Positive photosensitive resin composition, positive photosensitive dry film and method for manufacturing the same, and pattern forming method

Abstract

The present invention relates to a positive photosensitive resin composition, a positive photosensitive dry film and a manufacturing method thereof, and a pattern forming method. The present invention aims to provide a positive photosensitive resin composition and a positive photosensitive dry film which can form a fine pattern, can obtain high resolution, have good mechanical properties even when hardened at low temperature, and do not have adhesion force deterioration before and after a high temperature and high humidity test. A positive photosensitive resin composition contains: (A) an alkali-soluble resin containing at least one or more structures selected from a polyimide structure, a polybenzoxazole structure, a polyamide-imide structure, and a precursor structure thereof; (B) a cross-linkable polymer compound containing a structural unit represented by the following general formula (1) and having a group that cross-links with the component (A); and (C) a photosensitizer that generates acid due to light and increases the dissolution rate in an aqueous alkali solution, which is a compound having a quinonediazide structure.

Description

Technical Field

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

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

[0003] In high-density mounting technologies such as three-dimensional stacking, photosensitive insulating materials that can be patterned on a substrate, such as polyimide films, have long been used as protective films and insulating layers. Their insulation, mechanical properties, and adhesion to the substrate continue to receive attention and are currently under active development. In particular, the Fan-out Wafer Level Package (FO-WLP) structure, which has advantages in terms of high-speed transmission, miniaturization, and thinning of devices, has attracted much attention, and various FO-WLP structures have been explored (Non-Patent Literature 1).

[0004] In recent years, for FO-WLP mass production at the 12-inch wafer size, there has been discussion on improving productivity by forming wiring on a substrate using thin film (Non-Patent Literature 2, Non-Patent Literature 3).

[0005] The characteristic of rewiring in FO-PLP is that wiring is formed on the surface of the mold material of the filling mold. Therefore, regarding the insulation material used for rewiring in this step, considering the heat resistance of the mold material with epoxy resin as the main component, low-temperature curing below 220°C is required. Furthermore, since FO-PLP typically forms wiring only on one side, warpage suppression is also a challenge.

[0006] With excellent electrical and mechanical properties and heat resistance exceeding 300°C, photosensitive polyimide materials are used as surface protective films for semiconductor devices, interlayer insulating films, and wiring protective insulating films for circuit formation. In particular, as a countermeasure to improve the above-mentioned problems, in order to lower the post-curing temperature, it has been proposed to use photosensitive polyimides with imidized solvent-soluble resins (Patent Document 1).

[0007] Patent document 1 proposes a positive photosensitive resin composition consisting of an alkali-soluble closed-ring polyimide, a quinone diazide compound, and a thermal crosslinking agent with hydroxymethyl groups. This material has excellent resolution, but there is room for improvement in the elongation at break during low-temperature curing.

[0008] Furthermore, in the dry film formation of photosensitive polyimide, some have proposed: a negative photosensitive resin composition obtained by adding a solubility modifier as a plasticizer to a solvent-soluble polyimide resin (Patent Document 2); a positive photosensitive resin composition obtained by using an alkali-soluble polyimide with a flexible chain diamine unit as a base resin and adding a thermal crosslinking agent with a flexible chain as a plasticizer (Patent Document 3); and a positive photosensitive resin composition obtained by mixing a polyimide resin with a hydroxystyrene-based crosslinking resin and adding an epoxy resin as a plasticizer (Patent Document 4), etc.

[0009] Patent Document 2 describes a material with excellent hardened film properties and electrical characteristics. However, the pattern-forming mechanism uses free radical polymerization, which makes it susceptible to oxygen hindrance in its photocuring mechanism, leaving room for improvement in terms of miniaturization requirements. Furthermore, Patent Documents 3 and 4 only discuss the properties of hardened films at curing temperatures of 250°C or 220°C, without mentioning the properties of hardened films cured at low temperatures or the photolithographic performance of fine patterns.

[0010] Furthermore, regarding the improvement of the mechanical strength of the hardened film, some have proposed adding (meth)acrylic resin to balance photolithographic properties and the physical properties of the hardened film (Patent Documents 5, 6, and 7). Patent Document 5 proposes a positive photosensitive resin composition obtained by adding crosslinking acrylic resin to an alkali-soluble resin with phenolic hydroxyl groups, but the exploration of miniaturization and pattern shape is insufficient, and there is room for improvement in photosensitive properties.

[0011] Patent documents 6 and 7 propose a positive photosensitive resin composition formed by a polymer selected from polyimide, polybenzoxazole and their precursors and acrylic resin. This composition is a material with excellent hardened film properties and stress, but there is no record of its photolithography performance.

[0012] Therefore, considering the increasing density and integration of chips in the future, the miniaturization of patterns in the rewiring technology of insulating protective films is also progressing. As for photosensitive resin compositions, there is a strong desire for compositions that can be thin-filmed and achieve high resolution without compromising the excellent characteristics of the protective film, such as mechanical properties and adhesion.

[0013] Existing technical documents

[0014] Patent documents

[0015] [Patent Document 1] Japanese Patent Application Publication No. 2006-313237

[0016] [Patent Document 2] International Publication No. 2016 / 172092

[0017] [Patent Document 3] International Publication No. 2016 / 158150

[0018] [Patent Document 4] International Publication No. 2017 / 170032

[0019] [Patent Document 5] International Publication No. 2013 / 118680

[0020] [Patent Document 6] Japanese Patent Application Publication No. 2015-129791

[0021] [Patent Document 7] Japanese Patent Application Publication No. 2015-200819

[0022] Non-patent literature

[0023] [Non-Patent Literature 1] 2015 Symposium on VLSI Technology Digest of Technical Papers, T46-47

[0024] [Non-Patent Literature 2] Proceedings of Electronic System-integration Technology Conference 2010, pp. 1-6

[0025] [Non-Patent Literature 3] Proceedings of Electronic Components and Technology Conference 2015, pp. 1077-1083 Summary of the Invention

[0026] The problem the invention aims to solve

[0027] The present invention is made in view of the above facts and aims to provide a positive photosensitive resin composition and a positive photosensitive dry film that is soluble in alkaline aqueous solution, can obtain high resolution without impairing the excellent characteristics such as mechanical properties and adhesion of the protective film, and has good mechanical properties and adhesion to the substrate even when cured at low temperature.

[0028] Solution for solving the problem

[0029] To address the aforementioned issues, the present invention provides a positive photosensitive resin composition comprising:

[0030] (A) An alkali-soluble resin containing at least one structure selected from polyimide structure, polyamide structure, polybenzoxazole structure, polyamide-imide structure, and their precursor structures.

[0031] (B) A cross-linked polymer containing a structural unit represented by the following general formula (1) and having a group that can cross-link with component (A);

[0032] (C) Photosensitive agent is a compound that produces acid due to light and has an increased solubility rate in alkaline aqueous solutions. It is a compound with a quinone diazide structure.

[0033] [Chemistry 1]

[0034]

[0035] In the formula, R 1 R represents a hydrogen atom or a methyl group. 2 It is a straight-chain, branched, or cyclic aliphatic saturated hydrocarbon group with a carbon number of 1 to 15 and a carbon number of 6 to 15, an aromatic hydrocarbon group, a benzyl group, or a naphthylmethyl group, with a carbon number of 1 to 15 and a carbon number of (n+1) valence. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups may also be replaced by oxygen atoms. n is an integer from 1 to 5. X1 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R) 3 OH)-. R 3 It consists of a divalent, linear, branched, or cyclic aliphatic saturated hydrocarbon groups with 1 to 12 carbon atoms, or aromatic hydrocarbon groups with 6 to 12 carbon atoms. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms. p is 0 or 1.

[0036] Such a positive-type photosensitive resin composition is soluble in alkaline aqueous solutions and can form fine patterns, achieving high resolution. Even when cured at low temperatures, it maintains good mechanical properties and adhesion to the substrate. Furthermore, it can impart flexibility to dry films while preserving photolithographic properties.

[0037] Furthermore, in the positive photosensitive resin composition of the present invention, the aforementioned component (B) is preferably a crosslinkable polymer compound containing a structural unit represented by the following general formula (2), and preferably containing a structural unit represented by the following general formula (3) having a group that can crosslink with the aforementioned component (A).

[0038] [Chemistry 2]

[0039]

[0040] In the formula, R 4 Representing a hydrogen atom or a methyl group, X2 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R) 5 OH)-. R 5It consists of a divalent, linear, branched, or cyclic aliphatic saturated hydrocarbon groups with 1 to 12 carbon atoms, or aromatic hydrocarbon groups with 6 to 12 carbon atoms. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms. p is 0 or 1.

[0041] [Chemistry 3]

[0042]

[0043] In the formula, R 6 R represents a hydrogen atom or a methyl group. 7 This indicates an oxazoline group, isocyanate group, terminal isocyanate group, oxacyclobutane group, or epoxy group. X3 is -C(=O)-O-, or phenylene or naphthylene. p is 0 or 1.

[0044] With such a positive photosensitive resin composition, the alkali solubility of the exposed area can be adjusted, finer patterns can be formed, and high resolution can be obtained. In addition, even when cured at low temperatures, the mechanical properties and adhesion to the substrate are good.

[0045] Furthermore, the aforementioned component (B) should preferably be a cross-linked polymer containing structural units represented by the following general formula (2) and the following general formula (4).

[0046] [Chemistry 4]

[0047]

[0048] In the formula, R 8 Representing a hydrogen atom or a methyl group, X4 is independently -C(=O)-O-, or phenylene or naphthylene. R 9 It may also contain hydroxyl, ester, ether, or aromatic hydrocarbons in the form of straight-chain, branched, or cyclic alkylene groups having 1 to 15 carbon atoms. 10 It is a straight-chain, branched, or cyclic alkyl group with hydrogen atoms and 1 to 6 carbon atoms, or it can be combined with R. 9 A ring is formed by bonding. R 11 R is a hydrogen atom, or a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms. 12 It consists of hydrogen atoms or straight-chain alkyl groups having 1 to 6 carbon atoms, and can also be combined with R. 9 A ring is formed by bonding. m is 0 or 1. p is 0 or 1. 0 <b2<1.0、0<b4<1.0、0<b2+b4≤1.0。R 4 Representing a hydrogen atom or a methyl group, X2 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R) 5 OH)-. R 5It consists of aliphatic saturated hydrocarbon groups with a carbon number of 1 to 12 in a divalent state, in the form of straight chains, branches, or rings, or aromatic hydrocarbon groups with a carbon number of 6 to 12. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms.

[0049] When such a cross-linking polymer compound is added to (A) an alkali-soluble resin containing at least one structure selected from polyimide, polyamide, polybenzoxazole, polyamide-imide, and their precursor structures, fine patterns can be obtained due to the excellent alkali solubility contrast of the exposed / unexposed areas. Furthermore, because of the presence of cross-linking groups with excellent cross-linking properties, it will undergo a cross-linking reaction with the phenolic hydroxyl groups of the alkali-soluble resin in (A), and the adhesion to the substrate after reliability testing will not deteriorate.

[0050] Furthermore, it should contain (D) thermal crosslinking agent.

[0051] In addition, the aforementioned component (D) preferably includes one or more crosslinking agents selected from amino condensates modified with formaldehyde or formaldehyde-alcohol, phenolic compounds having an average of more than two hydroxymethyl or alkoxyhydroxymethyl groups per molecule, compounds obtained by substituting the hydrogen atoms of the hydroxyl groups of polyphenols with glycidyl groups, compounds obtained by substituting the hydrogen atoms of the hydroxyl groups of polyphenols with substituents represented by formula (D-1), and compounds containing more than two nitrogen atoms of glycidyl groups represented by formula (D-2).

[0052] [Chemistry 5]

[0053]

[0054] In the formula, the dotted line represents the bond, and R c It indicates a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, where v indicates 1 or 2.

[0055] By adding component (D), the alkali solubility of the exposed / unexposed portions can be adjusted. Furthermore, by cross-linking with components (A) and (B) during post-curing, the cross-linking density of the cured film can be increased, resulting in excellent mechanical strength.

[0056] In addition, relative to 100 parts by mass of the aforementioned component (A), it is preferable to contain 1 to 50 parts by mass of the aforementioned component (B).

[0057] Within this range, while maintaining excellent photolithography characteristics and hardened film properties, sufficient mechanical properties of the hardened film can be obtained, especially elongation and tensile strength.

[0058] In addition, relative to 100 parts by mass of the aforementioned component (A), it is preferable to contain 1 to 100 parts by mass of the aforementioned component (D).

[0059] If within this range, when the positive photosensitive resin composition is dried and thinned, the film can be made flexible while maintaining the photolithographic properties.

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

[0061] (E) Component generates alkaline compounds during high-temperature curing, acting as a catalyst for the cross-linking reaction and promoting its progress. (F) Component further enhances the mechanical strength, chemical resistance, and adhesion of the obtained pattern or film through cross-linking and curing reactions. (G) Component suppresses the degradation of physical properties caused by oxidation of the cured film during reliability tests such as high humidity and thermal shock tests, resulting in a more ideal cured film. (H) Component further improves the adhesion of the obtained pattern or film to the substrate.

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

[0063] (1) The above positive photosensitive resin composition is coated on the substrate to form a photosensitive film;

[0064] (2) After heat treatment, the photomask exposes the photosensitive film using high-energy rays or electron beams with wavelengths of 190–500 nm; and

[0065] (3) After irradiation, develop the solution using an alkaline aqueous solution.

[0066] If such a pattern forming method is used, by using the above-mentioned positive photosensitive resin composition, which is soluble in alkaline aqueous solution, fine patterns can be formed, and high resolution can be obtained.

[0067] In addition, the present invention provides a positive photosensitive dry film, which is a positive photosensitive dry film having a structure in which a photosensitive resin layer with a thickness of 5 to 100 μm is sandwiched between a support film and a protective film, and the composition used to form the photosensitive resin layer is the above-mentioned positive photosensitive resin composition.

