy-9-ylidene)bisphenol, 2,2'-dimethyl-4,4'-(9H-enoxy-9-ylidene)bisphenol -9-yl)bisphenol, 2,2'-diallyl-4,4'-(9H-furo-9-yl)bisphenol, 2,2'-difluoro-4,4'-(9H-furo-9-yl)bisphenol, 2,2'-diphenyl-4,4'-(9H-furo-9-yl)bisphenol, 2,2'-dimethoxy-4,4'-(9H-furo-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 compounds in phenolic varnish resin are obtained by epoxy propylene etherification.

[0274] Specific examples of melamine compounds include: hexamethylolmelamine, hexamethoxymethylmelamine, compounds of hexamethylolmelamine in which 1 to 6 hydroxymethyl groups are methylated with methoxy groups, or mixtures thereof; hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds of hexamethylolmelamine in which 1 to 6 hydroxymethyl groups are methylated with acyloxy groups, or mixtures thereof. Examples of guanidine compounds include: tetramethylolguanidine, tetramethoxymethylguanidine, compounds of tetramethylolguanidine in which 1 to 4 hydroxymethyl groups are methylated with methoxy groups, or mixtures thereof; tetramethoxyethylguanidine, tetraacyloxyguanidine, compounds of tetramethylolguanidine in which 1 to 4 hydroxymethyl groups are methylated with acyloxy groups, or mixtures thereof. Examples of urea compounds include: tetrahydroxymethyl urea, tetramethoxy urea, tetramethoxymethyl urea, compounds formed by methylating 1 to 4 hydroxymethyl groups of tetrahydroxymethyl urea with methoxy groups, or mixtures thereof; compounds formed by methylating 1 to 4 hydroxymethyl groups of tetrahydroxymethyl urea with acyloxy groups, or mixtures thereof. Examples of urea compounds include: tetrahydroxymethyl urea, tetramethoxymethyl urea, compounds formed by methylating 1 to 4 hydroxymethyl groups of tetrahydroxymethyl urea with methoxy groups, or mixtures thereof; tetramethoxyethyl urea, etc.

[0275] 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.

[0276] 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.

[0277] Further 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, which describe cyclic epoxy compounds; Japanese Patent Application Publication No. 2006-348252, which describes crosslinking agents having ethylene oxide rings bonded to the ring; and Japanese Patent Application Publication No. 2008-24920, which describes dendrimers and hyperbranched polymers. The crosslinking agents based on polymers include epoxy crosslinking agents, crosslinking agents containing both hydroxyl and oxetane groups as described in Japanese Patent Application Publication No. 2001-310937, and crosslinking agents containing both hydroxyl and epoxy groups as described in Japanese Patent Publication No. 3824286.

[0278] Epoxy groups exhibit high ring strain and reactivity, while oxetanes are highly basic and readily bond with acids. Reports have indicated that combining epoxy groups with oxetanes can significantly improve the reactivity of cationic polymerization.

[0279] Furthermore, it is preferable that component (D) in the negative photosensitive resin composition of the present invention is one or more crosslinking agents selected from amino condensates modified with formaldehyde or formaldehyde-alcohol, or phenolic compounds having an average of more than two hydroxymethyl or alkoxyhydroxymethyl groups per molecule.

[0280] Examples of amino condensates modified with formaldehyde or formaldehyde-alcohol include melamine condensates modified with formaldehyde or formaldehyde-alcohol, and urea condensates modified with formaldehyde or formaldehyde-alcohol.

[0281] The preparation of the melamine condensate modified with formaldehyde or formaldehyde-alcohol, for example, involves first modifying the melamine monomer with formaldehyde by hydroxymethylation using a known method, or by further modifying it with an alcohol by alkoxylation, to prepare the modified melamine represented by the following general formula (26). Furthermore, the alcohol is preferably a lower alcohol, such as an alcohol having 1 to 4 carbon atoms.

[0282] [Chemistry 40]

[0283]

[0284] In the formula, R 31 It may be the same or different from hydroxymethyl, alkoxymethyl containing alkoxy groups of 1 to 4 carbon atoms or hydrogen atoms, but at least one of them is hydroxymethyl or the above-mentioned alkoxymethyl.

[0285] The above R 31Examples include: hydroxymethyl, methoxymethyl, ethoxymethyl, alkoxymethyl, and hydrogen atoms.

[0286] The modified melamine represented by the above general formula (26) can be specifically listed as: trimethoxymethyl monohydroxymethyl melamine, dimethoxymethyl monohydroxymethyl melamine, trihydroxymethyl melamine, hexahydroxymethyl melamine, hexamethoxymethyl melamine, etc.

[0287] Then, the modified melamine or its polymers (e.g., dimers, trimers, etc.) represented by the above general formula (26) are subjected to addition condensation polymerization with formaldehyde in accordance with conventional methods until the desired molecular weight is achieved, thereby obtaining a melamine condensate modified with formaldehyde or formaldehyde-alcohol.

[0288] Furthermore, the preparation of the urea condensate modified with formaldehyde or formaldehyde-alcohol can be carried out, 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.

[0289] Specific examples of urea condensates modified with formaldehyde or formaldehyde-alcohol include: methoxymethylated urea condensates, ethoxymethylated urea condensates, propoxymethylated urea condensates, etc.

[0290] Alternatively, one or more of these modified melamine condensates and modified urea condensates may be used.

[0291] Then, examples of phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups per molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and compounds represented by formulas (D-3) to (D-7).

[0292] [Chemistry 41]

[0293]

[0294] In addition, one type of crosslinking agent or two or more types can be used in combination.

