PHOTOSENSITIVE RESIN COMPOSITION, METHOD FOR PRODUCING CURED Relief PATTERN USING SAME, AND METHOD FOR PRODUCING POLYIMIDE FILM

Abstract

According to the present invention, provided is a photosensitive resin composition which achieves high copper adhesion, suppresses the occurrence of copper voids at the interface between a copper layer and a resin layer after a high-temperature storage test, and has little copper migration in a b-HAST test. This photosensitive resin composition contains the following components: (A) a polyimide precursor and / or a polyimide resin, (B) a tetrazole compound, (C) a photopolymerization initiator, and (D) a solvent. The tetrazole compound (B) has a pKa of 1.3 to 4.1, or is represented by general formula (1) or (2), or has a polar surface area (tPSA) of 81 to 200. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a method for manufacturing a cured relief pattern using the same, a method for manufacturing a polyimide film, and the like. This international application claims priority based on Japanese Patent Application No. 2022-174360 filed on October 31, 2022, and incorporates the entire contents of the Japanese patent application into this international application. Background Art

[0002] Conventionally, in insulating materials for electronic components, passivation films for semiconductor devices, surface protective films, interlayer insulating films, etc., polyimide resins, polybenzoxazole resins, phenolic resins, etc. that have excellent heat resistance, electrical properties, and mechanical properties are used. Among these resins, resins provided in the form of a photosensitive resin composition can easily form a heat-resistant relief pattern film through coating, exposure, development, and thermal imidization treatment using curing of the composition. Such a photosensitive resin composition has the following characteristics: compared with conventional non-photosensitive materials, the process can be significantly shortened.

[0003] On the other hand, in recent years, from the viewpoints of improving integration and computing functions and miniaturizing chip sizes, the method of mounting a semiconductor device on a printed wiring board (package structure) is also changing. It has changed from the conventional mounting method using metal pins and lead-tin eutectic solder to a structure in which a polyimide film is in direct contact with solder bumps for higher-density mounting such as BGA (Ball Grid Array) and CSP (Chip Scale Package). Furthermore, a structure such as FO (fan out) in which multiple rewiring layers are provided on the surface of a semiconductor chip has been proposed, and the rewiring layer has an area larger than the area of the semiconductor chip (see Patent Document 1).

[0004] Copper is often used for wiring in semiconductor devices, but in a package structure with a large area, due to stress caused by differences in the coefficients of thermal expansion of different materials, a decrease in electrical properties accompanied by the peeling of copper from the interlayer insulating material becomes particularly problematic. Therefore, high adhesion to copper is required for the material used for the interlayer insulating film.

[0005] Furthermore, in recent years, the application of semiconductor devices has been particularly prominent in automotive applications or mobile phone applications, and semiconductor devices in this field require high reliability, and reliability tests in a high-temperature environment are being carried out.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: US Patent No. 10658199 Specification

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 2012-194520 SUMMARY OF THE INVENTION

[0010] Problems to be Solved by the Invention

[0011] However, in the conventional high-temperature storage test in the above reliability test, there has been a case where voids (hereinafter, also referred to as "copper voids" in the present invention) are generated at the interface between the copper layer and the resin layer of the rewiring due to migration after the test. If copper voids are generated at the interface between the copper layer and the resin layer, the adhesion between the two decreases. Further, if copper migrates to the resin layer (hereinafter, also referred to as "copper migration" in the present invention), particularly in a semiconductor device with fine wiring, it causes a short circuit between wirings and the performance as an insulating film cannot be fully exhibited. Therefore, a polyimide film with less copper migration and no short circuit for a long time in a reliability test under high temperature and high humidity (b-HAST: Biased Hughly Accelerated Stress Test) is desired.

[0012] One object of the present invention is to provide a photosensitive resin composition that achieves high copper adhesion, suppresses the generation of copper voids at the interface between the copper layer and the resin layer after a high-temperature storage test, and has less copper migration in a b-HAST test. Suppression of copper migration in the b-HAST test is related to the formation of a polyimide film that is not easily short-circuited for a long time. Further, one object is also to provide a method for forming a cured relief pattern using the photosensitive resin composition of the present invention and a method for manufacturing a polyimide film.

[0013] Means for Solving the Problems

[0014] The present inventors have found that the above problems can be solved by adding a specific tetrazole compound to the photosensitive resin composition. Examples of the embodiments of the present invention are listed in the following items [1] to

[18] . [1]

[0016] A photosensitive resin composition containing the following components:

[0017] (A) A polyimide precursor and / or a polyimide resin,

[0018] (B) A tetrazole compound,

[0019] (C) A photoinitiator, and

[0020] (D) A solvent,

[0021] The pKa of the above (B) tetrazole compound is 1.3 to 4.1. [2]

[0023] A photosensitive resin composition containing the following components:

[0024] (A) A polyimide precursor and / or a polyimide resin,

[0025] (B) A tetrazole compound,

[0026] (C) A photoinitiator, and

[0027] (D) A solvent,

[0028] The above-mentioned (B) tetrazole compound contains a compound represented by the following general formula (1) or the following general formula (2).