[0068] Such positive-type photosensitive dry films are soluble in alkaline developing solutions and can form fine patterns, thus achieving high resolution.

[0069] Furthermore, the present invention provides a method for manufacturing a positive photosensitive dry film, comprising the following steps:

[0070] (1) The above positive photosensitive resin composition is continuously coated on a support film to form a photosensitive resin layer;

[0071] (2) The aforementioned photosensitive resin layer is continuously dried; and

[0072] (3) Further attach a protective film to the aforementioned photosensitive resin layer.

[0073] If such a positive-type photosensitive dry film is manufactured, the aforementioned dry film can be manufactured in stable mass production with good capacity.

[0074] In addition, the present invention provides a pattern forming method, comprising the following steps:

[0075] (1) The photosensitive resin layer exposed by peeling the protective film from the above-mentioned positive photosensitive dry film is closely attached to the substrate.

[0076] (2) While the aforementioned support film is in place, or while the aforementioned support film is peeled off, the aforementioned photosensitive resin layer is exposed using high-energy rays or electron beams with wavelengths of 190–500 nm, separated by a photomask; and

[0077] (3) After irradiation, develop the solution using an alkaline aqueous solution.

[0078] With such a pattern formation method, the above-mentioned positive photosensitive dry film can be attached to the substrate without bubbles or wrinkles, and fine patterns can be formed by optical lithography.

[0079] Furthermore, the present invention provides a method for forming a hardened film, comprising the following steps:

[0080] The patterned film obtained by the above patterning method is heated and then hardened at a temperature of 100–300°C.

[0081] Such a method of forming a hardened film can produce a hardened film (pattern) with good mechanical properties even when hardened at low temperatures.

[0082] Furthermore, the present invention provides an interlayer insulating film, which is composed of the above-mentioned positive photosensitive resin composition or a hardened film formed by curing the above-mentioned positive photosensitive dry film.

[0083] Furthermore, the present invention provides a surface protective film, which is composed of the above-mentioned positive photosensitive resin composition or a hardened film formed by curing the above-mentioned positive photosensitive dry film.

[0084] The positive photosensitive resin composition of the present invention and the cured coating formed by curing the positive photosensitive dry film have excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength and chemical resistance to alkaline stripping solutions, etc. The reliability of semiconductor devices 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 devices, etc.

[0085] Furthermore, the present invention provides an electronic component having the aforementioned interlayer insulating film or surface protective film.

[0086] Such protective films (interlayer insulating films or surface protective films) are effective in insulating films for semiconductor components, including those used for rewiring, and for insulating films for multilayer printed circuit boards, due to their heat resistance, chemical resistance, and insulation properties, and can be used to manufacture electronic components with high reliability.

[0087] The effects of the invention

[0088] As described above, the present invention can provide a positive photosensitive resin composition and a positive photosensitive dry film that are soluble in alkaline aqueous solutions, can achieve high resolution without compromising the mechanical properties, adhesion and other excellent characteristics of the protective film, and maintain good mechanical properties and adhesion to the substrate even when cured at low temperatures. Attached Figure Description

[0089] [ Figure 1 [ ] is an explanatory diagram showing the method for measuring contact strength. Detailed Implementation

[0090] As mentioned above, we seek a photosensitive resin composition that is soluble in alkaline aqueous solutions, can be thin-filmed, and can achieve high resolution without compromising the excellent characteristics of the protective film, such as mechanical properties and adhesion.

[0091] The inventors of this application have made efforts to achieve the above-mentioned objectives and have discovered a positive photosensitive resin composition that can be dry-filmed and, even when cured at low temperatures, can obtain high resolution without compromising the mechanical properties and adhesion of the protective film. The positive photosensitive resin composition contains: (A) an alkali-soluble resin containing at least one structure selected from polyimide, polyamide, polybenzoxazole, polyamide-imide, and their precursor structures; (B) a crosslinking polymer compound containing a structural unit represented by the following general formula (1) and having a group that can crosslink with component (A); and (C) a photosensitizer that produces acid due to light and has an increased solubility rate in alkaline aqueous solutions, and is a compound having a quinone diazide structure.

[0092] [Chemistry 6]

[0093]

[0094] In the formula, R 1 R represents a hydrogen atom or a methyl group. 2It is a straight-chain, branched, or cyclic aliphatic saturated hydrocarbon group with a carbon number of 1 to 15 and a carbon number of 6 to 15, an aromatic hydrocarbon group, a benzyl group, or a naphthylmethyl group, with a carbon number of 1 to 15 and a carbon number of (n+1) valence. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups may also be replaced by oxygen atoms. n is an integer from 1 to 5. X1 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R) 3 OH)-. R 3 It consists of a divalent, linear, branched, or cyclic aliphatic saturated hydrocarbon groups with 1 to 12 carbon atoms, or aromatic hydrocarbon groups with 6 to 12 carbon atoms. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms. p is 0 or 1.

[0095] Furthermore, it was discovered that the protective film obtained by pattern formation and heating using the aforementioned positive photosensitive resin composition and positive photosensitive dry film exhibits excellent mechanical properties and superior adhesion after high temperature and humidity testing. In other words, the hardened film obtained by patterning using the aforementioned positive photosensitive resin composition and positive photosensitive dry film is found to be excellent as a protective film for electrical and electronic components and an insulating protective film, thus completing the present invention. In addition, in this specification, electrical-electronic components are generally referred to as "electronic components".

[0096] That is, the present invention is a positive photosensitive resin composition containing:

[0097] (A) An alkali-soluble resin containing at least one structure selected from polyimide structure, polyamide structure, polybenzoxazole structure, polyamide-imide structure, and their precursor structures.

[0098] (B) A cross-linked polymer containing a structural unit represented by the above general formula (1) and having a group that can cross-link with component (A); and

[0099] (C) Photosensitive agent is a compound that produces acid due to light and has an increased solubility rate in alkaline aqueous solutions. It is a compound with a quinone diazide structure.

[0100] The present invention will now be described in detail, but it is not limited thereto.

[0101] [Positive-type photosensitive resin composition]

[0102] The positive photosensitive resin composition of the present invention will be described.

[0103] The positive photosensitive resin composition of the present invention contains:

[0104] (A) An alkali-soluble resin containing at least one structure selected from polyimide structure, polyamide structure, polybenzoxazole structure, polyamide-imide structure, and their precursor structures.

[0105] (B) A cross-linked polymer containing a structural unit represented by the following general formula (1) and having a group that can cross-link with component (A); and

[0106] (C) Photosensitive agent is a compound that produces acid due to light and has an increased solubility rate in alkaline aqueous solutions. It is a compound with a quinone diazide structure.

[0107] [Chemistry 7]

[0108]

[0109] In the formula, R 1 R represents a hydrogen atom or a methyl group. 2 It is a straight-chain, branched, or cyclic aliphatic saturated hydrocarbon group with a carbon number of 1 to 15 and a carbon number of 6 to 15, an aromatic hydrocarbon group, a benzyl group, or a naphthylmethyl group, with a carbon atom of the above aliphatic saturated hydrocarbon group being replaceable with an oxygen atom. n is an integer from 1 to 5. X1 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R 3 OH)-. R 3 It consists of a divalent, linear, branched, or cyclic aliphatic saturated hydrocarbon groups with 1 to 12 carbon atoms, or aromatic hydrocarbon groups with 6 to 12 carbon atoms. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms. p is 0 or 1.

[0110] The above-mentioned positive photosensitive resin composition can be developed with alkali. Furthermore, in addition to components (A), (B), and (C) mentioned above, the above-mentioned positive photosensitive resin composition may also contain, as needed, (D) a thermal crosslinking agent, (E) a protected amine compound, (F) a thermal acid generating agent, (G) an antioxidant, and (H) a silane compound. These components will be described in detail below.

[0111] [(A) Alkali-soluble resin]

[0112] The alkali-soluble resin (A) of the present invention contains at least one structure selected from polyimide structure, polyamide structure, polybenzoxazole structure, polyamide-imide structure, and their precursor structures. If the resin (A) is an alkali-soluble resin containing the above-mentioned structures, there is no particular limitation, but it is preferable to contain structures represented by the following general formulas (5) and / or (6).

[0113] [Chemistry 8]

[0114]

[0115] In the formula, X5 is a tetravalent organic group, s represents 0 or 1, Z is a divalent bonding group, and when s = 0, the two aromatic rings in the formula are directly bonded without the bonding group.

[0116] [Chemistry 9]

[0117]

[0118] In the formula, X6 is a divalent organic group, and s and Z are the same as above.

[0119] In the above general formula (5), X5 is a tetravalent organic group, and there is no limitation as long as it is a tetravalent organic group. It is preferably a tetravalent organic group of alicyclic aliphatic group or aromatic group with 4 to 40 carbon atoms, and is especially preferred to be a tetravalent organic group represented by the following formula (7). Furthermore, the structure of X5 can be one type or a combination of two or more types.

[0120] [Chemistry 10]

[0121]

[0122] In the formula, the dotted line represents the bond.

[0123] In the above general formula (5), s represents 0 or 1. When s = 0, the two aromatic rings in the above general formula (5) are directly bonded without passing through the divalent bonding group Z.

[0124] On the other hand, when s = 1, the two aromatic rings in the above general formula (5) are bonded via a divalent bonding group Z. Z is not limited as long as it is a divalent group. It is preferably a divalent organic group of an alicyclic aliphatic group or an aromatic group with 4 to 40 carbon atoms, and is especially preferred to be a divalent bonding group represented by the following formula (8). Furthermore, the structure of Z can be one type or a combination of two or more types.

[0125] [Chemistry 11]

[0126]

[0127] 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.

[0128] The divalent bonding group Z is particularly preferably a divalent group represented by the following general formula (9) or (10).

[0129] [Chemistry 12]

[0130]

[0131] In the formula, the dotted line represents the bond.

[0132] Regarding the structural unit represented by the above general formula (5), when Z in the above general formula (5) is a group represented by the above formula (9), it is preferably a structural unit represented by the following general formula (5-1). When Z in the above general formula (5) is a group represented by the above formula (10), it is preferably a structural unit represented by the following general formula (5-2).

[0133] [Chemistry 13]

[0134]

[0135] [Chemistry 14]

[0136]

[0137] In the formula, X5 is the same as above.

[0138] As in the general formula (5-1) above, when the Z of the divalent bonding group is the hexafluoropropylene group represented by the formula (9) above, and is located at the para position of the phenolic hydroxyl group, since the hexafluoropropylene group is an electron-attracting group, the acidity of the phenolic hydroxyl group becomes higher, and the solubility of the developer in the alkaline aqueous solution is improved, which is better.

[0139] Similarly, as in the above general formula (5-2), when the Z of the divalent bonding group is the sulfone group represented by the above formula (10), and is located at the para position of the phenolic hydroxyl group, the sulfone group is also an electron-attracting group. Therefore, the acidity of the above phenolic hydroxyl group increases, and the solubility of the developer in the alkaline aqueous solution is improved, which is better.

[0140] In the above general formula (6), X6 is a divalent organic group. If it is a divalent organic group, there is no limitation. It is preferably a divalent organic group with a long aliphatic chain structure of 4 to 40 carbon atoms, an alicyclic aliphatic group, or an aromatic group. It is especially preferred to be a divalent organic group represented by the following formula (11). Furthermore, the structure of X6 can be one type or a combination of two or more types.

[0141] [Chemistry 15]

[0142]

[0143] In the formula, R 13 R 14 Each is independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, q6 is an integer from 1 to 30, and the dotted line indicates the bond.

[0144] When X6 in the above general formula (6) is a divalent organic group with an aliphatic long chain structure, the mechanical strength, especially the elongation, of the hardened film of the positive photosensitive resin composition of the present invention becomes higher, which is better.

[0145] In the above general formula (6), s and Z are the same as above. Considering the solubility of the developer in alkaline aqueous solution, Z should preferably be the above general formula (9) or (10). In this case, similar to the cases of formulas (5-1) and (5-2) above, the acidity of the phenolic hydroxyl group becomes higher, and the solubility of the developer in alkaline aqueous solution is improved, so it is better.

[0146] Furthermore, in addition to containing the structural units represented by the above general formulas (5) and (6), the alkali-soluble resin (A) of the present invention may also contain the structural units represented by the following general formula (12) (hereinafter also referred to as structural units (12)).

[0147] [Chemistry 16]

[0148]

[0149] In the formula, X6 is the same as above. X7 is a divalent organic group.

[0150] In the above general formula (12), X7 is a divalent organic group. If it is a divalent organic group, there is no limitation. It is preferably a divalent organic group with 6 to 40 carbon atoms, and it is more preferably a cyclic organic group containing 1 to 4 aromatic or aliphatic rings with substituents, or an aliphatic group or siloxane group without a cyclic structure. As a more ideal X7, the structure represented by the following formula (13) or (14) can be listed. In addition, the structure of X7 can be one type or a combination of two or more types.

[0151] [Chemistry 17]

[0152]

[0153] In the formula, the dotted line represents the bond with the amino group.

[0154] [Chemistry 18]

[0155]

[0156] In the formula, the dotted line represents the bond with the amino group, R 15 Each can be independently represented as methyl, ethyl, propyl, n-butyl, or trifluoromethyl, and q7 represents a positive number from 2 to 20.

[0157] Furthermore, in addition to containing the structural units represented by the above general formulas (5) and (6), the alkali-soluble resin (A) of the present invention preferably contains the structural units represented by the following general formula (15) (hereinafter also referred to as structural units (15)).

[0158] [Chemistry 19]

[0159]

[0160] In the formula, X8 is a tetravalent organic group that is the same as or different from X5 above, and X9 is a group represented by the following general formula (16).