[0295] In the PEB step of the negative photosensitive resin composition of the present invention, component (D) uses the acid generated from component (C) as a catalyst to induce a crosslinking reaction with components (A) and (B). Furthermore, it is a component that continues to induce a crosslinking reaction during post-curing, further improving the strength of the cured product. Considering both photocurability and heat resistance, the weight-average molecular weight of component (D) is preferably 150 to 10,000, and particularly 200 to 3,000.

[0296] Furthermore, the amount of component (D) in the negative photosensitive resin composition of the present invention is preferably 0.5 to 50 parts by mass, and more preferably 1 to 30 parts by mass, relative to 100 parts by mass of component (A).

[0297] [(E) Basic compounds]

[0298] In addition to being formulated with the aforementioned components (A), (B), (C), and (D) containing the necessary ingredients, the negative photosensitive resin composition of the present invention can also be formulated to contain an additional basic compound (E). The basic compound of component (E) is preferably a compound 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, resolution is improved, sensitivity changes after exposure are suppressed, substrate and environmental dependence is reduced, and exposure latitude and pattern outline are improved.

[0299] The basic compounds mentioned above include: 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.

[0300] 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, hexadecylamine, methylenediamine, ethylenediamine, tetraethylenepentylamine, etc. Examples of secondary aliphatic amines include: dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di(sec-butyl)amine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, di(dodecyl)amine, di(hexadecyl)amine, etc. Alkylamines, 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-butyl)amine, tripentamine, tricyclopentamine, trihexylamine, tricyclohexylamine, triheptamine, trioctylamine, trinonamine, tridecylamine, tri(dodecyl)amine, tri(hexadecyl)amine, N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyltetraethylenepentamine, etc.

[0301] Furthermore, examples of mixed amines include: dimethylethylamine, methylethylpropylamine, benzylamine, phenylethylamine, benzyl dimethylamine, 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-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives. (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (e.g., oxazole, isoxazole, etc.), thiazole derivatives (e.g., thiazole, isothiazole, etc.), imidazole derivatives (e.g., imidazole, 4-methylimidazolium, 4-methyl-2-phenylimidazolium, etc.), pyrazole derivatives, furazan derivatives, pyrrolidone derivatives (e.g., pyrrolidone, 2-methyl-1-pyrrolidone, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolide 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-pyrrolidinylpyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoles Phosphorus 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, cyclophosphine 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, uridine derivatives, etc.

[0302] In addition, examples of nitrogen-containing compounds containing carboxyl groups include: aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (e.g., 3-pyridinecarboxylic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.), etc.; examples of nitrogen-containing compounds containing sulfonyl groups include: 3-pyridinesulfonic acid, p-toluenesulfonic acid pyridinium, etc.; examples of nitrogen-containing compounds with hydroxyl groups, nitrogen-containing compounds with hydroxyphenyl groups, and alcoholic nitrogen-containing compounds include: 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2'- Iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)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-pyrrolylalkyl-1,2-propanediol, 8-hydroxyjulolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridinylethanol, 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, benzamide, etc. Examples of imide derivatives include: phthalimide, succinimide, maleimide, etc.

[0303] In addition, one type of alkaline compound may 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). When compounding, it is preferable to mix 0.01 to 2 parts by mass, and it is especially preferable to mix 0.01 to 1 parts by mass. If the amount of the compound is less than 2 parts by mass, the sensitivity can be adequately maintained.

[0304] [(F) Thermal acid generating agent]

[0305] The negative photosensitive resin composition of the present invention may be configured to contain more of a heat-generating compound (thermal acid generator) (F). The heat-generating compound (F) may be added to thermally promote the crosslinking reaction of component (A), component (B), and component (D) during the heating and post-curing step at a temperature of 100 to 300°C applied after the above pattern formation.

[0306] In particular, regarding component (F), it is preferable that it does not promote film curing or hinder pattern formation until pattern formation is achieved through development. To achieve this, component (F) is preferable that does not generate acid at the temperature of the solvent removal and drying step after coating the photosensitive resin composition, but only begins to generate acid and promote the curing of the pattern or film of the negative photosensitive resin composition after heat treatment following pattern formation. Specifically, it is preferable that it is a compound that decomposes and generates acid using heat treatment at 100°C to 300°C, and more preferably 150°C to 300°C. By containing such component (F), the pattern or film of the negative photosensitive resin composition can be transformed into a pattern or film that undergoes further cross-linking and curing reactions during the heating and post-curing step applied at a temperature of 100°C to 300°C after pattern formation. By further promoting the cross-linking and curing reactions, component (F) can further improve the mechanical strength, chemical resistance, adhesion, etc., of the resulting pattern or film.

[0307] The ideal compound that produces an acid upon heating can be the compound described in paragraphs

[0061] to

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

[0308] The amount of the compound that produces acid due to heat 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, if the content is 30 parts by mass or less, the alkaline developability of the composition will not deteriorate, and developing residue will not be generated.

[0309] (G) Antioxidants

[0310] The negative photosensitive resin composition of the present invention can be configured to contain more antioxidants, specifically component (G). The antioxidants containing component (G) inhibit the oxidative degradation of the aliphatic groups and phenolic hydroxyl groups of component (A). Furthermore, due to its rust-preventive effect on metallic materials, it inhibits metal oxidation caused by external moisture, photoacid generators, thermal acid generators, etc., or the associated reduction in adhesion and peeling associated with metal oxidation.

[0311] Ideally, hindered phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants could be listed as examples of antioxidants that can be used. However, they are not limited to these. Furthermore, these antioxidants can be used alone or in combination of two or more.