[0029]

[0030] {In formula (1), R 1 is a hydrogen atom, or a monovalent organic group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms. The hydrogen atoms of the above-mentioned alkyl group and the above-mentioned aryl group are each independently optionally substituted or unsubstituted by at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxysilyl group, and an amino group.}

[0031]

[0032] {In formula (2), R 2 is a hydrogen atom, or a monovalent organic group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms. R 3 is an alkylene group having 1 to 10 carbon atoms. The hydrogen atoms of the above-mentioned alkyl group, the above-mentioned aryl group, and the above-mentioned alkylene group are each independently optionally substituted or unsubstituted by at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxysilyl group, and an amino group.} [3]

[0034] A photosensitive resin composition containing the following components:

[0035] (A) A polyimide precursor and / or a polyimide resin,

[0036] (B) A tetrazole compound,

[0037] (C) A photoinitiator, and

[0038] (D) A solvent,

[0039] The polar surface area (tPSA) of the above-mentioned (B) tetrazole compound is 81 to 200. [4]

[0041] The photosensitive resin composition according to any one of Items 1 to 3, wherein the content of the component (B) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A). [5]

[0043] The photosensitive resin composition according to any one of Items 1 to 4, wherein the (B) tetrazole compound contains a compound represented by the following general formula (3).

[0044]

[0045] {In formula (3), R 4 is a hydrogen atom or a monovalent organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms. The hydrogen atoms of the alkyl group and the aryl group are each independently optionally substituted or unsubstituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxysilyl group, and an amino group.} [6]

[0047] The photosensitive resin composition according to any one of Items 1 to 5, wherein the (B) tetrazole compound contains a compound represented by the following formula:

[0048] [7]

[0050] The photosensitive resin composition according to any one of Items 1 to 6, further comprising (E) a radically polymerizable compound. [8]

[0052] The photosensitive resin composition according to Item 7, wherein the content of the component (E) is 20 to 80 parts by mass with respect to 100 parts by mass of the component (A). [9]

[0054] The photosensitive resin composition according to any one of Items 1 to 8, wherein the photosensitive resin composition contains the polyimide precursor represented by the following general formula (4).

[0055]

[0056] {In formula (4), X 1 is a tetravalent organic group, Y 1 is a divalent organic group, n 1 is an integer of 2 to 150, and R 11 and R 12 are each independently a hydrogen atom or a monovalent organic group.};

[0057] and / or

[0058] The above photosensitive resin composition contains the above polyimide resin, and the polyimide resin has a structural unit represented by the following general formula (4'):

[0059]

[0060] {In formula (4'), X 1 is a tetravalent organic group, Y 1 is a divalent organic group, and n is an integer from 1 to 150.}

[10]

[0062] The photosensitive resin composition according to item 9, wherein, in the above general formula (4), at least one of R 11 and R 12 has a structural unit represented by the following general formula (5).

[0063]

[0064] {In formula (5), L 1 , L 2 and L 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m 1 is an integer from 2 to 10.}

[11]

[0066] The photosensitive resin composition according to item 9 or 10, wherein X 1 in the above general formula (4') is at least one selected from the structures represented by the following general formulas (6) to (14), or Y 1 in the above general formula (4') is at least one selected from the structures represented by the following general formulas (15) to (23);

[0067]

[0068]

[0069]

[12]

[0071] The photosensitive resin composition according to any one of items 1 to 11 further contains (F) a thermal crosslinking agent.

[13]

[0073] The photosensitive resin composition according to any one of items 1 to 12 further contains (K) an adhesion aid.

[14]

[0075] The photosensitive resin composition according to any one of Items 1 to 13, wherein the photosensitive resin composition is a photosensitive resin composition for forming a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure.

[15]

[0077] A method for manufacturing a cured relief pattern, comprising the following steps:

[0078] (1) A step of coating the photosensitive resin composition according to any one of Items 1 to 14 on a substrate to form a photosensitive resin layer on the substrate;

[0079] (2) A step of exposing the photosensitive resin layer;

[0080] (3) A step of developing the exposed photosensitive resin layer to form a relief pattern; and

[0081] (4) A step of heat-treating the relief pattern to form a cured relief pattern.

[16]

[0083] According to the method for manufacturing a cured relief pattern described in Item 15 above, wherein the heat treatment in step (4) is a heat treatment at 350 °C or lower.

[17]

[0085] A cured film containing a cured product of the photosensitive resin composition according to any one of Items 1 to 14.

[18]

[0087] A method for manufacturing a polyimide film, comprising curing the photosensitive resin composition according to any one of Items 1 to 14.

[0088] Effects of the Invention

[0089] According to the present invention, a photosensitive resin composition can be provided that exhibits high copper adhesion, suppresses the generation of copper voids at the interface between the copper layer and the resin layer after a high-temperature storage test, and has less copper migration in a b-HAST test. Further, a method for manufacturing a cured relief pattern using the photosensitive resin composition and a method for manufacturing a polyimide film can be provided. Detailed Description

[0090] Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments and can be implemented with various changes within the scope of its gist. It should be noted that throughout the present invention, when there are multiple structures represented by the same symbol in the general formula in the molecule, they may be the same or different from each other. Moreover, the upper and lower limit values in each numerical range of the present invention can be arbitrarily combined to form any numerical range.

[0091] <Photosensitive Resin Composition>

[0092] The photosensitive resin composition of the present invention contains (A) a polyimide precursor and / or a polyimide resin, (B) a tetrazole compound, (C) a photoinitiator, and (D) a solvent.

[0093] (A) Polyimide Precursor

[0094] (A) The polyimide precursor is a resin component contained in the photosensitive resin composition and is converted into polyimide by performing a heat cyclization treatment. The structure of (A) the polyimide precursor is not limited as long as it is a resin that can be used in the photosensitive resin composition, and it is preferably non-alkali-soluble. By making the polyimide precursor non-alkali-soluble, high chemical resistance can be obtained.