[0161] [Chemistry 20]

[0162]

[0163] In the formula, R16 ~R 19 Each is an independent linear or branched alkylene group having 2 to 10 carbon atoms, m1 is an integer from 1 to 40, and m2 and m3 are independent integers from 0 to 40.

[0164] In formula (15), X8 can be any of the tetravalent organic groups listed for X5, such as the tetravalent organic group represented by formula (7) above. Also, the organic groups that can be ideally used in X9 (the group represented by the general formula (16) above) are specifically listed below. However, it is not limited to these.

[0165] [Chemistry 21]

[0166]

[0167] By using an alkali-soluble resin (A) containing such structural units (15), flexibility is achieved, resulting in a hardened film with high elongation and low warpage.

[0168] In addition, the alkali-soluble resin (A) of the present invention may contain structural units represented by the following general formula (17) or (18) (hereinafter referred to as structural unit (17) and structural unit (18)).

[0169] [Chemistry 22]

[0170]

[0171] [Chemistry 23]

[0172]

[0173] In the formula, X 10 It is a tetravalent organic group that is the same as or different from X5 mentioned above, X 11 It is a divalent organic group that is the same as or different from X7; s and Z are the same as above. R 20 and R 21 Each is independently a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group represented by the following general formula (19), R 20 and R 21 At least one of them is an organic group represented by the following general formula (19).

[0174] [Chemistry 24]

[0175]

[0176] In the formula, the dotted line represents the bond. R 22 R is a hydrogen atom or an organic group having 1 to 3 carbon atoms. 23 and R 24 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.

[0177] X in the above structural units (17) and (18) 10 It is a tetravalent organic group, which may be the same as or different from X5 above. If it is a tetravalent organic group, there is no limitation. It is preferably a tetravalent organic group of alicyclic aliphatic group or aromatic group with 4 to 40 carbon atoms, and is especially preferred to be a tetravalent organic group represented by formula (7) above. Also, X 10 The structure can be one type or a combination of two or more types.

[0178] On the other hand, X in the above structural unit (18) 11 It is a divalent organic group, which may be the same as or different from X7 above. If it is a divalent organic group, there is no limitation. It is preferably a divalent organic group with 6 to 40 carbon atoms, and more preferably a cyclic organic group containing 1 to 4 aromatic or aliphatic rings with substituents, or an aliphatic group or siloxane group without a cyclic structure. As a more ideal X... 11 The structures represented by equations (13) or (14) above can be listed. Also, X 11 The structure can be one type or a combination of two or more types.

[0179] R in the above structures (17) and (18) 20 and R 21 Each is independently a hydrogen atom or a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group represented by the above general formula (19), R 20 and R 21 At least one of them is an organic group represented by the above general formula (19).

[0180] In the above general formula (19), R 22 There are no restrictions as long as it is a hydrogen atom or a monovalent organic group with 1 to 3 carbon atoms. However, considering the photosensitivity of positive photosensitive resin components, it is preferable to use a hydrogen atom or a methyl group.

[0181] In the above general formula (19), R 23 and R 24 There are no restrictions as long as each component is an independent hydrogen atom or a monovalent organic group with 1 to 3 carbon atoms. However, considering the photosensitivity of positive photosensitive resin components, hydrogen atoms are preferable.

[0182] In the above general formula (19), o is an integer from 2 to 10. Considering the photosensitivity, it is preferable to be an integer from 2 to 4. O is especially preferred to be 2.

[0183] [(B) Cross-linked polymers]

[0184] The cross-linked polymer (B) used in this invention is not particularly limited as long as it contains a structural unit represented by the following general formula (1) and contains a group that can cross-link with component (A).

[0185] [Chemistry 25]

[0186]

[0187] Here, in general formula (1), R 1 R represents a hydrogen atom or a methyl group. 2 The carbon atoms of the aliphatic saturated hydrocarbon group (n+1) with 1 to 15 carbon atoms can be linear, branched, or cyclic, or have an aromatic hydrocarbon group with 6 to 15 carbon atoms, benzyl, or naphthylmethyl. The carbon atoms of these aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms. Furthermore, n is an integer from 1 to 5, and X1 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R) 3 OH)-. R 3 It consists of aliphatic saturated hydrocarbon groups with a carbon number of 1 to 12 and a carbon number of 6 to 12, in a divalent form. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms, and p is 0 or 1.

[0188] Furthermore, regarding the monomers used to obtain the structure represented by general formula (1), as an example of an ideal user, the following can be specifically exemplified.

[0189] [Chemistry 26]

[0190]

[0191] In the formula, R 1 As mentioned above.

[0192] [Chemistry 27]

[0193]

[0194] In the formula, R 1 As mentioned above.

[0195] [Chemistry 28]

[0196]

[0197] In the formula, R 1 As mentioned above.

[0198] Furthermore, there are no particular limitations on the groups that crosslink with the alkali-soluble resin of component (A), but examples include oxazolinyl, isocyanate, terminal isocyanate, oxetane, and epoxy groups, which are described later.

[0199] In addition, regarding component (B), in order to maintain alkali solubility and improve crosslinking density, it is preferable to contain structural units represented by the following general formula (2) and the following general formula (3).

[0200] [Chemistry 29]

[0201]

[0202] Here, in general formula (2), R 4 Representing a hydrogen atom or a methyl group, X2 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R) 5 OH)-. R 5 It consists of a divalent, linear, branched, or cyclic aliphatic saturated hydrocarbon groups with 1 to 12 carbon atoms, or aromatic hydrocarbon groups with 6 to 12 carbon atoms. The carbon atoms of the aforementioned aliphatic saturated hydrocarbon groups can also be replaced by oxygen atoms. p is 0 or 1.

[0203] [Chemistry 30]

[0204]

[0205] Here, in general formula (3), R 6 R represents a hydrogen atom or a methyl group. 7 This indicates an oxazoline group, isocyanate group, terminal isocyanate group, oxacyclobutane group, or epoxy group. X3 is -C(=O)-O-, or phenylene or naphthylene. p is 0 or 1.

[0206] Furthermore, the aforementioned terminated isocyanate group refers to an organic group in which the isocyanate group (-N=C=O) is terminated using an appropriate protecting group. The terminated isocyanate group can be formed by reacting the isocyanate group with a terminating agent.

[0207] When reacting with the hydroxyl or carboxyl groups in component (A), the capping agent detaches, and the hydroxyl or carboxyl groups 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.

[0208] Ideally, a capped isocyanate group is described in paragraphs

[0015] to

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

[0209] On the other hand, if the structure represented by general formula (2) has a carbonyl group or an amide group, which is an electron-attracting group, at the para position of the phenolic hydroxyl group, the acidity of the phenolic hydroxyl group increases, and the solubility in alkaline aqueous solutions for developers is improved. Examples of monomers that can ideally be used to form structural units of general formula (2) are shown below. However, this is not a limitation.

[0210] [Chemistry 31]

[0211]

[0212] In the formula, R 4 As mentioned above.

[0213] As for general formula (2), in addition to improving alkali solubility, it is effective as a unit to promote cross-linking, and can further improve hardening properties by using it in combination with cross-linking groups.

[0214] In addition, in order to improve the crosslinking density, it is advisable to copolymerize monomers having epoxy groups or oxobutane groups represented by the following general formula (4).

[0215] [Chemistry 32]

[0216]

[0217] Here, in general formula (4), R 8 Representing a hydrogen atom or a methyl group, X4 is independently -C(=O)-O-, or phenylene or naphthylene. R 9 It may also contain hydroxyl, ester, ether, or aromatic hydrocarbons in the form of straight-chain, branched, or cyclic alkylene groups having 1 to 15 carbon atoms. 10 It is a straight-chain, branched, or cyclic alkyl group with hydrogen atoms and 1 to 6 carbon atoms, or it can be combined with R. 9 A ring is formed by bonding. R 11 R is a hydrogen atom, or a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms. 12 It consists of hydrogen atoms or straight-chain alkyl groups having 1 to 6 carbon atoms, and can also be combined with R. 9 A ring is formed by bonding. m is 0 or 1. p is 0 or 1. Examples of units in equation (4) can be listed below.

[0218] [Chemistry 33]

[0219]

[0220] In the formula, R 8 As mentioned above.

[0221] [Chemistry 34]

[0222]

[0223] In the formula, R 8 As mentioned above.

[0224] [Chemistry 35]

[0225]

[0226] In the formula, R 8 As mentioned above.

[0227] Furthermore, a subset of monomers used to obtain repeating units having epoxy groups and oxetyl groups are disclosed in Japanese Patent Application Publication Nos. 2003-55362, 2005-8847, and 2005-18012.

[0228] The structural unit represented by general formula (2) has excellent solvent and alkali solubility, but lacks crosslinking properties, so it must be copolymerized with the structural unit represented by general formula (4) which has crosslinking properties. Polymers composed only of epoxy groups and oxetane groups represented by general formula (4) which have crosslinking properties have excellent crosslinking properties, but lack alkali solubility, so they must be copolymerized with the structural unit represented by general formula (2).

[0229] Therefore, when repeating units are co-aggregated in this way, repeating units of the following formula (1a) are preferred.

[0230] [Chemistry 36]

[0231]

[0232] In the formula, R 4 R 8 ~R 12 X2, X4, m, and p are the same as above, 0 <b2<1.0、0<b4<1.0、0<b2+b4≤1.0。

[0233] The crosslinkable polymer compound of the present invention is based on repeating units formed by monomers having repeating units with hydroxyl groups as represented by the above general formula (1) (hereinafter referred to as b1) and monomers having repeating units having repeating units with groups that can crosslink with alkali-soluble resins of component (A) as represented by the above general formula (4) (hereinafter referred to as b4). In order to improve adhesion to the substrate, flexibility of the hardened film, and further improve mechanical properties and thermal shock resistance, monomers having repeating units represented by the following general formula (20) can also be copolymerized.

[0234] [Chemistry 37]

[0235]

[0236] Here, in general formula (20), R 25 R represents a hydrogen atom or a methyl group.26 It is a monovalent organic group having a primary, secondary, or tertiary amine 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 It should be -C(=O)-O- or -C(=O)-NH-. b5 is 0≤b5<1.

[0237] Monomers that obtain the repeating unit represented by the above general formula (20) can be exemplified by the following specific examples: (meth)acrylate aminoethyl ester, (meth)acrylate N-methylaminoethyl ester, (meth)acrylate N,N-dimethylaminoethyl ester, (meth)acrylate N-ethylaminoethyl ester, (meth)acrylate N,N-diethylaminoethyl ester, (meth)acrylate aminopropyl ester, (meth)acrylate N-methylaminopropyl ester, (meth)acrylate N,N-dimethylaminopropyl ester, (meth)acrylate N-ethylaminopropyl ester, (meth)acrylate N,N-diethylaminopropyl ester, aminoethyl(meth)acrylamide, N-methylaminoethyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N-ethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, aminopropyl(meth)acrylamide, N-methylaminopropyl(meth)acrylamide, N,N-dimethyl ... N-ethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, piperidine-4-ester (meth)acrylate, 1-methylpiperidine-4-ester (meth)acrylate, 2,2,6,6-tetramethylpiperidine-4-ester (meth)acrylate, 1,2,2,6,6-pentamethylpiperidine-4-ester (meth)acrylate, (piperidine-4-yl)methyl methacrylate, 2-(piperidine-4-yl)ethyl methacrylate, (meth)acrylate, 1-methylpiperidine-4-ester (meth)acrylate, 2,2,6,6-tetramethylpiperidine-4-ester (meth)acrylate, 1,2,2,6,6-pentamethylpiperidine-4-ester (meth)acrylate, (piperidine-4-yl)methyl methacrylate, 2-(piperidine-4-yl)ethyl methacrylate, etc.

[0238] In addition, as the monomer for obtaining the repeating unit represented by the above general formula (20), (meth)acrylic acid alkyl esters can be used, and specific examples include: butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc.

[0239] In addition, in order to improve the mechanical strength of the cured film, olefins b6 having an aromatic group such as styrenes, vinyl naphthalenes, vinyl anthracenes, vinyl carbazoles, vinyl naphthalenes, indenes, etc., and alicyclic olefins b7 such as norbornenes and norbornadienes can be copolymerized.

[0240] Among the above repeating units b1, b4, b5, b6, and b7, the ratio of the repeating units is 0 < b1 < 1.0, 0 < b1 + b4 ≤ 1.0, 0 ≤ b4 < 1.0, 0 ≤ b5 ≤ 0.8, 0 ≤ b6 ≤ 0.8, 0 ≤ b7 ≤ 0.8. It is preferably 0 < b1 ≤ 0.5, 0.1 ≤ b4 ≤ 0.9, more preferably 0.2 ≤ b4 ≤ 0.8, 0.1 ≤ b1 + b4 ≤ 1.0, 0 ≤ b5 ≤ 0.7, 0 ≤ b6 ≤ 0.7, 0 ≤ b7 ≤ 0.7. More preferably, it is in the range of 0 < b1 ≤ 0.4, 0.5 ≤ b4 ≤ 0.8, 0.2 ≤ b1 + b,4 ≤ 1.0, 0 ≤ b5 ≤ 0.6, 0 ≤ b6 ≤ 0.6, 0 ≤ b7 ≤ 0.6. In addition, b1 + b4 + b5 + b6 + b7 = 1, and the sum of these repeating units is 100 mol% of the total amount of all repeating units.

[0241] The crosslinkable polymer compound (B) used in the present invention has a polystyrene-reduced weight average molecular weight of 1,000 to 500,000 obtained by gel permeation chromatography (GPC), and is particularly preferably 2,000 to 30,000. If the weight average molecular weight is larger than the lower limit of these, the glass transition temperature is high enough, and the pattern will not deform during the thermal crosslinking after development of the positive photosensitive resin composition. If it is smaller than the upper limit, there will be no concern about pinhole defects during coating.

[0242] In addition, two or more kinds of polymers having different composition ratios, molecular weight distributions, and molecular weights can also be blended.