[0312] Among the specific examples of the aforementioned antioxidants, further examples of hindered phenolic antioxidants include: neopentyl tetroxide tetra[3-(3,5-di(tert-butyl)-4-hydroxyphenyl)propionate] (BASF JAPAN, IRGANOX 1010), bis(3,5-di(tert-butyl)-4-hydroxyphenyl)propionate thiodiethylene ester (BASF JAPAN, IRGANOX 1035), octadecyl 3-(3,5-di(tert-butyl)-4-hydroxyphenyl)propionate (BASF JAPAN, IRGANOX 1076), 1-octyl 3,5-di(tert-butyl)-4-hydroxy-hydrocinnamate (BASF JAPAN, IRGANOX 1135), and 4,6-bis(octylthiomethyl o-cresol) (BASF...). JAPAN (stock), IRGANOX1520L), Sumilizer GA80 (manufactured by Sumitomo Chemical (stock), trade name), ADK STAB AO-20 (manufactured by ADEKA (stock), trade name), ADK STAB AO-30 (manufactured by ADEKA (stock), trade name), ADK STAB AO-40 (manufactured by ADEKA (stock), trade name), ADKSTAB AO-50 (manufactured by ADEKA (stock), trade name), ADK STAB AO-60 (manufactured by ADEKA (stock), trade name), ADK STABAO-80 (manufactured by ADEKA (stock), trade name), ADK STAB AO-330 (manufactured by ADEKA (stock), trade name), and hindered phenolic antioxidants as described in Japanese Patent Application Publication No. WO2017 / 188153A1, etc.

[0313] 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, tridecyl phosphite, tri(2-ethylhexyl) phosphite, tri(nonylphenyl) phosphite, tri(octylphenyl) phosphite, tridecyl poly(oxyethylene) phosphite, tri(cyclohexylphenyl) phosphite, tricyclohexyl phosphite, tridecyl thiophosphite, and triisodecyl thiophosphite. Esters, phenyl bis(2-ethylhexyl) phosphite, phenyl diisodecyl phosphite, tetradecyl poly(oxyethylidene) bis(ethylphenyl) phosphite, phenyl dicyclohexyl phosphite, phenyl diisooctyl phosphite, phenyl di(tridecyl) phosphite, diphenyl cyclohexyl phosphite, diphenyl isooctyl phosphite, diphenyl-2-ethylhexyl phosphite, diphenyl isodecyl phosphite, diphenyl cyclohexyl phosphite, diphenyl thiophosphite, etc.

[0314] Among the specific examples of the antioxidants mentioned above, sulfur-based antioxidants can be further exemplified as follows: ADK STABAO-412S (manufactured by ADEKA Corporation, trade name), AO-503S (manufactured by ADEKA Corporation, trade name), Sumilizer TP-D (manufactured by Sumitomo Chemical Corporation, trade name), etc.

[0315] Sulfur-based and phosphorus-based antioxidants are expected to decompose peroxides.

[0316] Furthermore, the antioxidant content of component (G) is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, relative to 100 parts by weight of the alkali-soluble resin of component (A). A content of 0.1 parts by weight or more will improve adhesion to metal materials and inhibit peeling. Furthermore, if the content is 10 parts by weight or less, there will be no deterioration in the alkali developability of the composition or the toughness of the hardened film.

[0317] [(H)silane compounds]

[0318] The negative photosensitive resin composition of the present invention can be configured as a silane compound containing more (H) components. By using silane compounds containing (H) components, not only can the adhesion to metal materials be improved, but the peeling of the hardened film during reliability tests such as thermal shock tests and high temperature and humidity tests can also be suppressed.

[0319] Any silane compound that has an alkoxysilane group may be used herein. Ideal specific examples are as follows: γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, bis(2-hydroxyethyl)-3-amino... Propyltriethoxysilane, triethoxysilylpropylethylcarbamate, 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 No. 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.

[0320] 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 can impart more sufficient adhesion to the substrate, while a content of 20 parts by weight or less can better suppress problems such as viscosity increase during room temperature storage. Moreover, a content of less than 10 parts by weight can more reliably suppress developing residues caused by the deterioration of the alkali developability of the composition.

[0321] [Other ingredients]

[0322] 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). Other components may include, for example, (I) a dissolution inhibitor, (J) a surfactant, and (K) a solvent. The compounds exemplified below are ideally used, but the invention is not limited thereto.

[0323] (I) Examples of dissolution inhibitors include: compounds in which the hydrogen atom of the phenolic hydroxyl group in a compound having a weight-average molecular weight of 100 to 1,000, preferably 150 to 800, and having two or more phenolic hydroxyl groups in the molecule is replaced by an acid-unstable group at an average rate of 0 to 100 mol% on the whole; or compounds in which the hydrogen atom of the carboxyl group in the molecule is replaced by an acid-unstable group at an average rate of 50 to 100 mol% on the whole.

[0324] Furthermore, the substitution rate of the hydrogen atom of the phenolic hydroxyl group by an acid-labile group should be at least 0 mol% of the total phenolic hydroxyl group, preferably at least 30 mol%, with an upper limit of 100 mol%, and more preferably 80 mol%. The substitution rate of the hydrogen atom of the carboxyl group by an acid-labile group should be at least 50 mol% of the total carboxyl group, preferably at least 70 mol%, with an upper limit of 100 mol%.

[0325] At this time, the compound having two or more phenolic hydroxyl groups or the compound having a carboxyl group is preferably represented by the following formulas (I1) to (I15).