[0095] The polyimide precursor is preferably a polyamide having a structure represented by the following general formula (4).

[0096]

[0097] {In formula (4), X 1 is a tetravalent organic group, Y 1 is a divalent organic group, n 1 is an integer from 2 to 150, and R 11 and R 12 are each independently a hydrogen atom or a monovalent organic group.}

[0098] In general formula (4), it is preferable that at least one of R 11 and R 12 has a structural unit represented by the following general formula (5).

[0099]

[0100] {In formula (5), L 1 , L 2 and L 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m 1 is an integer from 2 to 10.}

[0101] In general formula (4), with R 11 and R12 Based on the total number of moles, R 11 and R 12 The ratio of hydrogen atoms is preferably 10% or less, more preferably 5% or less, and further preferably 1% or less. In addition, in General Formula (4), based on the total number of moles of R 11 and R 12 The ratio of R 11 and R 12 being a monovalent organic group represented by the above General Formula (5) is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. From the viewpoints of photosensitive characteristics and storage stability, it is preferable that the ratio of hydrogen atoms and the ratio of the organic group of General Formula (5) are within the above ranges.

[0102] In General Formula (4), n 1 If it is an integer from 2 to 150, there is no limitation. From the viewpoints of the photosensitive characteristics and mechanical characteristics of the photosensitive resin composition, it is preferably an integer from 3 to 100, and more preferably an integer from 5 to 70.

[0103] In General Formula (4), the tetravalent organic group represented by X 1 From the viewpoints of achieving both heat resistance and photosensitive characteristics, it is preferably an organic group having 6 to 40 carbon atoms, more preferably a -COOR 11 group and a -COOR 12 group and an aromatic group or an alicyclic aliphatic group in which the -CONH- group is adjacent to each other. As the tetravalent organic group represented by X 1 Specific examples include organic groups having 6 to 40 carbon atoms containing an aromatic ring, such as a group having the structure represented by the following General Formula (24), but are not limited thereto. In addition, the structure of X 1 can be one type or a combination of two or more types. From the viewpoints of achieving both heat resistance and photosensitive characteristics, an X 1 group having the structure represented by the following Formula (24) is particularly preferred.

[0104]

[0105] {In the formula, R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorinated hydrocarbon group having 1 to 10 carbon atoms, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4.}

[0106] From the viewpoints of the imidization rate during low-temperature heating, degassing property, copper adhesion, chemical resistance, etc., as the X 1 group, in the structure represented by the above Formula (24), a tetravalent organic group represented by the following formula is particularly preferred.

[0107]

[0108] {In the formula, R6 is at least one selected from the group consisting of a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorinated hydrocarbon group having 1 to 10 carbon atoms, and m is an integer selected from 0 to 3.}

[0109] From the viewpoint of achieving both heat resistance and photosensitive characteristics, in the above general formula (4), Y 1 The divalent organic group represented is preferably an aromatic group having 6 to 40 carbon atoms. For example, the structure represented by the following formula (25) can be cited, but is not limited thereto. In addition, the structure of Y1 can be one kind, or a combination of two or more kinds. From the viewpoint of achieving both heat resistance and photosensitive characteristics, a Y1 group having the structure represented by the following formula (25) is particularly preferred.

[0110]

[0111] {In the formula, R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorinated hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4.}

[0112] From the viewpoints of imidization rate at low-temperature heating, outgassing property, copper adhesion property, chemical resistance, etc., as the Y 1 group, in the structure represented by the above formula (25), a divalent group represented by the following formula is particularly preferred.

[0113]

[0114] {In the formula, R6 is at least one selected from the group consisting of a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorinated hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4.}

[0115] As the L 1 in the above general formula (5), L 2 and L 3 The monovalent organic group having 1 to 3 carbon atoms is, for example, a hydrocarbon group having 1 to 3 carbon atoms, and is preferably an alkyl group. L 1 is preferably a hydrogen atom or a methyl group, and L 2 and L 3 From the viewpoint of photosensitive characteristics, are preferably hydrogen atoms. And, from the viewpoint of photosensitive characteristics, m1 is an integer of 2 or more and 10 or less, and is preferably an integer of 2 or more and 4 or less.

[0116] In one embodiment, the (A) polyimide precursor is preferably a polyimide precursor having a structural unit represented by the following general formula (26).

[0117]

[0118] {wherein R 11 , R 12 and n 1 are as defined above.}

[0119] In the general formula (26), it is more preferable that at least one of R 11 and R 12 is a monovalent organic group represented by the general formula (5) above. By making the (A) polyimide precursor contain the polyimide precursor represented by the general formula (6), the chemical resistance is particularly increased.

[0120] In one embodiment, from the viewpoint of thermal properties, it is preferable that the (A) polyimide precursor is a polyimide precursor having a structural unit represented by the following general formula (27).

[0121]

[0122] {wherein R 11 , R 12 and n 1 are as defined above.}

[0123] In the general formula (27), it is more preferable that at least one of R 11 and R 12 is a monovalent organic group represented by the general formula (5) above.

[0124] (A) When the polyimide precursor contains both the structural unit represented by the general formula (26) and the structural unit represented by the general formula (27), there is a tendency for the resolution to be particularly increased. For example, the (A) polyimide precursor may contain a copolymer of the structural unit represented by the general formula (26) and the structural unit represented by the general formula (27), or may be a mixture of the polyimide precursor represented by the general formula (26) and the polyimide precursor represented by the general formula (27).