[0243] Furthermore, at this point, the amount of cross-linking polymer compound (B) added should preferably be 1 part by mass or more and 50 parts by mass or less relative to 100 parts by mass of alkali-soluble resin (A). If the amount added is 1 part by mass or more, the toughness of the hardened film with the alkali-soluble resin (A) as described above is high; if it is 50 parts by mass or less, the tensile strength of the hardened film will not decrease. Therefore, the amount of cross-linking polymer compound (B) added should preferably be within the above range. The amount of component (B) added is more preferably 1 part by mass or more and 35 parts by mass, and even more preferably 1 part by mass or more and 25 parts by mass. Within this range, a good balance is achieved between photolithographic patterning performance and the physical properties of the hardened film.

[0244] [(C) Photosensitive agent]

[0245] Component (C) in the positive photosensitive resin composition of the present invention is a photosensitive agent that generates acid due to light and has an increased solubility rate in alkaline aqueous solutions, and is a compound having a quinone diazide structure. Component (C) can be exemplified by compounds having a 1,2-naphthoquinone diazidesulfonyl group in their molecule.

[0246] As compounds having a 1,2-naphthoquinone diazidosulfonyl group in the molecule, examples can be listed of compounds having a 1,2-naphthoquinone diazidosulfonyl group represented by the following general formula (21) or (22).

[0247] [Chemistry 38]

[0248]

[0249] [Chemistry 39]

[0250]

[0251] The compound to be introduced with the above-mentioned 1,2-naphthoquinone diazidosulfonyl group, specifically, is preferably a phenolic varnish resin with a weight average molecular weight in the range of 2,000 to 20,000, more preferably 3,000 to 10,000, of which trihydroxybenzophenone or tetrahydroxybenzophenone, a ballast molecule having a phenolic hydroxyl group represented by the following general formula (23), or a repeating unit having a repeating unit represented by the following formula (28). That is, the resins having phenolic hydroxyl groups listed below, and compounds obtained by substituting the hydrogen atoms of the phenolic hydroxyl groups with the above-mentioned 1,2-naphthoquinone diazidosulfonyl group, can ideally be used as component (C).

[0252] [Chemistry 40]

[0253]

[0254] Here, R 101 ~R 106Each is independently a hydrogen atom, a methyl group, a group represented by formula (24) or a group represented by formula (25). w is an integer from 0 to 2, z is an integer from 0 to 2, and when z is 0, w is 1 or 2. For A, when z is 0 and w is 1, it is a hydrogen atom, a methyl group, or a group represented by formula (24); when z is 0 and w is 2, one of them is a methylene group or a group represented by formula (26), and the other is a hydrogen atom, a methyl group or a group represented by formula (24); when z is 1, it is a methylene group or a group represented by formula (26). In the case of z being 2, when w is 1, A is a methine group or a group represented by formula (27); when w is 2, one of A is a methylene group or a group represented by formula (26), and the other is a methine group or a group represented by formula (27).

[0255] [Chemistry 41]

[0256]

[0257] In the formula, a1, a2, a3, a4, a5, a6, and a7 are each independent integers from 0 to 3, and a1+a2≤5, a3+a4≤4, and a6+a7≤3.

[0258] At this point, for the low-nuclear body (ballast molecule) of the above formula (23), the number of benzene rings is 2 to 20, more preferably 2 to 10, and even more preferably 3 to 6, and the ratio of the number of phenolic hydroxyl groups to the number of benzene rings is 0.5 to 2.5, more preferably 0.7 to 2.0, and even more preferably 0.8 to 1.5.

[0259] Specifically, the following can be listed as such low-nuclear (ballast) molecules.

[0260] [Chemistry 42]

[0261]

[0262] [Chemistry 43]

[0263]

[0264] [Chemistry 44]

[0265]

[0266] [Chemistry 45]

[0267]

[0268] [Chemistry 46]

[0269]

[0270] [Chemistry 47]

[0271]

[0272] [Chemistry 48]

[0273]

[0274] Among the low-nuclear bodies (ballast molecules) exemplified above, (C-3), (C-29), (C-33), (C-38), etc., are ideally used. Compounds obtained by substituting the hydrogen atoms of the phenolic hydroxyl groups of these ballast molecules with 1,2-naphthoquinone diazidosulfonyl groups are ideally used in component (C) of the positive photosensitive resin composition of the present invention.

[0275] [Chemistry 49]

[0276]

[0277] In the formula, mm is an integer from 0 to 3.

[0278] The phenolic varnish resin having the repeating unit represented by the above formula (28) can be synthesized by condensing at least one of the phenols represented by the following formula (29), specifically o-cresol, m-cresol, p-cresol, 3,5-xylenol, etc., with an aldehyde using conventional methods.

[0279] [Transformation 50]

[0280]

[0281] In the formula, mm is an integer from 0 to 3.

[0282] At this point, regarding aldehydes, such as formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde, formaldehyde is the most ideal.

[0283] Furthermore, the ratio of phenols to aldehydes expressed in the above formula (29) is preferably a molar ratio of 0.2 to 2, and more preferably 0.3 to 2.

[0284] For the method of introducing 1,2-naphthoquinone diazidosulfonyl group into the compound to which the above-mentioned 1,2-naphthoquinone diazidosulfonyl group is to be introduced, it is preferable to use a dehydrochlorination condensation reaction of 1,2-naphthoquinone diazidosulfonyl chloride with phenolic hydroxyl group using an alkaline catalyst. In the case of the ballast molecule represented by the above formula (23), trihydroxybenzophenone or tetrahydroxybenzophenone, the proportion of hydrogen atom of phenolic hydroxyl group replaced by 1,2-naphthoquinone diazidosulfonyl group is 10 to 100 mol%, preferably 50 to 100 mol%. In the case of phenolic varnish resin having repeating unit represented by the above formula (28), the proportion of hydrogen atom of phenolic hydroxyl group replaced by 1,2-naphthoquinone diazidosulfonyl group is 2 to 50 mol%, preferably 3 to 27 mol%.

[0285] The amount of component (C) added is preferably 1 to 60 parts by weight, more preferably 10 to 50 parts by weight, relative to 100 parts by weight of component (A). Furthermore, component (C) may be used alone or in combination of two or more.

[0286] By incorporating such a (C) component, the solubility of the alkaline aqueous solution is inhibited before exposure due to the solubility inhibition of the (C) component, making the system alkaline insoluble. During exposure, the photosensitizer of the (C) component produces acid due to light, increasing the solubility rate of the alkaline aqueous solution, making the system alkaline soluble.

[0287] In other words, when using an alkaline aqueous solution as the developer, the unexposed areas do not dissolve in the developer, while the exposed areas do dissolve in the developer, thus forming a positive pattern.

[0288] [(D) Thermal crosslinking agent]

[0289] In addition to the essential components (A), (B), and (C) mentioned above, the positive photosensitive resin composition of the present invention preferably contains (D) one or more crosslinking agents selected from the following: an amino condensate modified with formaldehyde or formaldehyde-alcohol; a phenolic compound having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups per molecule; a compound obtained by substituting the hydrogen atom of the hydroxyl group of a polyphenol with an epoxypropyl group; a compound obtained by substituting the hydrogen atom of the hydroxyl group of a polyphenol with a substituent represented by formula (D-1); and a compound containing two or more nitrogen atoms of an epoxypropyl group represented by formula (D-2).

[0290] [Chemistry 51]

[0291]

[0292] In the formula, the dotted line represents the bond, and R c It indicates a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, where v indicates 1 or 2.

[0293] The aforementioned amine condensates modified with formaldehyde or formaldehyde-alcohol include, for example, melamine condensates modified with formaldehyde or formaldehyde-alcohol, or urea condensates modified with formaldehyde or formaldehyde-alcohol.

[0294] The preparation of the above-mentioned melamine condensate modified with formaldehyde or formaldehyde-alcohol involves, for example, first modifying the melamine monomer by hydroxymethylation with formalin using a known method, or further modifying it by alkoxylation with an alcohol, to prepare the modified melamine represented by the following general formula (30). Furthermore, the alcohol is preferably a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms.

[0295] [Chemistry 52]

[0296]

[0297] In the formula, R 27 They may be the same or different, and can be hydroxymethyl, alkoxymethyl containing alkoxy groups with 1 to 4 carbon atoms, or hydrogen atoms, with at least one being hydroxymethyl or the above-mentioned alkoxymethyl.

[0298] As mentioned above, R 27 Examples include hydroxymethyl, methoxymethyl, ethoxymethyl, and other alkoxymethyl groups, as well as hydrogen atoms.

[0299] The modified melamine represented by the above general formula (30) can be specifically listed as: trimethoxymethyl monohydroxymethyl melamine, dimethoxymethyl monohydroxymethyl melamine, trihydroxymethyl melamine, hexahydroxymethyl melamine, hexamethoxymethyl melamine, etc.

[0300] Then, the modified melamine or its polymers (e.g., dimers, trimers, etc.) represented by the above general formula (30) 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.

[0301] Furthermore, the preparation of the above-mentioned urea condensate modified with formaldehyde or formaldehyde-alcohol can be achieved, for example, by following known methods, modifying the urea condensate of the desired molecular weight by hydroxymethylation with formaldehyde, or by further modifying it by alkoxylation with an alcohol.

[0302] Specific examples of the urea condensates modified with formaldehyde or formaldehyde-alcohols mentioned above include, for example, methoxymethylated urea condensates, ethoxymethylated urea condensates, propoxymethylated urea condensates, etc.

[0303] Furthermore, these modified melamine condensates and modified urea condensates can be used in combination, either one or two or more.

[0304] Then, phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups per molecule, such as (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and compounds represented by formulas (D-3) to (D-7).

[0305] [Chemistry 53]

[0306]

[0307] In addition, one or more of the above-mentioned crosslinking agents may be used.

[0308] On the other hand, compounds obtained by substituting the hydrogen atom of the hydroxyl group of a polyphenol with an epoxypropyl group can be exemplified by reacting the hydroxyl groups of bisphenol A, tris(4-hydroxyphenyl)methane, and 1,1,1-tris(4-hydroxyphenyl)ethane with epichlorohydrin in the presence of a base. Ideal examples of compounds obtained by substituting the hydrogen atom of the hydroxyl group of a polyphenol with an epoxypropyl group can be exemplified by compounds represented by formulas (D-8) to (D-14).

[0309] [Chemistry 54]

[0310]

[0311] In the formula, t is 2≤t≤3.

[0312] Furthermore, ideal examples of compounds other than those in formulas (D-8) to (D-14) can be listed as follows: EPICLON 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON EXA-4710, EPICLON HP-4770, EPICLON EXA-859CRP, EPICLON EXA-4880, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822 (these are trade names, manufactured by Dai Nippon Inki Chemical Co., Ltd.), RIKARESIN BPO-20E, RIKARESIN BEO-60E (the above are product names, manufactured by Shin Nippon Rikka Co., Ltd.), EP-4003S, EP-4000S, EP-4000S, EP-4000L (the above are product names, manufactured by ADEKA Co., Ltd.), jER828EL, YX7105 (the above are product names, manufactured by Mitsubishi Chemical Co., Ltd.), etc.

[0313] One or two of these compounds obtained by substituting the hydroxyl groups of polyphenols with epoxy propoxy groups (compounds obtained by substituting the hydrogen atoms of the hydroxyl groups of polyphenols with epoxy propoxy groups) can be used as crosslinking agents.

[0314] Compounds obtained by substituting the hydrogen atom of the hydroxyl group of a polyphenol with a substituent represented by the following formula (D-1) may be listed, including those containing two or more of the above substituents and represented by the following formula (D-15).

[0315] [Chemistry 55]

[0316]

[0317] In the formula, the dotted line represents the bond.

[0318] [Chemistry 56]

[0319]

[0320] In the formula, 1≤u≤3.

[0321] Furthermore, ideal examples of compounds other than those in formula (D-15) above include: 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetane)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenediacarboxylic acid-bis[(3-ethyl-3-oxetane)methyl] ester, and the Aron Oxetane series manufactured by Toa Synthetic Co., Ltd., etc.

[0322] On the other hand, compounds containing two or more nitrogen atoms with an epoxypropyl group, represented by the following formula (D-2), can be exemplified by those represented by the following formula (D-16).

[0323] [Chemistry 57]

[0324]

[0325] In the formula, the dotted line represents the bond, and R c It indicates a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, where v indicates 1 or 2.

[0326] [Chem.58]

[0327]

[0328] In the formula, W represents a straight-chain, branched, cyclic alkylene group or a divalent aromatic group having 2 to 12 carbon atoms. Furthermore, W here applies only in the above formula.

[0329] The compounds represented by the above formula (D-16) can be exemplified, for example, by compounds represented by the following formulas (D-17) to (D-20).

[0330] [Chemistry 59]

[0331]

[0332] Furthermore, on the other hand, for compounds containing two or more nitrogen atoms with an epoxypropyl group as represented by the above formula (D-2), compounds represented by the following formulas (D-21) and (D-22) can ideally be used.

[0333] [Transformation 60]

[0334]

[0335] These compounds containing two or more nitrogen atoms with glycidyl groups as represented by the above formula (D-2) can be used as crosslinking agents, one or two of which can be used.

[0336] Regarding epoxy groups, the rings are highly deformable and reactive, while oxetanes are highly basic and readily bond with acids. It has been reported that combining oxetanes with epoxy groups significantly improves the reactivity of cationic polymerization.

[0337] Component (D) is a component that, after the pattern of the positive photosensitive resin composition of the present invention is formed, undergoes a cross-linking reaction during post-curing, thereby further improving the strength of the cured product. The weight-average molecular weight of such component (D), considering photocurability and heat resistance, is preferably 150 to 10,000, and particularly preferably 200 to 3,000.

[0338] Regarding the amount of component (D), in the positive photosensitive resin composition of the present invention, it is preferably 0.5 to 100 parts by mass relative to 100 parts by mass of component (A), more preferably 1 to 100 parts by mass, and especially preferably 1 to 80 parts by mass.