[0326] [Chemistry 42]

[0327]

[0328] However, R in the above formula 201 R 202 Represents a hydrogen atom, or a straight-chain or branched alkyl or alkenyl group having 1 to 8 carbon atoms, respectively. 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 R represents a hydrogen atom, a straight-chain or branched alkyl group, an alkenyl group, or a phenyl or naphthyl group, each substituted with a hydroxyl group. 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” respectively satisfy s+t=8, s'+t'=5, and s”+t”=4, and are the numbers that have at least one hydroxyl group in each phenyl skeleton. a is a number that sets the molecular weight of the compounds of formulas (I8) and (I9) to be 100 to 1,000.

[0329] The amount of dissolution inhibitor incorporated relative to 100 parts by weight of the alkali-soluble resin of component (A) is 0 to 50 parts by weight, preferably 5 to 50 parts by weight, and more preferably 5 to 20 parts by weight. It can be used alone or in combination with two or more components. If the amount of incorporation is 5 parts by weight or more, the resolution will be improved more effectively. If it is less than 50 parts by weight, no pattern loss will occur, and a high resolution can be obtained.

[0330] (J) Surfactants should preferably be nonionic, such as fluorinated surfactants, including perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkyl amine oxides, fluorinated organosiloxane compounds, and nonfluorinated organosiloxane compounds.

[0331] These surfactants can be commercially available, 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), MEGAFACE F-8151 (manufactured by DIC Co., Ltd., trade name), X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), etc. Among them, the following are recommended: 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), and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name).

[0332] 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.

[0333] (K) The solvent is not limited if it 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 monotert-butyl ether acetate, and γ-butyrolactone, etc. One or more of these solvents may be used. It is particularly well-suited as a solvent for ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, or mixtures thereof.

[0334] 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 is particularly preferably 100 to 1,000 parts by mass.

[0335] (Pattern Formation Method)

[0336] This invention provides a pattern forming method, comprising the following steps:

[0337] (1) The above-mentioned negative photosensitive resin composition is coated on a substrate to form a photosensitive film.

[0338] (2) Then, after heat treatment, the above-mentioned photosensitive film is exposed to high-energy rays or electron beams with wavelengths of 190–500 nm using a spacer photomask, and

[0339] (3) After irradiation, the substrate that has undergone heat treatment is developed using an alkaline aqueous solution.

[0340] The following describes a pattern forming method using the negative photosensitive resin composition of the present invention.

[0341] 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, the negative photosensitive resin composition can be coated onto a silicon wafer or a SiO2 substrate, a SiN substrate, or a substrate with a pattern of copper wiring, etc., by spin coating, and pre-baking is performed at a temperature of about 80 to 130°C for 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.

[0342] Spin coating involves dispensing approximately 5 mL of a negative photosensitive resin composition onto a silicon substrate and then rotating the substrate to coat the composition. The thickness of the photosensitive film on the substrate can be easily adjusted by changing the rotation speed.

[0343] Then, a mask for forming the desired pattern is placed on the aforementioned photosensitive film, and the film is irradiated with high-energy rays such as i-rays and gamma rays with wavelengths of 190–500 nm, or with electron beams, so that the exposure dose reaches approximately 1–5,000 mJ / cm. 2 It should reach approximately 100–2,000 mJ / cm³. 2 .

[0344] Then, a post-exposure heating treatment (post-exposure baking (PEB)) is performed on a heating plate for, for example, 60–150°C for 50–600 seconds, preferably 80–120°C for 60–300 seconds.

[0345] Subsequently, 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.

[0346] On the other hand, an ideal alkaline aqueous solution for alkaline development is a 2.38% tetramethylhydroxyammonium (TMAH) aqueous solution. Development can be carried out using conventional methods such as spraying or immersion, or by immersion in the developer solution. Subsequently, cleaning, rinsing, drying, etc., can be performed as needed to obtain a resist film with the desired pattern.

[0347] (Method for forming a hardened coating)

[0348] Furthermore, by heating and curing the patterned film obtained using the above-described patterning method in an oven and on a heating plate at a temperature of 100–300°C, preferably 150–300°C, and more preferably 180–250°C, a cured film can be formed. A curing temperature of 100–300°C can increase the crosslinking density of the negative photosensitive resin composition film and remove residual volatile components, which is ideal considering the adhesion to the substrate, heat resistance or strength, and electrical properties. Moreover, the curing time can be set from 10 minutes to 10 hours.

[0349] The patterns formed above can be used as protective films for covering wiring, circuits, and substrates. The patterns and protective films formed by them have excellent insulation properties and exhibit excellent adhesion on 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. Furthermore, while possessing the corresponding mechanical strength as a protective film, the resolution performance of the fine patterns that can be formed can be greatly improved.

[0350] (hardened membrane)

[0351] 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. It also provides excellent reliability for semiconductor devices when used as a protective coating, and in particular, it can prevent cracking during temperature cycling tests. It is ideally suited for use as a protective coating (interlayer insulating film or surface protective film) for electrical and electronic components, semiconductor devices, etc.

[0352] That is, the present invention provides an interlayer insulating film or surface protective film, which is composed of a hardened film formed by curing the above-mentioned negative photosensitive resin composition.

[0353] The aforementioned protective films are effective in applications such as insulating films for semiconductor components used in rewiring, insulating films for multilayer printed circuit boards, solder masks, and cover films due to their heat resistance, chemical resistance, and insulation properties.

[0354] 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 presence of a protective coating (interlayer insulating film or surface protective film) that provides heat resistance, chemical resistance, and insulation.

[0355] [Example]

[0356] The present invention is specifically illustrated below with examples of synthesis, embodiments, and comparative examples, but the present invention is not limited to the examples described below. Additionally, the weight-average molecular weight (Mw) represents the weight-average molecular weight converted from polystyrene using GPC.