[0125] (A) The polyimide precursor is preferably a polyimide precursor having a structural unit represented by the following general formula (28).

[0126]

[0127] {wherein R 11 , R 12 and n 1 are as defined above.}

[0128] (A) The polyimide precursor is preferably a polyimide precursor having a structural unit represented by the following general formula (29).

[0129]

[0130] {In the formula, R 11 and R 12 and n 1 are as defined above.}

[0131] (A) The polyimide precursor has a particularly high chemical resistance by containing the polyimide precursor represented by the general formula (29).

[0132] Based on the total mass of the photosensitive resin composition containing a solvent, (A) the polyimide precursor preferably contains 10% by mass to 70% by mass, more preferably 20% by mass to 65% by mass.

[0133] (A) Preparation method of the polyimide precursor

[0134] (A) The polyimide precursor is obtained as follows: First, a tetracarboxylic dianhydride containing the above-mentioned tetravalent organic group X 1 is reacted with an alcohol having a photopolymerizable unsaturated double bond and, optionally, an alcohol not having an unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester body). Thereafter, the partially esterified tetracarboxylic acid is subjected to amide polycondensation with a diamine containing the above-mentioned divalent organic group Y1.

[0135] (Preparation of the acid / ester body)

[0136] As the tetracarboxylic dianhydride preferably used for preparing (A) the polyimide precursor and containing the tetravalent organic group X 1 , starting from the tetracarboxylic dianhydride represented by the above general formula (24), for example, pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (ODPA), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc. are exemplified. However, it is not limited to these. Among these, as the tetracarboxylic dianhydride, preferably, pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (ODPA), and biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA) are exemplified. Of course, these can be used alone or two or more of them can be used in combination.

[0137] Examples of the alcohols having a photopolymerizable unsaturated double bond that are preferably used for preparing (A) a polyimide precursor include 2-acryloyloxyethanol, 1-acryloyloxy-3-propanol, 2-acrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-methacrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and the like.

[0138] It is also possible to mix a part of alcohols that do not have an unsaturated double bond, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol, etc., in the above alcohols having a photopolymerizable unsaturated double bond and use them.

[0139] In addition, as the polyimide precursor, a non-photosensitive polyimide precursor prepared only from the above alcohols that do not have an unsaturated double bond can be mixed with a photosensitive polyimide precursor and used. From the viewpoint of resolution, based on 100 parts by mass of the photosensitive polyimide precursor, the non-photosensitive polyimide precursor is preferably 200 parts by mass or less. The above-mentioned preferred tetracarboxylic dianhydride and the above alcohols are stirred and dissolved and mixed in the following solvent in the presence of a basic catalyst such as pyridine at a temperature of 20 to 50 °C for 4 to 24 hours, thereby performing the esterification reaction of the acid anhydride to obtain the desired acid / ester body.

[0140] (Preparation of Polyimide Precursor)

[0141] In the above acid / ester body (typically a solution in the following solvent), while cooling in an ice bath, a suitable dehydrating condensing agent is added and mixed, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-dibutanimidyl carbonate, etc. After converting the acid / ester body into a polyanhydride, a divalent organic group Y-containing substance is added dropwise thereto. 1A substance obtained by dissolving or dispersing the diamine in another solvent is subjected to amide polycondensation to obtain the target polyimide precursor. Alternatively, thionyl chloride or the like is used for the above acid / ester compound, the acid moiety is subjected to acyl chloride formation, and then the reaction is carried out with a diamine compound in the presence of a base such as pyridine to obtain the target polyimide precursor.

[0142] As containing a divalent organic group Y 1Diamines, starting with the diamine having the structure represented by the above general formula (21), include, for example: p-phenylenediamine (1,4-benzenediamine (pPD)), m-phenylenediamine, 4,4'-oxydianiline (ODA), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene (APB), bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene (BAFL), and substances in which a part of the hydrogen atoms on the benzene rings of these are substituted with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof, etc., but are not limited thereto. Preferred diamines include: 4,4'-oxydianiline (ODA), 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB), and 1,4-benzenediamine (pPD). These diamines can be used alone or in combination of two or more.

[0143] After the amide polycondensation reaction is completed, the water-absorbing by-products of the dehydrating condensing agent coexisting in the reaction solution are filtered and separated as needed, and then a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof is added to the obtained polymer component to precipitate the polymer component. Further, operations such as re-dissolution and re-precipitation are repeated to purify the polymer, followed by vacuum drying to separate the target polyimide precursor. To improve the purification degree, the solution of the polymer can be passed through a column filled with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0144] Regarding the molecular weight of the above-mentioned (A) polyimide precursor, when measured by the polystyrene equivalent weight-average molecular weight by gel permeation chromatography, it is preferably 8,000 to 150,000, more preferably 9,000 to 50,000. When the weight-average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developer is good and the resolution performance of the relief pattern is good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the weight-average molecular weight is obtained by using a calibration curve prepared with standard monodisperse polystyrene. As the standard monodisperse polystyrene, those selected from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko K.K. are recommended.

[0145] (A) Polyimide resin

[0146] The photosensitive resin composition of the present invention may contain (A) polyimide resin simultaneously with or in place of (A) polyimide precursor.

[0147] (A) Polyimide resin does not generate resin-derived detachment components, so the curing shrinkage of the photosensitive resin composition can be suppressed. Therefore, compared with the polyimide precursor, a photosensitive resin composition having a high cured film residue rate and improved flatness after curing can be obtained.