[0339] [(E) Protected amine compounds]

[0340] The positive photosensitive resin composition of the present invention, in addition to containing the aforementioned essential components (A), (B), and (C), may further contain the protected amine compound (E). The protected amine compound of component (E) is any nitrogen-containing organic compound that can be deprotected by heat or acid and bonded to a nitrogen atom. In particular, it is not particularly limited to those having a carbamate structure represented by the following general formulas (31) or (32).

[0341] [Chemistry 61]

[0342]

[0343] Here, in the formula, R 28 R 29 R 30 and R 31 Each can independently represent hydrogen, or be a substituent of an alkyl group having 1 to 8 carbons, a cycloalkyl group having 3 to 8 carbons, an alkoxy group having 1 to 8 carbons, an alkenyl group having 2 to 8 carbons, an alkynyl group having 2 to 8 carbons, an aryl group having 2 to 8 carbons, or a heterocyclic group having substituted groups, R 32 and R 33Each of the following can independently represent hydrogen, an alkyl group having 1 to 8 carbon atoms that may have substituents, a cycloalkyl group having 3 to 8 carbon atoms that may have substituents, an alkoxy group having 1 to 8 carbon atoms that may have substituents, an alkenyl group having 2 to 8 carbon atoms that may have substituents, an alkynyl group having 2 to 8 carbon atoms that may have substituents, an aryl group having 2 to 8 carbon atoms that may have substituents, a heterocyclic group having 2 to 8 carbon atoms that may have substituents, a monocyclic ring having 2 to 8 carbon atoms that may have substituents formed by bonding together, or a polycyclic ring having 2 to 8 carbon atoms that may have 2 to 8 carbon atoms that may have substituents formed by bonding together. However, the total number of carbon atoms in the formula should preferably be 10 or less. Also, R 34 This indicates that the substituent may be an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, an alkenyl group with 2 to 12 carbon atoms, an alkynyl group with 2 to 12 carbon atoms, an aryl group with 1 to 3 carbon atoms as a substituent, an aralkyl group with 1 to 3 carbon atoms as a substituent, or a heterocyclic group. However, the constituent R 34 The total number of carbon atoms is 12 or less. The substituents that the above-mentioned group may have can be any type.

[0344] [Chemistry 62]

[0345]

[0346] Specific examples of the above formulas (31) and (32) can be listed below. For example, there are: N-(isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(isopropoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(isopropoxycarbonyl)diisopropylamine, N-(isopropoxycarbonyl)pyrrolidine, N-(isopropoxycarbonyl)-2,5-dimethylpyrrolidine, N-(isopropoxycarbonyl)-tetrahydroacetidine, N-(1-ethylpropoxycarbonyl)-2,6-dimethylpiperidine, N-(1-ethylpropoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(1-ethylpropoxycarbonyl)diisopropylamine, N-(1-ethylpropoxycarbonyl)pyrrolidine, N-(1-ethylpropoxycarbonyl)-2 5-Dimethylpyrrolidine, N-(1-ethylpropoxycarbonyl)-tetrahydroacridine, N-(1-propylbutoxycarbonyl)-2,6-dimethylpiperidine, N-(1-propylbutoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(1-propylbutoxycarbonyl)diisopropylamine, N-(1-propylbutoxycarbonyl)pyrrolidine, N-(1-propylbutoxycarbonyl)-2,5-dimethylpyrrolidine, N-(1-propylbutoxycarbonyl)-tetrahydroacridine, N-(cyclopentoxycarbonyl)-2,6-dimethylpiperidine, N-(cyclopentoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(cyclopentoxycarbonyl)diisopropylamine Amine, N-(cyclopentoxycarbonyl)pyrrolidine, N-(cyclopentoxycarbonyl)-2,5-dimethylpyrrolidine, N-(cyclopentoxycarbonyl)-tetrahydroacridine, N-(cyclohexylcarbonyl)-2,6-dimethylpiperidine, N-(cyclohexylcarbonyl)-2,2,6,6-tetramethylpiperidine, N-(cyclohexylcarbonyl)diisopropylamine, N-(cyclohexylcarbonyl)pyrrolidine, N-(cyclohexylcarbonyl)-2,5-dimethylpyrrolidine, N-(cyclohexylcarbonyl)-tetrahydroacridine, N-(tert-butoxycarbonyl)-2,6-dimethylpiperidine, N-(tert-butoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(tert-butoxycarbonyl)diisopropylamine, N-(cyclohexylcarbonyl)-2,6-dimethylpiperidine, N-(tert-butoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(tert-butoxycarbonyl)-diisopropylamine, N-(cyclohexylcarbonyl)-2,6-di ... Isopropylamine, N-(tert-butoxycarbonyl)pyrrolidine, N-(tert-butoxycarbonyl)-2,5-dimethylpyrrolidine, N-(tert-butoxycarbonyl)-tetrahydroacridine, N-(benzyloxycarbonyl)-2,6-dimethylpiperidine, N-(benzyloxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(benzyloxycarbonyl)diisopropylamine, N-(benzyloxycarbonyl)pyrrolidine, N-(benzyloxycarbonyl)-2,5-dimethylpyrrolidine, N-(benzyloxycarbonyl)-tetrahydroacridine, 1,4-bis(N,N'-diisopropylaminocarbonyloxy)cyclohexane, and the imidazole compounds disclosed in Japanese Patent No. 5609815, etc.

[0347] The protected amine compound of this embodiment is preferably one that decomposes 100% below 200°C. This allows for more efficient generation of alkali compounds and promotes the imidization of polyimide precursors or the crosslinking reaction between thermal crosslinking agents and resins. The boiling point of the alkali and other decomposition products obtained by heating the protected amine compound at 1 atmosphere (0.1 GPa) is preferably below 200°C. Because the temperature is below 200°C, low-temperature treatment can be used to volatilize the decomposition products from the coating film. There is no particular limitation on the lower limit of the boiling point of the decomposition products at 1 atmosphere; however, considering the ease of synthesis of the protected amine compound, a boiling point above -150°C is preferable.

[0348] When amine compounds are directly added to the positive photosensitive resin composition of the present invention, the crosslinking polymer of component (B) or the thermal crosslinking agent of component (D) reacts with the amine compound at room temperature, causing the viscosity of the composition to increase over time, raising concerns about deterioration in storage stability. On the other hand, if the amine compound is protected by a protecting group to maintain its basicity, it will not react with components (B) and (D) at room temperature, just as it would not be heated, thus improving the storage stability of the photosensitive resin composition over time. Furthermore, the initial formation of alkali upon heating acts as a catalyst for the imide ring-closure reaction and the crosslinking reaction with the alkali-soluble resin of component (A), effectively promoting the crosslinking reaction.

[0349] Furthermore, the protected amine compound can be used alone or in combination of two or more, with a doping amount of 0 to 10 parts by mass relative to 100 parts by mass of the alkali-soluble resin of component (A). Ideally, the doping amount should be 0.01 to 10 parts by mass, especially 0.01 to 5 parts by mass. Doping amounts below 10 parts by mass will not reduce the alkali solubility of the composition or degrade the photolithographic patterning characteristics.

[0350] [(F) Thermal acid generating agent]

[0351] The positive photosensitive resin composition of the present invention may further contain (F) a compound that generates acid upon heat (a heat-generating agent). The heat-generating compound (F) may be added to promote the crosslinking reaction of components (A), (B), and (D) during the heating and post-curing steps performed at a temperature of 100–300°C after the above-mentioned pattern is formed.

[0352] Regarding component (F), it is particularly preferable that it does not promote film curing until pattern formation is achieved through development, and does not hinder pattern formation. To achieve this, component (F) is preferably one that does not generate acid at the temperature of the solvent removal and drying step after the photosensitive resin composition is coated, but generates acid for the first time through heat treatment after pattern formation, and promotes the curing of the pattern and film of the positive photosensitive resin composition. Specifically, it is preferable that it is a compound that decomposes and generates acid through heat treatment at 100°C to 300°C, preferably 150°C to 300°C. By containing such component (F), the step of heating and curing the pattern and film of the positive photosensitive resin composition at a temperature of 100°C to 300°C after pattern formation can be changed to a pattern and film in which cross-linking and curing reactions further occur. Through further cross-linking and curing reactions, component (F) can further improve the mechanical strength, chemical resistance, adhesion, etc. of the obtained pattern or film.

[0353] Ideally, a compound that produces an acid upon heating can be used, and the compound described in paragraphs

[0061] to

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

[0354] The amount of the compound that produces acid upon heating is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and more preferably 30 parts by mass or less, more preferably 5 parts by mass or less, relative to 100 parts by mass of component (A) in the positive photosensitive resin composition of the present invention. A content of 0.1 parts by mass or more promotes the cross-linking reaction. Furthermore, a content of 30 parts by mass or less prevents degradation of the alkaline developability of the composition and avoids the formation of developing residues.

[0355] (G) Antioxidants

[0356] The positive photosensitive resin composition of the present invention may further contain an antioxidant (G). The antioxidant containing component (G) can inhibit the oxidative degradation of the aliphatic groups and phenolic hydroxyl groups of component (A). Furthermore, through its rust-preventive effect on metal materials, it can inhibit metal oxidation caused by external moisture, photoacid generators, thermal acid generators, etc., and the associated reduction in adhesion and peeling.

[0357] Specific examples of antioxidants that can be used here include hindered phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. However, they are not limited to these. Furthermore, these antioxidants can be used alone or in combination of two or more.

[0358] Among the specific examples of the antioxidants mentioned above, hindered phenolic antioxidants can be further exemplified as follows: neopentyl tetroxide [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan, IRGANOX 1010), thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan, IRGANOX 1035), octadecyl [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan, IRGANOX 1076), octyl 1-3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamic acid (BASF Japan, IRGANOX 1135), 4,6-bis(octylthiomethyl-o-cresol) (BASF Japan, IRGANOX 1520L), Sumilizer GA80 (manufactured by Sumitomo Chemical Co., Ltd., trade name), ADEKASTAB AO-20 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-30 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-40 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-50 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-60 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-80 (manufactured by ADEKA Co., Ltd., trade name), ADEKASTAB AO-330 (manufactured by ADEKA Co., Ltd., trade name), and hindered phenolic antioxidants as described in Japanese Patent Application Publication No. WO2017 / 188153A1, etc.

[0359] Among the specific examples of the antioxidants mentioned above, phosphorus-based antioxidants can be further exemplified as follows: triphenyl phosphite, tri(methylphenyl) phosphite, triisooctyl phosphite, tridecanyl phosphite, tri(2-ethylhexyl) phosphite, tri(nonylphenyl) phosphite, tri(octylphenyl) phosphite, tri[decyl poly(oxyethylene) phosphite, tri(cyclohexylphenyl) phosphite, tricyclohexyl phosphite, tri(decyl) thiophosphite, triisodecyl thiophosphite, and phosphorus... Phenyl bis(2-ethylhexyl) ester, phenyl diisodecyl phosphite, tetradecyl poly(oxyethylidene)-bis(ethylphenyl) ester, phenyl dicyclohexyl phosphite, phenyl diisooctyl phosphite, phenyl di(tetrazyl) ester, diphenyl cyclohexyl phosphite, diphenyl isooctyl phosphite, diphenyl-2-ethylhexyl phosphite, diphenyl isodecyl phosphite, diphenyl cyclohexyl phenyl phosphite, diphenyl thiophosphite, di(tetrazyl) ester, etc.

[0360] Among the specific examples of antioxidants mentioned above, sulfur-based antioxidants can be further exemplified by ADEKASTAB AO-412S (manufactured by ADEKA Corporation, trade name), AO-503S (manufactured by ADEKA Corporation, trade name), and Sumilizer TP-D (manufactured by Sumitomo Chemical Corporation, trade name), etc.

[0361] For sulfur-based and phosphorus-based antioxidants, the effect of decomposing peroxides can be expected.

[0362] Furthermore, the antioxidant content of (G) is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass, relative to 100 parts by mass of the alkali-soluble resin of component (A). A content of 0.1 parts by mass or more improves adhesion to metallic materials and inhibits peeling. Furthermore, a content of 10 parts by mass or less does not deteriorate the alkali developability of the composition or the toughness of the hardened film.

[0363] [(H)silane compounds]

[0364] The positive photosensitive resin composition of the present invention may contain more silane compounds containing (H). By using silane compounds containing (H), not only can the adhesion to metallic materials be improved, but the peeling of the hardened film in reliability tests such as thermal shock tests and high temperature and humidity tests can also be suppressed.

[0365] Any silane compound used here that has an alkoxysilane group is acceptable. Ideal examples are listed below: γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, etc. Silanes include triethoxysilanes, triethoxysilylpropylethylaminocarbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilanes, phenyltrimethoxysilanes, N-phenyl-3-aminopropyltrimethoxysilanes, 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.

[0366] Furthermore, the content of the silane compound in (H) relative to 100 parts by weight of the alkali-soluble resin in component (A) is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, and even more preferably 3 to 6 parts by weight. A content of 0.1 parts by weight or more imparts more sufficient adhesion to the substrate, while a content of 20 parts by weight or less further suppresses problems such as viscosity increase during storage at room temperature. Also, by having a content of less than 10 parts by weight, the alkali developability of the composition will not deteriorate, and no developing residue will be generated.

[0367] [Other ingredients]

[0368] Furthermore, the positive photosensitive resin composition of the present invention may also contain components other than (A), (B), (C), (D), (E), (F), (G), and (H). Examples of other components include (I) dissolution inhibitors, (J) surfactants, and (K) solvents. The compounds exemplified below are ideally used, but the invention is not limited thereto.