[0357] I. Synthesis of Alkali-Soluble Resin (A)

[0358] The chemical structural formulas and names of the compounds used in the following synthesis examples are shown below.

[0359] [Chemistry 43]

[0360]

[0361] [Synthesis Example 1] Synthesis of polyimide resin (A1)

[0362] Add 30 g (81.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.9 g (8.6 mmol) of 4-aminophenol (PAP), and 125 g of N-methyl-2-pyrrolidone to a 1 L flask equipped with a stirrer and thermometer, and stir to dissolve at room temperature. Then, add dropwise a solution prepared by dissolving 26.7 g (86.2 mmol) of 3,3',4,4'-oxophthalic dianhydride (s-ODPA) in 270 g of N-methyl-2-pyrrolidone at room temperature. After the addition is complete, stir at room temperature for 3 hours. Subsequently, add 40 g of xylene to the reaction solution, and heat under reflux at 170 °C for 3 hours while removing the generated water from the system. After cooling to room temperature, the reaction solution was added dropwise to 2 L of ultrapure water under stirring. The precipitate was filtered and washed appropriately with water, then 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, was 35,000 based on polystyrene.

[0363] [Synthesis Example 2] Synthesis of polyimide resin (A2)

[0364] 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 polyimide resin (A2) was obtained otherwise using the same formulation. The molecular weight of this polymer, determined by GPC, was 34,000 (weight-average) converted to polystyrene.

[0365] [Synthesis Example 3] Synthesis of Polyamide-Imide Resin (A3)

[0366] 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 to a 500 ml flask equipped with a stirrer and thermometer and stirred at room temperature to dissolve. Then, a solution prepared by dissolving 19.0 g (61.4 mmol) of 3,3',4,4'-oxophthalic dianhydride (s-ODPA) in 192 g of N-methyl-2-pyrrolidone was added dropwise at room temperature. 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 while draining 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 sebacate dichlorodichloro (DC-1) at a temperature maintained below 5°C. After the addition was complete, the mixture was allowed to return to room temperature, and then added dropwise to 2 L of ultrapure water under 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 (weight-average) converted to polystyrene.

[0367] [Synthesis Example 4] Synthesis of Polyamide Resin (A4)

[0368] 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 to a 500 ml flask equipped with a stirrer and thermometer and stirred at room temperature to dissolve. Then, 13.0 g (163.8 mmol) of pyridine was added, and 19.6 g (81.9 mmol) of sebacate dichloro(DC-1) was added dropwise while maintaining the temperature below 5 °C. After the addition was complete, the mixture was brought back to room temperature, and the reaction solution was added dropwise to 2 L of ultrapure water under 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 (weight-average) converted to polystyrene.

[0369] [Synthetic Example 5] Synthesis of tetracarboxylic acid diester compound (X-1)

[0370] 100 g (322 mmol) of 3,3',4,4'-oxophthalic 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 to a 3 L flask equipped with a stirrer and a thermometer. Then, 83.8 g (644 mmol) of hydroxyethyl methacrylate (HEMA) was added dropwise at room temperature with stirring, and the mixture was stirred for 24 hours at room temperature. Subsequently, the reaction was stopped by adding 370 g of 10% hydrochloric acid aqueous solution dropwise under ice-cold conditions. 800 g of 4-methyl-2-pentanone was added to the reaction mixture, and the organic layer was separated and extracted, then washed six times with 600 g of water. The solvent of the obtained organic layer was distilled off to obtain 180 g of a tetracarboxylic acid diester compound (X-1).

[0371] [Synthetic Example 6] Synthesis of polyimide precursor (A5)

[0372] Add 57.1 g (100 mmol) of (X-1) and 228 g of N-methyl-2-pyrrolidone to a 1 L flask equipped with a stirrer and thermometer, and stir to dissolve at room temperature. Then, add 24.4 g (205 mmol) of thionyl chloride dropwise while maintaining the reaction solution temperature below 10 °C under ice-cold conditions. After the addition is complete, stir under ice-cold conditions for 2 hours. Then, add dropwise a solution prepared by dissolving 34.8 g (95 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 1.1 g (10 mmol) of 4-aminophenol (PAP), and 32.4 g (410 mmol) of pyridine in 144 g of N-methyl-2-pyrrolidone while maintaining the reaction solution temperature below 10 °C under ice-cold conditions. 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 under stirring. The precipitate was filtered and washed appropriately with water, and then 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 based on polystyrene.

[0373] II. Synthesis of polymer (B)

[0374] [Synthesis example]

[0375] Regarding cross-linking polymers (polymer additives), various monomers are combined and copolymerized in tetrahydrofuran solvent, followed by crystallization in hexane and drying to obtain polymers with the compositions shown below (polymers B1-B14, comparative polymers C1 and C2). The composition of the obtained polymers is determined by utilizing... 1 The results were confirmed by ¹H-NMR, and the molecular weight was confirmed by gel permeation chromatography.