[0148] (A) Polyimide resin may have a polymerizable group in the side chain, but from the viewpoints of the elongation rate of the cured film and storage stability, it preferably does not have a polymerizable group in the side chain. The polyimide resin preferably substantially does not contain a polyamic acid or polyamic acid ester structure. In the present invention, the so-called "substantially does not contain" means that, for example, the imidization rate of the polyimide resin is 90% or more, preferably 95% or more.

[0149] The imidization rate of the polyimide resin can be measured by a known method and is calculated by the following method in the present invention. First, the infrared absorption spectrum of the polyimide resin is measured, and the absorption peaks of the imide structure (around 1780 cm -1 and around 1377 cm -1The presence near). Subsequently, the polyimide resin was heat-treated at 350 °C for 1 hour, and the infrared absorption spectrum after the heat treatment was measured. The peak intensity near 1377 cm -1 was compared with the peak intensity before the heat treatment, and the imidization rate of the polyimide resin was calculated therefrom.

[0150] In terms of the solubility in solvents and the flatness during coating, the polyimide resin (A) preferably contains a structure represented by the general formula (4'). Moreover, it is a structure suitable for a solvent-developable photosensitive resin composition.

[0151]

[0152] {In the formula (4'), X 1 is a tetravalent organic group, Y 1 is a divalent organic group, and n is an integer from 1 to 150.}

[0153] X 1 is a tetravalent organic group. As long as it is a known structure derived from a tetracarboxylic dianhydride, there is no particular limitation. From the viewpoints of high copper adhesion of the cured film, suppression of copper voids after the high-temperature storage test, suppression of copper migration in the b-HAST test, excellent elongation, chemical resistance, and solubility in the following solvents, it preferably has at least one structure represented by the following formulas (6) to (14).

[0154]

[0155]

[0156] In addition, from the viewpoints of suppression of copper voids after the high-temperature storage test of the cured film obtained from the photosensitive resin composition of the present invention, suppression of copper migration in the b-HAST test, elongation, and chemical resistance, X 1 preferably has at least one structure represented by the formulas (6) to (13). Furthermore, from the viewpoint of the heat resistance of the cured film obtained from the photosensitive resin composition of the present invention, X 1 more preferably has one or more structures represented by the formulas (6) to (8) and (10) to (13). In addition, in terms of the particularly excellent coating film uniformity of the photosensitive resin composition of the present invention and the elongation of the cured film, X 1 is particularly preferably to have at least one structure represented by the formulas (6) and (11) to (13).

[0157] Y in the formula (4') 1is a divalent organic group and is not particularly limited as long as it is a known structure derived from diamine. From the viewpoints of high copper adhesion of the cured film, suppression of copper voids after high-temperature storage test, suppression of copper migration in b-HAST test, elongation at break, excellent chemical resistance, and solubility in solvents, it preferably has at least one structure represented by the following formulas (15) to (23).

[0158]

[0159]

[0160] Moreover, from the viewpoints of suppression of copper voids after high-temperature storage test of the cured film obtained from the photosensitive resin composition of the present invention, suppression of copper migration in b-HAST test, elongation at break, and chemical resistance, Y 1 preferably has at least one structure represented by the formulas (15) to (21). Further, from the viewpoint of the mechanical properties of the cured film obtained from the photosensitive resin composition of the present invention, Y 1 more preferably has at least one structure represented by the formulas (15) to (20). In addition, in terms of the particularly excellent coating film uniformity of the negative photosensitive resin composition of the present invention and the elongation at break of the cured film, Y 1 particularly preferably has at least one structure represented by the formulas (17) to (20). The structures represented by the formulas (17) to (20) have excellent solubility in solvents because these structures have side-chain phenyl structures.

[0161] n in the formula (4') is an integer of 2 to 150, preferably an integer of 3 to 100, more preferably an integer of 5 to 70. n is preferably an integer that satisfies the following (A) weight-average molecular weight of the polyimide resin.

[0162] From the viewpoint of solubility in the following solvents, with respect to the terminals of the (A) polyimide resin, preferably the main-chain terminals of the (A) polyimide resin, it preferably has at least one structure selected from the group consisting of an acid anhydride group, a carboxyl group, an amino group, and the following general formulas (30) to (32).

[0163]

[0164] {In the formula (30), R 1 and R 2 are each independently selected from a hydrogen atom and a monovalent organic group having 1 to 3 carbon atoms, R 3 is an organic group having 1 to 20 carbon atoms optionally containing a hetero atom, k is an integer of 1 to 2; R 4 is a hydrogen atom and an organic group having 1 to 4 carbon atoms, and * represents the bonding site to the terminal of the (A) polyimide resin.}

[0165]

[0166] {In formula (31), R 5 and R 6 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms; and * represents a bonding site to the terminal of the (A) polyimide resin.}

[0167]

[0168] {In formula (32), R 7 , R 8 and R 9 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and j is an integer of 2 to 10; and * represents a bonding site to the terminal of the (A) polyimide resin.}

[0169] Preferably, the acid anhydride group is derived from the starting tetracarboxylic dianhydride, the carboxyl group is obtained by ring-opening of the above acid anhydride group, and the amino group is derived from the starting diamine. As a more detailed specific example in the case where the terminal of the (A) polyimide resin has the structure represented by the general formula (30), the structures represented by the following formulas (33) to (36) can be cited.