[0369] Regarding (I) dissolution inhibitors, examples include: compounds with a weight-average molecular weight of 100 to 1,000, preferably 150 to 800, and having two or more phenolic hydroxyl groups in the molecule, wherein the hydrogen atoms of the aforementioned phenolic hydroxyl groups in the compound are replaced by acid-labile groups in an average proportion of 0 to 100 mol%; or compounds having a carboxyl group in the molecule, wherein the hydrogen atoms of the aforementioned carboxyl group in the compound are replaced by acid-labile groups in an average proportion of 50 to 100 mol%.

[0370] Furthermore, the substitution rate of the hydrogen atoms of the phenolic hydroxyl group by acid-labile groups is on average 0 mol% or more of the total phenolic hydroxyl group, preferably 30 mol% or more, with an upper limit of 100 mol%, and more preferably 80 mol%. The substitution rate of the hydrogen atoms of the carboxyl group by acid-labile groups is on average 50 mol% or more of the total carboxyl group, preferably 70 mol% or more, with an upper limit of 100 mol%.

[0371] At this time, compounds having two or more phenolic hydroxyl groups or compounds having carboxyl groups are preferably represented by the following formulas (I1) to (I14).

[0372] [Chemistry 63]

[0373]

[0374] However, in the above formula, R 201 R 202 Each can independently represent a hydrogen atom, or a straight-chain or branched alkyl or alkenyl group having 1 to 8 carbon atoms. R 203Represents a hydrogen atom, or a straight-chain or branched alkyl or alkenyl group having 1 to 8 carbon atoms. R 204 It represents -(CH2) i -(i=2~10), arylene, carbonyl, sulfonyl, oxygen or sulfur atoms with 6~10 carbon atoms. R 205 R represents an alkylene group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom, or a sulfur atom. 206 Represents a hydrogen atom, a straight-chain or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or a phenyl or naphthyl group substituted with a hydroxyl group, respectively. R 208 Represents a hydrogen atom or a hydroxyl group. j is an integer from 0 to 5. u and h are 0 or 1. s, t, s', t', s”, and t” each independently satisfy s+t=8, s'+t'=5, and s”+t”=4, and are numbers such as having at least one hydroxyl group in each phenyl skeleton. α is a number that makes the molecular weight of the compounds of formulas (I8) and (I9) between 100 and 1,000.

[0375] The amount of dissolution inhibitor incorporated is 0 to 50 parts by weight, preferably 5 to 50 parts by weight, and more preferably 5 to 20 parts by weight, relative to 100 parts by weight of the alkali-soluble resin of component (A). It can be used alone or in combination with two or more components. If the amount of incorporation is sufficient, the resolution is improved; if it is less than 50 parts by weight, no pattern loss will occur, and high resolution can be obtained.

[0376] (J) Surfactants should preferably be nonionic, such as fluorinated surfactants, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkyl amine oxides, fluorinated organosiloxane compounds, and nonfluorinated organosiloxane compounds.

[0377] These surfactants can be commercially available products, such as: Fluorad FC-4430 (manufactured by Sumitomo 3M Co., Ltd., trade name), PF-6320 (manufactured by OMNOVA Co., Ltd., trade name), PF-636 (manufactured by OMNOVA Co., Ltd., trade name), Surflon S-141 and S-145 (manufactured by Asahi Glass Co., Ltd., trade names), Unidyne DS-401, DS-4031 and DS-451 (manufactured by Daikin Industries, Ltd., trade names), Megafac F-8151 (manufactured by DIC Co., Ltd., trade name), X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), etc. Among them, 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) are recommended.

[0378] 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.

[0379] (K) The solvent is not limited to any solvent that can dissolve components (A), (B), and (C). Examples of solvents include: ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone, etc. One or more of these solvents may be used. Especially suitable solvents include ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, or mixtures thereof.

[0380] The amount of component (K) is preferably 50 to 2,000 parts by mass relative to the total amount of components (A), (B) and (C) of 100 parts by mass, and more preferably 100 to 1,000 parts by mass.

[0381] [Positive-type photosensitive dry film]

[0382] The positive photosensitive dry film of the present invention comprises a support film and a protective film, and a photosensitive resin film (photosensitive resin layer) obtained from the positive photosensitive resin composition is provided between the support film and the protective film.

[0383] The aforementioned photosensitive dry film (support film, protective film, and photosensitive resin film) is a solid. The photosensitive resin film does not contain solvent, so there is no risk of bubbles remaining inside the photosensitive resin film or between the uneven substrate due to its evaporation.

[0384] The thickness of the aforementioned photosensitive resin film, taking into account the flatness of the substrate with unevenness, the coverage of height differences, and the substrate stacking spacing, is preferably 5 to 200 μm, more preferably 5 to 100 μm, and even more preferably 10 to 100 μm.

[0385] Furthermore, the viscosity of the aforementioned photosensitive resin film is closely related to its flowability. Within an appropriate viscosity range, the photosensitive resin film exhibits suitable flowability, allowing it to penetrate deep into narrow gaps or enhance adhesion to the substrate through resin softening. Therefore, considering its flowability, the viscosity of the aforementioned photosensitive resin film at 80–120°C is preferably 10–5,000 Pa·s, more preferably 30–2,000 Pa·s, and even more preferably 50–300 Pa·s. In addition, in this invention, the viscosity is a measured value obtained using a rotational viscometer.

[0386] When the protective film of the present invention is peeled off and adhered to a substrate with unevenness, the photosensitive resin film follows and covers the unevenness, achieving high flatness. In particular, the photosensitive resin film has low viscoelasticity, thus achieving even higher flatness. Furthermore, adhering the photosensitive resin film to the substrate under vacuum conditions can more effectively prevent gaps from forming.

[0387] [Method for manufacturing positive-type photosensitive dry film]

[0388] Furthermore, the present invention provides a method for manufacturing a positive photosensitive dry film, comprising the following steps:

[0389] (1) The above positive photosensitive resin composition is continuously coated on a support film to form a photosensitive resin layer;

[0390] (2) The above-mentioned photosensitive resin layer is continuously dried; and

[0391] (3) Further attach a protective film to the above-mentioned photosensitive resin layer.

[0392] The photosensitive dry film of the present invention can be manufactured by coating the above-mentioned photosensitive resin composition onto a support film and drying it to form a photosensitive resin film. The apparatus for manufacturing the above-mentioned photosensitive dry film can be a film coating machine generally used for manufacturing adhesive products. Examples of such film coating machines include: a corner-roll coating machine, a corner-roll reverse coating machine, a multi-coating machine, a die-coating machine, a lip coating machine, a lip reverse coating machine, a direct gravure printing coating machine, a lithographic gravure printing coating machine, a 3-roll bottom reverse coating machine, and a 4-roll bottom reverse coating machine.

[0393] The support film is wound from the roll-out shaft of the film coating machine and passed through the coating head of the film coating machine. A photosensitive resin composition is coated onto the support film to a predetermined thickness. Then, the support film is dried in a hot air circulating oven at a predetermined temperature and time to form a photosensitive resin film. Next, the photosensitive resin film and a protective film wound from another roll-out shaft of the film coating machine are passed together under a predetermined pressure through laminating rollers to bond the photosensitive resin film and the protective film on the support film. Finally, the film is wound onto the winding shaft of the film coating machine, thereby producing a photosensitive dry film with a protective film attached. At this time, the temperature is preferably 25–150°C, the time is preferably 1–100 minutes, and the pressure is preferably 0.01–5 MPa.

[0394] The aforementioned support film can be a single-layer film composed of a single film, or a multilayer film obtained by laminating multiple films. The materials of the aforementioned film can include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Among these, polyethylene terephthalate is preferred considering its appropriate flexibility, mechanical strength, and heat resistance. These films can also undergo various treatments such as corona treatment and release agent coating. Commercially available products can be used, such as: Cerapeel WZ(RX), Cerapeel BX8(R) (manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (manufactured by Toyobo Co., Ltd.), Purex G31, Purex G71T1 (manufactured by Teijin DuPont Film Co., Ltd.), PET38×1-A3, PET38×1-V8, PET38×1-X08 (manufactured by Nippa Co., Ltd.), etc.

[0395] The protective film mentioned above can be the same as the aforementioned support film. Considering the need for appropriate flexibility, polyethylene terephthalate and polyethylene are preferable. These can be commercially available products. Examples of polyethylene terephthalate include GF-8 (manufactured by Tamapoly), and PE film type O (manufactured by Nippa).

[0396] The thickness of the aforementioned support film and protective film, taking into account the stability of the photosensitive dry film manufacturing process and the tendency of the winding core to be wound, i.e., the so-called prevention of curling, should preferably be 10 to 100 μm, and more preferably 10 to 50 μm.

[0397] (Pattern Formation Method)

[0398] The present invention provides a pattern forming method, comprising the following steps.

[0399] (1) The above positive photosensitive resin composition is coated on the substrate to form a photosensitive film;

[0400] (2) After heat treatment, the photomask exposes the photosensitive film using high-energy rays or electron beams with wavelengths of 190–500 nm; and

[0401] (3) After irradiation, the substrate is developed using an alkaline aqueous solution.

[0402] The following describes a pattern forming method using the positive photosensitive resin composition of the present invention.

[0403] In the positive photosensitive resin composition of the present invention, in order to form a pattern, a known photolithography technique can be used, for example, on a silicon wafer or SiO2 substrate, SiN substrate, or substrate with a pattern formed of copper wiring, the photosensitive resin composition is coated by spin coating and pre-baked at 80 to 130°C for about 50 to 600 seconds to form a photosensitive film with a thickness of 1 to 50 μm, preferably 1 to 30 μm, and more preferably 1 to 20 μm.

[0404] In spin coating, approximately 5 mL of photosensitive resin composition is dispensed onto a silicon substrate, and then the substrate is rotated to coat the substrate with the photosensitive resin composition. The thickness of the photosensitive film on the substrate can be easily adjusted by changing the rotation speed.

[0405] Then, a mask for forming the desired pattern is placed over the aforementioned photosensitive film, with an exposure dose of approximately 1 to 5,000 mJ / cm. 2 The preferred value is approximately 100–2,000 mJ / cm³. 2 Irradiation with high-energy rays or electron beams with wavelengths of 190–500 nm, such as i-rays and g-rays.

[0406] After irradiation, development is performed. In the positive photosensitive resin composition of the present invention described above, alkaline development can be performed using an alkaline aqueous solution.

[0407] On the other hand, an ideal alkaline aqueous solution for alkaline development is a 2.38% tetramethylhydroxyammonium (TMAH) aqueous solution. Development can be performed using conventional methods such as spraying, immersion, or soaking in the developing solution. Afterward, washing, rinsing, and drying are performed as needed to obtain a resist film with the desired pattern.

[0408] (Pattern formation method using positive photosensitive dry film)

[0409] The present invention provides a pattern forming method, comprising the following steps.

[0410] (1) The photosensitive resin layer exposed by peeling off the protective film from the positive photosensitive dry film of the present invention is closely attached to the substrate.

[0411] (2) Then, with the support film in between, or with the support film peeled off, the photosensitive resin layer is exposed using high-energy rays or electron beams with wavelengths of 190–500 nm with a photomask in between; and

[0412] (3) After irradiation, develop the solution using an alkaline aqueous solution.

[0413] The following describes a pattern formation method using the positive photosensitive dry film of the present invention.

[0414] In step (1), a photosensitive resin film is formed on the substrate using a photosensitive dry film. Specifically, a photosensitive resin film is formed on the substrate by attaching the photosensitive dry film to the substrate. The substrate described above may be the same as that described in the pattern formation method using the aforementioned positive photosensitive resin composition.

[0415] When the aforementioned photosensitive dry film has a protective film, after peeling off the protective film from the photosensitive dry film, the photosensitive resin film of the photosensitive dry film is attached to the substrate. Attachment can be performed, for example, using a film attaching apparatus. The film attaching apparatus is preferably a vacuum laminator. For example, the protective film of the aforementioned photosensitive dry film is peeled off, and the exposed photosensitive resin film is placed in a vacuum chamber with a predetermined vacuum level, and using an attaching roller at a predetermined pressure on a platform at a predetermined temperature, it is brought into close contact with the substrate. Furthermore, the aforementioned temperature is preferably 60–120°C, the aforementioned pressure is preferably 0–5.0 MPa, and the aforementioned vacuum level is preferably 50–500 Pa.

[0416] To obtain a photosensitive resin film of the required thickness, the film can be applied multiple times as needed. With approximately 1 to 10 applications, a photosensitive resin film with a thickness of 10 to 1,000 μm can be obtained, and more particularly, a film thickness of approximately 100 to 500 μm can be obtained.

[0417] To improve the adhesion between the photosensitive resin film and the substrate, pre-baking may be performed as needed. Pre-baking can be carried out, for example, at 40–140°C for about 1 minute to 1 hour.

[0418] Then, a mask for forming the desired pattern is applied to the aforementioned photosensitive resin film, with an exposure dose of approximately 1 to 5,000 mJ / cm. 2 The preferred value is approximately 100–2,000 mJ / cm³. 2 The film is irradiated with high-energy rays or electron beams with wavelengths of 190–500 nm, such as i-rays or gamma rays. Furthermore, the support film for the photosensitive dry film can be peeled off before pre-baking or before PEB processing, or removed using other methods, depending on the processing requirements.

[0419] After irradiation, the photosensitive resin film is developed using a developing solution to form a pattern, similar to the pattern forming method using the above-mentioned photosensitive resin composition.

[0420] (Method for forming a hardened coating)

[0421] Furthermore, the patterned film obtained using the above-described patterning method is heated and cured, for example, using an oven or heating plate, at a temperature of 100–300°C, preferably 150–300°C, and most preferably 180–250°C, thereby forming a cured film. A curing temperature of 100–300°C can increase the crosslinking density of the photosensitive resin composition film and remove residual volatile components, which is beneficial for the substrate's adhesion, heat resistance, strength, and consequently, electrical properties. The curing time can be set from 10 minutes to 10 hours.