[0376] [Synthesis Example 7] Polymer B1

[0377] Molecular weight (Mw) = 11,400

[0378] [Chemistry 44]

[0379]

[0380] [Synthesis Example 8] Polymer B2

[0381] Molecular weight (Mw) = 11,000

[0382] [Chemistry 45]

[0383]

[0384] [Synthesis Example 9] Polymer B3

[0385] Molecular weight (Mw) = 11,500

[0386] [Chemistry 46]

[0387]

[0388] [Synthesis Example 10] Polymer B4

[0389] Molecular weight (Mw) = 11,400

[0390] [Chemistry 47]

[0391]

[0392] [Synthesis Example 11] Polymer B5

[0393] Molecular weight (Mw) = 10,300

[0394] [Chemistry 48]

[0395]

[0396] [Synthesis Example 12] Polymer B6

[0397] Molecular weight (Mw) = 12,000

[0398] [Chemistry 49]

[0399]

[0400] [Synthesis Example 13] Polymer B7

[0401] Molecular weight (Mw) = 11,800

[0402] [Transformation 50]

[0403]

[0404] [Synthesis Example 14] Polymer B8

[0405] Molecular weight (Mw) = 10,800

[0406] [Chemistry 51]

[0407]

[0408] [Synthesis Example 15] Polymer B9

[0409] Molecular weight (Mw) = 12,300

[0410] [Chemistry 52]

[0411]

[0412] [Synthesis Example 16] Polymer B10

[0413] Molecular weight (Mw) = 11,800

[0414] [Chemistry 53]

[0415]

[0416] [Synthesis Example 17] Polymer B11

[0417] Molecular weight (Mw) = 10,700

[0418] [Chemistry 54]

[0419]

[0420] [Synthesis Example 18] Polymer B12

[0421] Molecular weight (Mw) = 10,400

[0422] [Chemistry 55]

[0423]

[0424] [Synthesis Example 19] Polymer B13

[0425] Molecular weight (Mw) = 9,400

[0426] [Chemistry 56]

[0427]

[0428] [Synthesis Example 20] Polymer B14

[0429] Molecular weight (Mw) = 11,000

[0430] [Chemistry 57]

[0431]

[0432] [Synthetic Example 21] Comparative polymer C1

[0433] Molecular weight (Mw) = 11,300

[0434] [Chem.58]

[0435]

[0436] [Synthesis Example 22] Comparison of polymer C2

[0437] Molecular weight (Mw) = 11,800

[0438] [Chemistry 59]

[0439]

[0440] III. Preparation of negative photosensitive resin compositions (Examples 1-20, Comparative Examples 1 and 2)

[0441] Using 70 parts by mass of the alkali-soluble resins (A1) to (A5) synthesized in Synthetic Examples 1 to 6 and 30 parts by mass of the crosslinking polymers (B1) to (B14), (C1), and (C2) synthesized in Synthetic Examples 7 to 22 as the base resin, a resin composition of 20% by mass was prepared according to the composition and blending amounts recorded in Table 1. Subsequently, after stirring, mixing, and dissolving, the mixture was precisely filtered using a 1.0 μm Teflon filter to obtain a negative photosensitive resin composition. In the table, PGMEA represents propylene glycol monomethyl ether acetate, and GBL represents γ-butyrolactone.

[0442] [Table 1]

[0443]

[0444] In addition, the details of the photoacid generator (PAG-1), crosslinking agent (CL-1), (CL-2), (CL-3), basic compound (E-1), hot acid generator (F-1), (F-2), antioxidant (G-1), silane compound (H-1), dissolution inhibitor (I-1), and surfactant (J-1) of the oxime sulfonate compounds in Table 1 are as follows.

[0445] Photoacid generator (PAG-1)

[0446] [Transformation 60]

[0447]

[0448] Crosslinking agent (CL-1)

[0449] [Chemistry 61]

[0450]

[0451] Crosslinking agent (CL-2)

[0452] [Chemistry 62]

[0453]

[0454] Crosslinking agent (CL-3)

[0455] Oxycyclic butane resin: OXT-121 manufactured by Toa Synthetic Co., Ltd.

[0456] Basic compounds (E-1)

[0457] [Chemistry 63]

[0458]

[0459] Hot acid generator (F-1)

[0460] [Chemistry 64]

[0461]

[0462] Hot acid generator (F-2)

[0463] [Chemistry 65]

[0464]

[0465] Antioxidant (G-1)

[0466] Hindered phenolic antioxidants: Sumitomo Chemical Co., Ltd.'s Sumilizer GA-80

[0467] Silane compounds (H-1)

[0468] Aminosilane coupling agent: KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.

[0469] Dissolution inhibitor (I-1)

[0470] [Chemistry 66]

[0471]

[0472] Surfactant (J-1)

[0473] Fluorinated surfactant: PF-6320 manufactured by OMNOVA

[0474] IV. Pattern Formation

[0475] By applying 5 mL of the aforementioned photosensitive resin compositions 1-20, and comparative photosensitive resin compositions 1 and 2, onto a silicon substrate treated with hexamethylsilazane, and then rotating the substrate, i.e., using spin coating, the film thickness after post-curing and heating, applied after patterning, is 2 μm. Specifically, the spin speed during coating is adjusted to address the potential reduction in film thickness after the post-curing step, ensuring that the final post-cured film thickness is 2 μm.

[0476] Then, pre-baking was performed at 100°C for 2 minutes on a heated plate. Following this, 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 a pattern capable of forming 2μm line and spacing patterns (hereinafter referred to as LS patterns) arranged in a 1:1 ratio (vertical and horizontal), and can form LS patterns with a spacing of 10μm to 2μm per 1μm.

[0477] Subsequently, using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution as the developer, an immersion development was performed for 1 minute until the unexposed parts of the coating film dissolved, followed by rinsing with ultrapure water.

[0478] Then, the patterned substrate is post-cured using an oven at 180°C for 2 hours while being purged with nitrogen.

[0479] Then, each substrate was cut to obtain an observable LS pattern shape, and the line pattern shape was observed using a scanning electron microscope (SEM). The shape of the 2μm LS line pattern after curing was evaluated. Furthermore, along with these results, the sensitivity and number of development cycles required to form a 2μm pattern are presented in Table 2.