[0170]

[0171] {* in the formula represents a bonding site to the terminal of the (A) polyimide resin.}

[0172] As a more detailed specific example of the structure represented by the general formula (31), the structures represented by the following formulas (37) and (38) can be cited.

[0173]

[0174] {* in the formula represents a bonding site to the terminal of the (A) polyimide resin.}

[0175] As a more detailed specific example of the structure represented by the general formula (32), the structures represented by the following formulas (39) to (42) can be cited.

[0176]

[0177] {* in the formula represents a bonding site to the terminal of the (A) polyimide resin.}

[0178] From the viewpoints of high copper adhesion of the cured film, suppression of copper voids after the high-temperature storage test, suppression of copper migration in the b-HAST test, elongation, chemical resistance, and solubility in solvents, it is preferred that X 1 in the general formula (4') has any structure represented by the general formulas (6) to (14), and Y1 Any structure represented by general formulae (15) to (23).

[0179] (A) The weight average molecular weight (Mw) of the polyimide resin is not particularly limited as long as it is within the range soluble in the solvent. From the viewpoints of the film physical properties of the cured film and the copper adhesion, the weight average molecular weight of the (A) polyimide resin is preferably 5,000 or more and 100,000 or less. From the viewpoint of mechanical properties, the lower limit value of the weight average molecular weight of the (A) polyimide resin is more preferably 6,000 or more, and further preferably 8,000 or more. In addition, from the viewpoints of solubility in the solvent and flatness during coating, the upper limit value of the weight average molecular weight of the (A) polyimide resin is more preferably 50,000 or less, and particularly preferably 30,000 or less.

[0180] (A) The molecular weight distribution (Mw / Mn) of the polyimide resin is preferably 1.0 or more and 2.0 or less. From the viewpoint of manufacturing efficiency, the lower limit value of the molecular weight distribution of the (A) polyimide resin is more preferably 1.15 or more, and further preferably 1.25 or more. Regarding the upper limit value of the molecular weight distribution of the (A) polyimide resin, from the viewpoint of resolution, the upper limit value is more preferably 1.8 or less, and further preferably 1.6 or less.

[0181] Based on the total mass of the photosensitive resin composition containing the solvent, the (A) polyimide resin preferably contains 10% by mass to 70% by mass, and more preferably contains 20% by mass to 65% by mass.

[0182] (A) Preparation method of polyimide resin

[0183] (A) The polyimide resin is obtained by subjecting the polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine to dehydration ring closure to effect imidization.

[0184] The method for dehydrating and closing the ring of the polyamic acid is not limited. For example, there can be mentioned: a thermal imidization method in which the polyamic acid is heated at a high temperature to effect dehydration ring closure, or a chemical imidization method in which acetic anhydride and a tertiary amine as a dehydration reducing agent are added to effect dehydration ring closure, etc.

[0185] The temperature in the thermal imidization method is not particularly limited. From the viewpoint of promoting the ring closure reaction, the lower limit value is preferably 150 °C or more, and further preferably 160 °C or more. On the other hand, from the viewpoint of suppressing side reactions, the upper limit value is preferably 200 °C or less, and more preferably 180 °C.

[0186] As the tetracarboxylic dianhydride, there is no particular limitation. Specific examples include: pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,4'-oxydiphthalic anhydride, 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,4'-biphenyltetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA), 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride (CpODA), bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD), 1,2,3,4-cyclobutanetetracarboxylic anhydride (CBDA), and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), etc. Among these, as the tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), and 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA), etc. are preferred.

[0187] As the diamine, there is no particular limitation. Specific examples include: 4,4'-diaminodiphenyl ether (DADPE), 3,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene (APB), 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 2-phenoxybenzene-1,4-diamine (PND), 9,9-bis(4-aminophenyl)fluorene (BAFL), 6-(4-aminophenoxy)biphenyl-3-amine (PDPE), 3,3'-diphenyl-4,4'-bis(4-aminophenoxy)biphenyl (APBP-DP), 2,2-bis[3-phenyl-4-(4-aminophenoxy)phenyl]propane (DAOPPA), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), and 2-(methacryloyloxy)ethyl-3,5-diaminobenzoate (MAEDAB), etc. Among these, as the diamine, 6-(4-aminophenoxy)biphenyl-3-amine (PDPE) and 9,9'-bis(4-aminophenyl)fluorene (BAFL), etc. are preferred.

[0188] When the ends of the (A) polyimide resin are acid anhydride groups, carboxyl groups, and amino groups, the (A) polyimide resin is a polyimide resin obtained by dehydrating and cyclizing the polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine to effect imidization. The acid anhydride groups, carboxyl groups, and amino groups at the ends of the (A) polyimide resin can be reacted with a specified compound to make the ends have the structures represented by the above general formulas (30) to (32).

[0189] The (A) polyimide resin having a structure represented by the general formula (30) at the end is obtained, for example, by reacting the amino group at the end of the polyimide with an isocyanate compound. Specific examples of the isocyanate compound include 2-methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate: MOI), 2-acryloyloxyethyl isocyanate, 1,1-bis(acryloxymethyl)ethyl isocyanate, and 2-(2-methacryloyloxyethoxy)ethyl isocyanate. The method of reacting with the isocyanate compound is not particularly limited, and the amino group of the polyimide after dehydration and ring closure can be reacted by adding the isocyanate compound to the polyimide solution after dehydration and ring closure and stirring at room temperature.