[0422] The patterns formed above are used for the purpose of covering wiring, circuits and substrates with protective films. These patterns and protective films have excellent insulation properties and exhibit excellent adhesion to metal layers such as Cu in the covered wiring and circuits, metal electrodes on the substrate, or insulating substrates such as SiN in the covered wiring and circuits. They also have mechanical strength suitable for use as protective films and can significantly improve the resolution of the micro-patterns that can be formed.

[0423] (hardened membrane)

[0424] The hardened coating obtained in this way has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance to alkaline stripping solutions. The reliability of semiconductor devices using it as a protective coating is also excellent. In particular, it can prevent cracking during temperature cycling tests. It can be ideally used as a protective coating (interlayer insulating film or surface protective film) for electrical and electronic parts, semiconductor devices, etc.

[0425] That is, the present invention provides an interlayer insulating film or surface protective film composed of a hardened film formed by curing the above-mentioned positive photosensitive resin composition.

[0426] The aforementioned protective films are effective in applications such as insulating films for semiconductor components, insulating films for multilayer printed circuit boards, solder mask, and surface coating films due to their heat resistance, chemical resistance, and insulation properties.

[0427] Furthermore, the present invention provides an electronic component having the aforementioned interlayer insulating film or surface protective film. Such an electronic component exhibits excellent reliability due to the protective coating (interlayer insulating film or surface protective film) possessing heat resistance, chemical resistance, and insulation properties.

[0428] [Example]

[0429] The present invention will be specifically described below with examples of synthesis, embodiments, and comparative examples, but the present invention is not limited to the following examples. Furthermore, the weight-average molecular weight (Mw) represents the weight-average molecular weight of polystyrene obtained using GPC.

[0430] I. Synthesis of Alkali-Soluble Resin (A)

[0431] The chemical structural formulas and names of the compounds used in the following synthesis examples are shown below.

[0432] [Chemistry 64]

[0433]

[0434] [Synthesis Example 1] Synthesis of polyimide resin (A1)

[0435] In a 1L flask equipped with a stirrer and thermometer, 30g (81.9mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.9g (8.6mmol) of 4-aminophenol (PAP), and 125g of N-methyl-2-pyrrolidone were added and stirred at room temperature until dissolved. Then, at room temperature, a solution obtained by dissolving 26.7g (86.2mmol) of 3,3',4,4'-oxyphthalic dianhydride (s-ODPA) in 270g of N-methyl-2-pyrrolidone was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 3 hours. Subsequently, 40g of xylene was added to the reaction solution, and the mixture was heated under reflux for 3 hours at 170°C to remove the generated water from the system. After cooling to room temperature, the reaction solution was added dropwise to 2 L of ultrapure water with stirring. The precipitate was filtered, washed appropriately with water, and dried under reduced pressure at 40 °C for 48 hours to obtain polyimide resin (A1). The molecular weight of this polymer, when determined by GPC, is 35,000 (converted to polystyrene).

[0436] [Synthesis Example 2] Synthesis of polyimide resin (A2)

[0437] In Synthesis Example 1, 30 g (81.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) was replaced with 21.2 g (81.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), and the same formulation was used to obtain polyimide resin (A2). The molecular weight of this polymer, determined by GPC, was 34,000 (weight average) converted to polystyrene.

[0438] [Synthesis Example 3] Synthesis of Polyamide-Imide Resin (A3)

[0439] In a 500 mL flask equipped with a stirrer and thermometer, 28.5 g (77.8 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.9 g (8.2 mmol) of 4-aminophenol (PAP), and 118 g of N-methyl-2-pyrrolidone were added and stirred at room temperature until dissolved. Then, at room temperature, a solution obtained by dissolving 19.0 g (61.4 mmol) of 3,3',4,4'-oxyphthalic dianhydride (s-ODPA) in 192 g of N-methyl-2-pyrrolidone was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 3 hours. Subsequently, 40 g of xylene was added to the reaction solution, and the mixture was heated under reflux at 170 °C for 3 hours to remove the generated water from the system. After cooling to room temperature, 3.2 g (41.0 mmol) of pyridine was added, followed by the dropwise addition of 4.9 g (20.5 mmol) of sebacyl chloride (DC-1) while maintaining the temperature below 5°C. After the addition was complete, the mixture was allowed to return to room temperature. The reaction solution was then added dropwise to 2 L of ultrapure water with stirring. The precipitate was filtered, washed appropriately with water, and dried under reduced pressure at 40°C for 48 hours to obtain polyamide-imide resin (A3). The molecular weight of this polymer, determined by GPC, was 35,000 (converted to polystyrene weight average).

[0440] [Synthesis Example 4] Synthesis of Polyamide Resin (A4)

[0441] In a 500 mL flask equipped with a stirrer and thermometer, 28.5 g (77.8 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.9 g (8.2 mmol) of 4-aminophenol (PAP), and 118 g of N-methyl-2-pyrrolidone were added and stirred at room temperature until dissolved. Then, 13.0 g (163.8 mmol) of pyridine was added, followed by dropwise addition of 19.6 g (81.9 mmol) of sebacate chloride (DC-1) while maintaining the temperature below 5 °C. After the addition was complete, the temperature was returned to room temperature, and the reaction solution was added dropwise to 2 L of ultrapure water with stirring. The precipitate was filtered, washed appropriately with water, and dried under reduced pressure at 40 °C for 48 hours to obtain polyamide resin (A4). The molecular weight of this polymer, determined by GPC, was 38,000 (converted to polystyrene).

[0442] [Synthetic Example 5] Synthesis of tetracarboxylic acid diester compound (X-1)

[0443] In a 3L flask equipped with a stirrer and thermometer, 100 g (322 mmol) of 3,3',4,4'-oxyphthalic dianhydride (s-ODPA), 65.2 g (644 mmol) of triethylamine, 39.3 g (322 mmol) of N,N-dimethyl-4-aminopyridine, and 400 g of γ-butyrolactone were added. The mixture was stirred at room temperature, and 83.8 g (644 mmol) of hydroxyethyl methacrylate (HEMA) was added dropwise. The mixture was stirred at room temperature for 24 hours. Then, 370 g of 10% hydrochloric acid aqueous solution was added dropwise under ice-cold conditions to stop the reaction. 800 g of 4-methyl-2-pentanone was added to the reaction solution, and the organic layer was separated and washed six times with 600 g of water. The solvent of the obtained organic layer was distilled off to obtain 180 g of tetracarboxylic acid diester compound (X-1).

[0444] [Synthetic Example 6] Synthesis of polyimide precursor (A5)

[0445] In a 1L flask equipped with a stirrer and thermometer, 57.1g (100mmol) of (X-1) and 228g of N-methyl-2-pyrrolidone were added and stirred at room temperature to dissolve. Then, 24.4g (205mmol) of thionyl chloride was added dropwise under ice-cold conditions to maintain the temperature of the reaction solution below 10°C. After the addition was completed, the mixture was stirred under ice-cold conditions for 2 hours. Then, under ice-cold conditions to maintain the temperature of the reaction solution below 10°C, a solution obtained by dissolving 34.8g (95mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 1.1g (10mmol) of 4-aminophenol (PAP), and 32.4g (410mmol) of pyridine in 144g of N-methyl-2-pyrrolidone was added dropwise. After the addition was complete, the mixture was brought back to room temperature. The reaction solution was then added dropwise to 3 L of water with stirring. The precipitate was filtered, washed appropriately with water, and dried under reduced pressure at 40 °C for 48 hours to obtain the polyimide precursor (A5). The molecular weight of this polymer, when determined by GPC, was 36,000 (converted to polystyrene).

[0446] II. Synthesis of cross-linked polymers (B)

[0447] [Synthesis example]

[0448] For cross-linked polymeric compounds (polymeric additives), the monomers were copolymerized in tetrahydrofuran solvent, followed by crystallization and drying in hexane to obtain polymeric compounds with the compositions shown below (polymers B1-B19, comparative polymers C1 and C2). The composition of the obtained polymeric compounds was confirmed by 1H-NMR, and the molecular weight was confirmed by gel permeation chromatography.

[0449] [Synthesis Example 7] Polymer B1

[0450] Molecular weight (Mw) = 11,600

[0451] [Chemistry 65]

[0452]

[0453] [Synthesis Example 8] Polymer B2

[0454] Molecular weight (Mw) = 11,800

[0455] [Chemistry 66]

[0456]

[0457] [Synthesis Example 9] Polymer B3

[0458] Molecular weight (Mw) = 11,000

[0459] [Chemistry 67]

[0460]

[0461] [Synthesis Example 10] Polymer B4

[0462] Molecular weight (Mw) = 10,800

[0463] [Chemistry 68]

[0464]

[0465] [Synthesis Example 11] Polymer B5

[0466] Molecular weight (Mw) = 11,300

[0467] [Chemistry 69]

[0468]

[0469] [Synthesis Example 12] Polymer B6

[0470] Molecular weight (Mw) = 9,800

[0471] [Chemistry 70]

[0472]

[0473] [Synthesis Example 13] Polymer B7

[0474] Molecular weight (Mw) = 9,500

[0475] [Chemistry 71]

[0476]

[0477] [Synthesis Example 14] Polymer B8

[0478] Molecular weight (Mw) = 10,200

[0479] [Chemistry 72]

[0480]

[0481] [Synthesis Example 15] Polymer B9

[0482] Molecular weight (Mw) = 12,300

[0483] [Chemistry 73]

[0484]

[0485] [Synthesis Example 16] Polymer B10

[0486] Molecular weight (Mw) = 11,800

[0487] [Chemistry 74]

[0488]

[0489] [Synthesis Example 17] Polymer B11

[0490] Molecular weight (Mw) = 9,000

[0491] [Chemistry 75]

[0492]

[0493] [Synthesis Example 18] Polymer B12

[0494] Molecular weight (Mw) = 9,300

[0495] [Chemistry 76]

[0496]

[0497] [Synthesis Example 19] Polymer B13

[0498] Molecular weight (Mw) = 9,500

[0499] [Chemistry 77]

[0500]

[0501] [Synthesis Example 20] Polymer B14

[0502] Molecular weight (Mw) = 10,400

[0503] [Chemistry 78]

[0504]

[0505] [Synthesis Example 21] Polymer B15

[0506] Molecular weight (Mw) = 12,300

[0507] [Chemistry 79]

[0508]

[0509] [Synthesis Example 22] Polymer B16

[0510] Molecular weight (Mw) = 12,300

[0511] [Chemistry 80]

[0512]

[0513] [Synthesis Example 23] Polymer B17

[0514] Molecular weight (Mw) = 11,300

[0515] [Chemistry 81]

[0516]

[0517] [Synthesis Example 24] Polymer B18

[0518] Molecular weight (Mw) = 11,700

[0519] [Chemistry 82]

[0520]

[0521] [Synthesis Example 25] Polymer B19

[0522] Molecular weight (Mw) = 11,300

[0523] [Chemistry 83]

[0524]

[0525] [Synthetic Example 26] Comparative polymer C1

[0526] Molecular weight (Mw) = 11,900

[0527] [Chemistry 84]

[0528]

[0529] [Synthesis Example 27] Comparison of polymer C2

[0530] Molecular weight (Mw) = 10,600

[0531] [Chemistry 85]

[0532]

[0533] III-1. Preparation of Positive Photosensitive Resin Compositions

[0534] The base resins obtained by adding the crosslinking polymers (B1) to (B19), (C1), and (C2) synthesized in Synthetic Examples 7 to 27 to the alkali-soluble resins (A1) to (A5) synthesized in Synthetic Examples 1 to 6 above were used to prepare resin compositions with the compositions and blending amounts listed in Table 1. After stirring, mixing, and dissolving, the mixtures were precisely filtered using a 1.0 μm filter made with Teflon (registered trademark) to obtain positive photosensitive resin compositions. In the table, PGMEA represents propylene glycol monomethyl ether acetate, and GBL represents γ-butyrolactone.

[0535] [Table 1]

[0536]

[0537] III-2. Preparation of Positive Photosensitive Dry Film

[0538] A corner-cutting roller coating machine was used as the film coating machine, and polyethylene terephthalate film AL-5 (manufactured by LINTEC Corporation, trade name, thickness 38 μm) was used as the support film. Photosensitive resin compositions 28-31 and comparative photosensitive resin composition 4, as listed in Table 1, were coated onto the support film. The film was then dried by passing it through a hot air circulating oven (6 m long) set to 55°C for 4 minutes to form a photosensitive resin film on the support film, resulting in a photosensitive dry film. A polyethylene film (10 μm thick) was then laminated onto the photosensitive resin film using a laminating roller at a pressure of 1 MPa to produce a photosensitive dry film with a protective film. To ensure a final film thickness of 10 μm after curing, the film thickness of each photosensitive resin film was set to 14 μm (the film thickness of the photosensitive resin film was measured using an optical interferometer thickness measurement machine).

[0539] In addition, Table 1 details the photosensitizers (PAC-1), crosslinking agents (CL-1)(CL-2)(CL-3), protected amine compounds (E-1), thermal acid generators (F-1)(F-2), antioxidants (G-1), silane compounds (H-1), dissolution inhibitors (I-1), and surfactants (J-1) of quinone diazide compounds.

[0540] Photosensitive agent (PAC-1)

[0541] [Chemistry 86]

[0542]

[0543] In the formula, Q represents the 1,2-naphthoquinone diazidosulfonyl group or hydrogen atom represented by the following formula (23), and 90% of Q is substituted with the 1,2-naphthoquinone diazidosulfonyl group represented by the following formula (23).

[0544] [Chemistry 87]

[0545]

[0546] Crosslinking agent (CL-1)

[0547] Epoxy resin: EP4000L manufactured by ADEKA (stock).