[0480] In addition, the shape of the LS pattern was evaluated according to the following criteria, and the evaluation results are shown in Table 2. The smallest LS line pattern cross-section was observed, and the widths of the uppermost and lowermost parts of the pattern 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.

[0481] V. Elongation at break and tensile strength

[0482] The above-mentioned photosensitive resin compositions 1 to 20, and comparative photosensitive resin compositions 1 and 2, were spin-coated onto an aluminum substrate to achieve a finished 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.

[0483] Subsequently, a Quintel UL-7000 contact aligner was used with a wideband wavelength of 500 mJ / cm². 2 The substrate was subjected to full-area contact exposure using an appropriate exposure level. After irradiation, a PEB treatment was performed at 110°C for 4 minutes, followed by cooling. Subsequently, curing was carried out in an oven under nitrogen-driven conditions of 180°C and 240°C for 2 hours to obtain a photosensitive resin curing film. Then, the wafer with the curing film was cut into strips with a width of 10 mm and a length of 60 mm, and the curing film was peeled off from the substrate by immersion in 20% hydrochloric acid. The obtained curing film was subjected to elongation at break and tensile strength measurements using an AUTOGRAPHAGX-1KN manufactured by Shimadzu Corporation. The measurements were performed 10 times per sample, and the average values ​​are shown in Table 2.

[0484] [Table 2]

[0485]

[0486] VI. Close Contact

[0487] Using the same procedure as described above for pattern formation, photosensitive resin compositions 1-20, and comparative photosensitive resin compositions 1 and 2, were applied to a 1 cm square pattern on a SiN substrate with a cured film thickness of 5 μm. This resulted in a grid-like pattern across the entire substrate. The exposure amount was set to the minimum exposure amount required to form the pattern as determined by the LS pattern evaluation. 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 a predetermined number of 1-minute cycles until the coating film in the unexposed areas dissolved.

[0488] Subsequently, nitrogen purging was performed at 180°C for 2 hours, followed by post-curing of the patterned substrate. The cured substrate was then monolithically processed according to a 1cm square pattern to obtain a wafer with a cured film. An aluminum pin with epoxy resin was erected on the obtained wafer, and the wafer was heated at 150°C for 1 hour to bond the aluminum pin to the wafer, thus obtaining the test sample. After cooling, the sample was analyzed using a ROMULUS instrument manufactured by QuadGroup, employing methods such as... Figure 1 The method shown (hereinafter referred to as the Stud-pull method) was used to determine the contact strength. The measurement conditions were carried out at a measurement speed of 20 N / sec. Figure 1 This is an explanatory diagram showing the method for measuring contact strength. Additionally, Figure 1In this 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 clamping point, and 6 represents the stretching direction. The obtained value is the average of 10 measurements; the higher the value, the stronger the adhesion of the hardened film to the SiN substrate. Furthermore, the adhesion is higher when the peel interface is hardened film / adhesive than when it is substrate / hardened film. Adhesion is evaluated by comparing the obtained values ​​and the peel interface.

[0489] Furthermore, 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. Subsequently, the adhesion strength after the test was evaluated using the Stud-pull method, and the results, together with the results before the test, are expressed in Table 3 as adhesion strength to the substrate.

[0490] [Table 3]

[0491]

[0492] As shown in Table 2, the negative photosensitive resin composition of the present invention can still produce a cured film with good mechanical properties even when cured at low temperatures below 200°C. Furthermore, the negative photosensitive composition of the present invention also maintains good mechanical properties when cured at higher temperatures within a low temperature range (100°C to 300°C) of 240°C. On the other hand, Comparative Examples 1 and 2 exhibit poor mechanical properties at 240°C compared to the negative photosensitive composition of the present invention.

[0493] Furthermore, as shown in Table 3, the negative photosensitive resin composition of the present invention can still produce a cured film with adhesion and high temperature and humidity resistance even when cured at low temperatures below 200°C. On the other hand, Comparative Examples 1 and 2 have poor adhesion compared to the negative photosensitive composition of the present invention.

[0494] The above results lead to the following conclusions: The compositions of Examples 1 to 20 exhibit excellent rectangularity and excellent resolution capable of resolving fine patterns as small as 2 μm. They demonstrate sufficient characteristics for photosensitive materials, and their hardened films possess substrate adhesion and good high-temperature and high-humidity resistance, making them effective as protective films for circuits and electronic components.

[0495] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative examples, and those having substantially the same structure and function as the technical concept described in the claims of the present invention are intended to be included within the technical scope of the present invention.

[0496] Explanation of reference numerals in the attached figures

[0497] 1:SiN substrate (substrate)