[0190] The (A) polyimide resin having a structure represented by the general formula (31) at the end is obtained, for example, by reacting the amino group at the end of the polyimide with a chloride compound. Examples of the chloride compound include acryloyl chloride and methacryloyl chloride. The method of reacting with the chloride compound is not particularly limited, and the polyimide solution after dehydration and ring closure can be cooled in an ice bath, and the chloride compound can be added dropwise to react with the amino group of the polyimide after dehydration and ring closure.

[0191] The (A) polyimide resin having a structure represented by the general formula (32) at the end is obtained, for example, by reacting the anhydride group and carboxyl group at the end of the polyimide with an alcohol compound. Examples of the alcohol compound include 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate: HEMA), 2-hydroxyethyl acrylate, 4-hydroxyethyl methacrylate, and 4-hydroxyethyl acrylate. The method of reacting with the alcohol compound is not particularly limited, and a condensing agent such as N,N'-dicyclohexylcarbodiimide (DCC) or an esterification catalyst such as p-toluenesulfonic acid can be used to react the anhydride group and carboxyl group of the polyimide after dehydration and ring closure with the alcohol compound.

[0192] In the production of the (A) polyimide resin, a reaction solvent can be used in order to efficiently carry out the reaction in a homogeneous system. The reaction solvent is not particularly limited as long as it is a solvent that can uniformly dissolve or suspend the tetracarboxylic dianhydride, diamine, and the compound having a polymerizable functional group at the end. Examples of the reaction solvent include γ-butyrolactone (GBL), dimethyl sulfoxide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide.

[0193] In the production of (A) polyimide resin, when the thermal imidization method is used, an azeotropic solvent can be used to promote the imidization reaction. The azeotropic solvent is not particularly limited as long as it is a solvent that forms an azeotrope with water, and examples thereof include toluene, ethyl acetate, N-dicyclohexylpyrrolidone, o-dichlorobenzene, xylene, and benzene.

[0194] (A) The polyimide resin can be purified by the method described in Patent Document 2 (Japanese Patent Application Laid-Open No. 2012-194520) and the like. For example, as the purification method, examples include a method of removing unreacted substances by reprecipitating the (A) polyimide resin solution by dropping it into water, a method of removing a condensing agent insoluble in the reaction solvent by filtration separation, and a method of removing a catalyst by an ion exchange resin. After these purifications, the (A) polyimide resin can be dried by a known method and separated in a powder state.

[0195] (B) Tetrazole compound

[0196] Regarding the (B) tetrazole compound, the pKa is 1.3 to 4.1, or it is represented by the following formula (1) or (2), or the polar surface area (tPSA) is 81 or more and 200 or less, and it has a combination of one or more of these characteristics. By containing such a (B) tetrazole compound, copper adhesion and copper migration inhibition effects are obtained. It should be noted that it is speculated that copper voids are the result of copper migration, so inhibiting copper migration also exerts an effect of inhibiting copper voids.

[0197] In one embodiment, the acid dissociation constant (pKa) of the (B) tetrazole compound is 1.3 or more and 4.1 or less. From the viewpoints of adhesion to copper and copper migration, the pKa is preferably 2.0 or more and 3.6 or less. The reason for exerting the above effects by using such a (B) tetrazole compound is not certain, and although it is not limited to theory, the inventors consider as follows. That is, it is speculated that the tetrazole compound coordinates with copper on the substrate to exert an effect, and at this time, if the pKa of the tetrazole compound is 4.1 or less, the interaction with the resin becomes stronger and the copper adhesion is improved. On the other hand, if the pKa of the tetrazole compound is 1.3 or more, the interaction is not too strong and copper migration can be inhibited. Therefore, it is speculated that by making the tetrazole compound have an appropriate acidity, the adhesion to copper and copper migration can be balanced. Regarding the pKa, the calculated value by Advanced Chemistry Software V11.02 (1994 - 2018 ACD / Labs) is used.

[0198] As the (B) tetrazole compound having an acid dissociation constant (pKa) of 1.3 or more and 4.1 or less, for example, 1H-tetrazole-5-carboxylic acid, 1H-tetrazole-5-acetic acid, ethyl 1H-tetrazole-5-carboxylate, methyl 1H-tetrazole-5-acetate, 1H-tetrazole-5-propionic acid, 2-[4-(1H-1,2,3,4-tetrazol-5-yl)phenyl]acetic acid, 2-(2H-tetrazol-5-yl)succinic acid, 2,2-bis(2-2H-tetrazol-5-yl)ethyl)malonic acid, and 4-(1H-tetrazol-5-yl)benzoic acid can be mentioned, but are not limited to these. Among these, from the viewpoints of copper adhesion and copper migration, 1H-tetrazole-5-carboxylic acid, 1H-tetrazole-5-acetic acid, and 4-(1H-tetrazol-5-yl)benzoic acid are preferred, and 1H-tetrazole-5-acetic acid is more preferred. It should be noted that when these compounds are added to the resin composition, they can be in the form of hydrates.

[0199] In one embodiment, the (B) tetrazole compound is represented by the following formula (1) or (2).