[0548] Crosslinking agent (CL-2)

[0549] Epoxy resin: Mitsubishi Chemical Co., Ltd. jER828EL

[0550] Crosslinking agent (CL-3)

[0551] [Chemistry 88]

[0552]

[0553] Protected amine compounds (E-1)

[0554] [Chemistry 89]

[0555]

[0556] Hot acid generator (F-1)

[0557] [Chemistry 90]

[0558]

[0559] Hot acid generator (F-2)

[0560] [Chemistry 91]

[0561]

[0562] Antioxidant (G-1)

[0563] Hindered phenolic antioxidants: Sumitomo Chemical Co., Ltd.'s Sumilizer GA-80

[0564] Silane compounds (H-1)

[0565] Aminosilane coupling agent: KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.

[0566] Dissolution inhibitor (I-1)

[0567] [Chemistry 92]

[0568]

[0569] Surfactant (J-1)

[0570] Fluorinated surfactant: PF-6320 manufactured by OMNOVA

[0571] IV. Pattern Formation

[0572] A photosensitive dry film, composed of the above-mentioned photosensitive resin compositions 1 to 27, comparative photosensitive resin compositions 1 to 3, the above-mentioned photosensitive resin compositions 28 to 31, and comparative photosensitive resin composition 4, is formed on a silicon substrate treated with hexamethylsilazane.

[0573] By dispensing 5 mL of a resin solution containing photosensitive resin compositions 1-27 and comparative photosensitive resin compositions 1-3 onto a silicon substrate, and then rotating the substrate (i.e., spin coating), the post-cured film thickness after pattern formation was 3 μm. Specifically, considering that the film thickness would decrease after the post-curing step, the coating speed was adjusted to achieve a final post-cured film thickness of 2 μm. Furthermore, the pre-baking conditions were set at 100°C for 2 minutes on a heated plate.

[0574] On the other hand, for the photosensitive dry film composed of photosensitive resin compositions 28-31 and comparative photosensitive resin composition 4, the protective film was peeled off, and a vacuum laminator TEAM-100RF manufactured by Takatori was used. The vacuum level in the vacuum chamber was set to 80 Pa, so that the photosensitive resin film on the support film was tightly adhered to the silicon substrate. In addition, the stage temperature was set to 110°C. After returning to normal pressure, the support film was peeled off, and in order to improve the adhesion to the substrate, it was preheated at 90°C for 1 minute using a heating plate.

[0575] After the coating is formed, i-ray exposure is performed using an AP300E i-ray stepper lithography machine manufactured by Veeco. A positive patterning mask is used for pattern formation. The above-mentioned mask has a pattern capable of forming a 2μm contact hole pattern (hereinafter referred to as hole pattern) arranged in a 1:1 ratio, and can form hole patterns in 1μm increments within a range of 10μm to 2μm.

[0576] Then, a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution was used as the developer, and the immersion development was carried out for 1 minute until the coating film of the exposed part was dissolved. Then, a rinsing was carried out using ultrapure water.

[0577] Then, the patterned substrate is post-cured by blowing nitrogen into an oven at 180°C for 2 hours.

[0578] Then, each substrate was cut out in such a way that the shape of the hole pattern could be observed, and the shape of the hole pattern was observed using a scanning electron microscope (SEM). The resulting hole pattern cross-sections of 10 μm, 8 μm, 6 μm, 4 μm, and 2 μm were observed, and the smallest hole pattern with holes extending to the bottom was taken as the limiting resolution. Furthermore, the perpendicularity of the pattern was evaluated from the obtained cross-sectional photographs. These results, along with the sensitivity and number of development cycles required to form the smallest aperture hole pattern, are shown in Table 2.

[0579] In addition, the shape of the hole pattern was evaluated according to the following criteria, and the evaluation results are shown in Table 2. The perpendicularity of the hole pattern with the smallest diameter was evaluated, with a perpendicular pattern rated as ◎, a slightly pulled shape rated as ○, a pulled shape rated as △, and a poor opening rated as ×.

[0580] V. Elongation at break and tensile strength

[0581] Using the same procedure as the pattern formation described above, a photosensitive dry film composed of the aforementioned photosensitive resin compositions 1-27, comparative photosensitive resin compositions 1-3, the aforementioned photosensitive resin compositions 28-31, and comparative photosensitive resin composition 4 was formed on an aluminum substrate. The resin solution was coated using a spin-coating method to achieve a final film thickness of 10 μm after curing. The photosensitive dry film was then bonded to the aluminum substrate, achieving a final film thickness of 10 μm after curing. Furthermore, the spin-coating pre-baking was performed at 100°C for 4 minutes, and the dry film bonding was performed under the same conditions as the pattern formation.

[0582] Subsequently, the photosensitive resin curing film was obtained by curing in an oven at 180°C while blowing nitrogen gas for 2 hours. Then, the wafer with the curing film was cut into strips 10 mm wide and 60 mm long, and immersed in 20% hydrochloric acid to peel the curing film off the substrate. The elongation at break and tensile strength of the obtained curing film were measured using an Autograph AGX-1KN instrument manufactured by Shimadzu Corporation. The measurements were performed 10 times per sample, and the average values ​​are shown in Table 2.

[0583] [Table 2]

[0584]

[0585] VI. Close Contact

[0586] Using the same procedure as the pattern formation described above, a photosensitive resin film was formed on a SiN substrate using photosensitive dry films composed of photosensitive resin compositions 1-27 and 28-31. The resin solution was spin-coated to achieve a final film thickness of 5 μm after curing. The photosensitive dry film was then bonded to the SiN substrate to achieve a final film thickness of 10 μm after curing. After film formation, a 1 cm square pattern was exposed to I-rays to obtain a pattern on the substrate in a grid pattern across the entire surface. The exposure amount was determined based on the hole pattern evaluation described above. The spin-coating pre-baking was performed at 100°C for 4 minutes, and the dry film bonding was performed under the same conditions as the pattern formation. Development was performed by immersion development for 1 minute until the coating film in the exposed area dissolved, and this process was repeated a predetermined number of times.

[0587] Next, nitrogen gas was blown in at 180°C for 2 hours to perform post-curing of the patterned substrate. Then, the cured substrate was monolithically processed according to a 1cm square pattern to obtain a wafer with a cured film. Epoxy resin-coated aluminum pins were attached to the obtained wafer, and the wafer was heated at 150°C for 1 hour to bond the aluminum pins to the wafer, thus preparing a test sample. After cooling, the sample was analyzed using a ROMULUS instrument manufactured by QuadGroup. Figure 1 The method shown (hereinafter referred to as the Stud-pull method) was used to determine the contact strength. The measurement conditions were as follows: a measurement speed of 20 N / sec. Figure 1 This is an explanatory diagram showing the method for measuring contact strength. In addition, Figure 1 In the diagram, 1 represents the SiN substrate (substrate), 2 represents the hardened film, 3 represents the aluminum pin with adhesive, 4 represents the support platform, 5 represents the gripping part, and 6 represents the stretching direction. The obtained values ​​are the average of 10 measurements; the higher the value, the stronger the adhesion of the hardened film to the copper-plated substrate. Furthermore, regarding the peel interface, the adhesion at the peel interface of the hardened film / adhesive is higher than that at the substrate / hardened film peel interface. Adhesion is evaluated by comparing the obtained values ​​and peel interfaces.

[0588] In addition, for the high temperature and high humidity test, the obtained wafers were placed in a pressure cooker at 2 atmospheres saturation, 120°C, and 100% RH for 168 hours. Afterwards, the adhesion strength after the test was evaluated using the Stud-pull method, and the results, together with the results before the test, are shown in Table 3 as the adhesion strength to the substrate.

[0589] [Table 3]

[0590]

[0591] As shown in Table 2, compared with the positive photosensitive resin compositions 1-2 which contain a polymer compound consisting only of crosslinking groups, and the positive photosensitive resin compositions 3-4 which contain a thermal crosslinking agent, and the photosensitive dry film, the positive photosensitive resin composition and the positive photosensitive dry film of the present invention have good rectangularity and can resolve pore patterns.

[0592] Furthermore, as shown in Tables 2 and 3, the positive photosensitive composition and photosensitive dry film of the present invention can obtain a cured film with good mechanical properties and high temperature and high humidity resistance even when cured at low temperature below 200°C.

[0593] The results above show that the compositions of Examples 1 to 31 achieved the following results: they exhibit excellent resolution in resolving fine patterns, demonstrate full characteristics as photosensitive materials, and their hardened films have good substrate adhesion and high temperature and humidity resistance, making them useful as protective films for circuits and electronic components.

[0594] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and those having substantially the same structure as the technical concept described in the claims of the present invention and achieving the same effect are all included within the technical scope of the present invention.

[0595] Explanation of reference numerals in the attached figures

[0596] 1:SiN substrate (substrate)

[0597] 2: Hardened membrane

[0598] 3: Aluminum pins with adhesive

[0599] 4: Support Taiwan

[0600] 5: Grasping section

[0601] 6: Tension direction

Claims

1. A positive photosensitive resin composition, comprising: (A) An alkali-soluble resin containing at least one structure selected from polyimide structure, polyamide-imide structure, and polybenzoxazole precursor structure; (B) Cross-linked polymers containing structural units represented by the following general formula (2) and the following general formula (4); and (C) Photosensitive agent is a photosensitive agent that produces acid due to light and has an increased solubility rate in alkaline aqueous solutions. It is a compound with a quinone diazide structure. In the formula, R 8 Representing a hydrogen atom or a methyl group, X4 is independently -C(=O)-O-, or phenylene or naphthylene; R 9 It may also contain hydroxyl, ester, ether, or aromatic hydrocarbons in the form of straight-chain, branched, or cyclic alkylene groups having 1 to 15 carbon atoms. 10 It is a straight-chain, branched, or cyclic alkyl group with hydrogen atoms and 1 to 6 carbon atoms, or it can be combined with R. 9 Bonded to form a ring; R 11 R is a hydrogen atom, or a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms. 12 It consists of hydrogen atoms or straight-chain alkyl groups having 1 to 6 carbon atoms, and can also be combined with R. 9 A ring is formed by bonding; m is 1; p is 0 or 1; 0 <b2<1.0、0<b4<1.0、0<b2+b4≤1.0;R 4 Representing a hydrogen atom or a methyl group, X2 is independently -C(=O)-O-, -C(=O)-NH-, or -C(=O)-N(R) 5 OH)-;R 5 It is a straight-chain, branched, or cyclic aliphatic saturated hydrocarbon group with 1 to 12 carbon atoms in a divalent state, or an aromatic hydrocarbon group with 6 to 12 carbon atoms. The carbon atoms of the aliphatic saturated hydrocarbon group can also be replaced by oxygen atoms.

2. The positive photosensitive resin composition according to claim 1, wherein, Component (B) contains structural units represented by the following general formula (3) having groups that can crosslink with component (A); In the formula, R 6 R represents a hydrogen atom or a methyl group. 7 It represents oxazolinyl, isocyanate group, terminal isocyanate group, oxacyclobutyl, epoxy group, X3 is -C(=O)-O-, or phenylene or naphthylene; p is 0 or 1.

3. The positive photosensitive resin composition according to claim 1 or 2 further contains (D) a thermal crosslinking agent.

4. The positive photosensitive resin composition according to claim 3, wherein, The (D) component contains one or more crosslinking agents selected from the following: amino condensates modified with formaldehyde or formaldehyde-alcohol; phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups in one molecule; compounds obtained by substituting the hydrogen atoms of the hydroxyl groups of polyphenols with glycidyl groups; compounds obtained by substituting the hydrogen atoms of the hydroxyl groups of polyphenols with substituents represented by formula (D-1); and compounds containing two or more nitrogen atoms of glycidyl groups represented by formula (D-2). In the formula, the dotted line represents the bond, and R c It indicates a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, where v indicates 1 or 2.

5. The positive photosensitive resin composition according to claim 1 or 2, wherein, The content of component (B) is 1 to 50 parts by mass relative to 100 parts by mass of component (A).

6. The positive photosensitive resin composition according to claim 3, wherein, The content of component (D) is 0.5 to 100 parts by mass relative to 100 parts by mass of component (A).

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

8. A method for forming a pattern, comprising the following steps: (1) The positive photosensitive resin composition according to any one of claims 1 to 7 is coated on a substrate to form a photosensitive film; (2) After heat treatment, the photosensitive film is exposed to high-energy rays or electron beams with wavelengths of 190–500 nm using a spacer photomask; and (3) After irradiation, develop the solution using an alkaline aqueous solution.

9. A positive photosensitive dry film having a structure in which a photosensitive resin layer with a thickness of 5 to 200 μm is sandwiched between a support film and a protective film, wherein the composition used to form the photosensitive resin layer is the positive photosensitive resin composition according to any one of claims 1 to 7.

10. A method for manufacturing a positive-type photosensitive dry film, comprising the following steps: (1) The positive photosensitive resin composition according to any one of claims 1 to 7 is continuously coated onto a support film to form a photosensitive resin layer; (2) The photosensitive resin layer is continuously dried; and (3) Further, a protective film is attached to the photosensitive resin layer.

11. A method for forming a pattern, comprising the following steps: (1) The photosensitive resin layer exposed by peeling the protective film from the positive photosensitive dry film according to claim 9 is closely attached to the substrate. (2) With the support film in between, or with the support film peeled off, the photosensitive resin layer is exposed using a high-energy ray or electron beam with a wavelength of 190–500 nm through a photomask; and (3) After irradiation, develop the solution using an alkaline aqueous solution.

12. A method for forming a hardened film, comprising the following steps: The patterned film obtained by the patterning method according to claim 8 or 11 is heated and then hardened at a temperature of 100 to 300°C.

13. An interlayer insulating film comprising a positive photosensitive resin composition according to any one of claims 1 to 7, or a hardened film formed by curing a positive photosensitive dry film according to claim 9.

14. A surface protective film comprising a positive photosensitive resin composition according to any one of claims 1 to 7, or a hardened film formed by curing a positive photosensitive dry film according to claim 9.

15. An electronic component having an interlayer insulating film according to claim 13 or a surface protective film according to claim 14.

Images