[0498] 2: Hardened membrane

[0499] 3: Aluminum pins with adhesive

[0500] 4: Support Taiwan

[0501] 5: Clipping point

[0502] 6: Tension direction

Claims

1. A negative photosensitive resin composition, characterized in that: contain: (A) An alkali-soluble resin containing at least one structure selected from polyimide, polyamide, polybenzoxazole, polyamide-imide, and their precursor structures. (B) Polymer compounds with structural units formed by cyclization polymerization (C) Compounds that produce acids due to light, and (D) Thermal crosslinking agent, The cyclized polymerized structural unit in component (B) is at least one of the structural units represented by the following general formulas (1), (2), (3) and (4); In the formula, R 1 R 2 R 3 R 4 R 5 and R 6 Each is independently a hydrogen atom or a straight-chain or branched alkyl group having 1 to 5 carbon atoms; The (B) component is an alkali-soluble, cross-linked polymeric compound that further contains structural units represented by the following general formula (5) or (5'), and further contains structural units represented by the following general formula (6) and structural units represented by the following general formula (α). In the formula, R 7 Representing a hydrogen atom or a methyl group, X1 represents -C(=O)-O- or -C(=O)-OR, respectively. 8 -, -C(=O)-NH-, -C(=O)-NH-R 8 -or-C(=O)-N(R) 8 OH)-;R 8 It is a straight-chain, branched, or cyclic aliphatic saturated hydrocarbon group with 1 to 12 carbon atoms in the formula, or an aromatic hydrocarbon group with 6 to 12 carbon atoms, and the carbon atoms of the aliphatic saturated hydrocarbon group can also be replaced with oxygen atoms; furthermore, the hydrogen atoms of the aromatic hydrocarbon group in the formula can also be replaced with methyl groups; p is 0 or 1. In the formula, R 9 Represents a hydrogen atom or a methyl group, X2 being -C(=O)-O-, or phenylene or naphthylene, respectively; R 10 It may also contain alkylene groups of 1 to 15 carbon atoms in the form of straight-chain, branched, or cyclic groups, such as ester, ether, or aromatic hydrocarbon groups. 11 It consists of hydrogen atoms, a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or may also contain R. 10 Bonding and forming loops; R 12 R is a hydrogen atom, or a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms. 13 It is a hydrogen atom or a straight-chain alkyl group having 1 to 6 carbon atoms, and can also be combined with R. 10 Bonding and forming a ring; m is 0 or 1; p is 0 or 1; R1' represents a hydrogen atom or a methyl group, R2' represents a single bond or an alkylene group, and R3' is a capped isocyanate group.

2. The negative photosensitive resin composition according to claim 1, wherein, The (B) component is a cross-linked alkali-soluble polymeric compound that further contains structural units represented by the following general formula (7); In the formula, R 14 R represents a hydrogen atom or a methyl group. 15 It is a straight-chain, branched, or cyclic aliphatic saturated hydrocarbon group with 1 to 13 carbon atoms, either with a single bond or a (1+1) valence, and the carbon atoms of this aliphatic saturated hydrocarbon group can also be replaced by oxygen atoms; X3 are -C(=O)-O- and -C(=O)-OR respectively. 16 -, -C(=O)-NH-, -C(=O)-N(R 16 OH)-, or phenylene or naphthylene; R 16 It is a divalent aliphatic saturated hydrocarbon group with 1 to 12 carbon atoms in a straight-chain, branched, or cyclic form, or an aromatic hydrocarbon group with 6 to 12 carbon atoms, and the carbon atom of the aliphatic saturated hydrocarbon group can also be replaced by an oxygen atom; l is 0 or 1.

3. The negative photosensitive resin composition according to claim 1 or 2, wherein, The (B) component is a cross-linked alkali-soluble polymer containing any one or both of the following general formulas (3), (5), (6) or (α), and the structural unit represented by the following general formula (7); In the formula, R 4 is a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms; R 7 represents a hydrogen atom or a methyl group, and X1 is each -C(=O)-O-, -C(=O)-O-R 8 -, -C(=O)-NH-, -C(=O)-NH-R 8 -, or -C(=O)-N(R 8 OH)-; R 8 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 also be substituted with oxygen atoms; further, the hydrogen atoms of the aromatic hydrocarbon group in the formula may also be substituted with methyl groups; R 9 represents a hydrogen atom or a methyl group, and X2 is each -C(=O)-O-, or a phenylene group or a naphthylene group; R 10 is a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may also contain an ester group, an ether group, or an aromatic hydrocarbon group, R 11 is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or may also bond with R 10 to form a ring; R 12 is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, R 13 is a hydrogen atom, or a linear alkyl group having 1 to 6 carbon atoms, and may also bond with R 10 to form a ring; R1' represents a hydrogen atom or a methyl group, R2' represents a single bond or an alkylene group, and R3' is a blocked isocyanate group; R 14 represents a hydrogen atom or a methyl group, R 15 is a single bond or an (l + 1)-valent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms, and the carbon atoms of the aliphatic saturated hydrocarbon group may also be substituted with oxygen atoms; X3 is each -C(=O)-O-, -C(=O)-O-R 16 -, -C(=O)-NH-, -C(=O)-N(R 16 OH)-, or a phenylene group or a naphthylene group; R 16 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 also be substituted with oxygen atoms; p is 0 or 1; m is 0 or 1; l is 0 or 1; and 0 < a1 < 1.0, 0 < a2 < 1.0, 0 ≤ a3 < 1.0, 0 ≤ b1 < 1.0, 0 < a3 + b1 < 1.0, 0 < a4 < 1.0, and satisfies any one of 0 < a1 + a2 + a3 + a4 ≤ 1.0, 0 < a1 + a2 + b1 + a4 ≤ 1.0, 0 < a1 + a2 + a3 + b1 + a4 ≤ 1.

0.

4. The negative photosensitive resin composition according to claim 1 or 2, wherein, The (D) component 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 per molecule.

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

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

7. A method for forming a pattern, characterized by comprising the following steps: (1) The negative photosensitive resin composition according to any one of claims 1 to 6 is coated onto a substrate to form a photosensitive film. (2) Then, 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.

8. A method for forming a hardened film, characterized by comprising the following steps: The patterned film obtained by the pattern forming method according to claim 7 is heated and then hardened at a temperature of 100 to 300°C.

9. An interlayer insulating film, characterized in that: It comprises a hardened film formed by curing a negative photosensitive resin composition according to any one of claims 1 to 6.

10. A surface protective film, characterized in that: It comprises a hardened film formed by curing a negative photosensitive resin composition according to any one of claims 1 to 6.

11. An electronic component, characterized in that it has an interlayer insulating film according to claim 9 or a surface protective film according to claim 10.

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