[0200]

[0201] {In formula (1), R 1 is a hydrogen atom or a monovalent organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms; the hydrogen atoms of the alkyl group and the aryl group are each independently optionally substituted or unsubstituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxysilyl group, and an amino group.}

[0202]

[0203] {In formula (2), R 2 is a hydrogen atom or a monovalent organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, and R 3 is an alkylene group having 1 to 10 carbon atoms; the hydrogen atoms of the alkyl group, the aryl group, and the alkylene group are each independently optionally substituted or unsubstituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxysilyl group, and an amino group.}

[0204] (B) The tetrazole compound can obtain excellent copper adhesion, copper migration inhibition effect, and copper void inhibition effect by containing the compound represented by the above formula (1) or (2). The reason is not certain. Although not limited to theory, it is considered that the lone pair of electrons attached to the nitrogen atom in the tetrazole acts on copper and preferentially exists at the copper interface, and the constituent atoms of the carboxylic acid and ester can form hydrogen bonds with the polyimide precursor. Therefore, the resin and copper interact with each other, thereby improving the copper adhesion. In addition, it is considered that by making the tetrazole compound preferentially exist at the copper interface, the oxidation reaction at the copper interface can be strongly inhibited, thereby suppressing copper migration and copper voids. In addition, it is speculated that if R in the general formula (2) 3 has 1 to 10 carbon atoms, the boiling point of the molecule is higher than that of the compound of the general formula (1), and it is not easily volatilized during pre-baking when coated on the substrate and can remain in the film. Furthermore, it is easily mobile in the film and easily preferentially exists at the interface, so it is more effective for copper adhesion or copper void inhibition.

[0205] Furthermore, especially from the viewpoint of copper adhesion, the (B) tetrazole compound preferably contains the compound represented by the following general formula (3).

[0206]

[0207] {In the formula, R 4 is a hydrogen atom or a monovalent organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms; the hydrogen atoms of the alkyl group and the aryl group are each independently optionally substituted or unsubstituted by at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxysilyl group, and an amino group.}

[0208] R 1 , R 2 and R 4 in the general formulas (1) to (3) having 1 to 10 carbon atoms in the alkyl group can be branched or linear. Preferred examples include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, and propyl. As the aryl group having 6 to 10 carbon atoms in R 1 , R 2 and R 4 in the general formulas (1) to (3), for example, phenyl, tolyl, xylyl, and naphthyl can be mentioned. R 3The C1-C10 alkylene group may be branched or linear. Preferred examples include C1-C5 alkylene groups such as methylene, ethylene, and propylene. The hydrogen atoms of these organic groups may each independently be optionally substituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxysilyl group, and an amino group, or may not be substituted. Among them, when there is an alkoxysilyl group as the carbon number of the organic group, the carbon number of the alkoxysilyl group is not included. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Examples of the alkoxysilyl group include a trialkoxysilyl group, a dialkoxysilyl group, and a monoalkoxysilyl group. Specifically, examples include trimethoxysilyl, triethoxysilyl, dimethoxysilyl, and methoxysilyl. From the viewpoints of copper adhesion, copper voids, and copper migration, in general formula (3), R 4 is more preferably a compound having a hydrogen atom.

[0209] Specific examples of the (B) tetrazole compound represented by general formulas (1) to (2) include 1H-tetrazole-5-carboxylic acid, α,α-difluoro-2H-tetrazole-5-acetic acid, α-hydroxy-2H-tetrazole-5-acetic acid, α-amino-2H-tetrazole-5-acetic acid, methyl 1H-tetrazole-5-carboxylate, ethyl 1H-tetrazole-5-carboxylate, 1H-tetrazole-5-acetic acid, methyl 1H-tetrazole-5-acetate, ethyl 1H-tetrazole-5-acetate, and propyl 1H-tetrazole-5-acetate, but are not limited thereto. Among these, from the viewpoints of copper adhesion and copper migration, 1H-tetrazole-5-carboxylic acid, ethyl 1H-tetrazole-5-carboxylate, 1H-tetrazole-5-acetic acid, and ethyl 1H-tetrazole-5-acetate are preferred, and 1H-tetrazole-5-acetic acid is more preferred. It should be noted that when these compounds are added to the resin composition, they may be in the form of hydrates.

[0210] In one embodiment, the topological polar surface area (tPSA) of the (B) tetrazole compound is 81 to 200. The topological polar surface area (topological PSA; tPSA) refers to the area of the polar part on the surface of a molecule and is mainly an index used in the evaluation of the cell membrane permeability of drugs in pharmaceutical chemistry. By containing a tetrazole compound having a tPSA of 81 or more and 200 or less in the photosensitive resin composition, a copper adhesion and copper migration inhibitory effect can be obtained. The reason is not certain, and although it is not limited to theory, it is considered that the tetrazole compound has a moderate polarity of 81 or more and 200 or less, and as described in the item of pKa, the interaction with the resin when coordinating with copper is moderate, and both copper adhesion and copper migration inhibition can be achieved. In addition, it is considered that when the tPSA is 200 or less, the molecular weight becomes smaller, so the dispersibility of the tetrazole compound in the photosensitive resin composition becomes good, and thus the copper adhesion and copper migration inhibitory effects are exerted.

[0211] The tPSA is calculated using software called "RDKit". The so-called "RDKit" is an open-source Python library used in the field of chemoinformatics. For detailed information about "RDKit", it is described, for example, in "G. Landrum, RDKit: Open-Source Cheminformatics (http: / / www.rdkit.org.)". In the calculation of tPSA in the present invention, the following program is used.

[0212] Python 3.8.8

[0213] RDkit 2023.03.3

[0214] Examples of the (B) tetrazole compound having a tPSA of 81 or more and 200 or less include: 1H-tetrazole-5-carboxylic acid, 1H-tetrazole-5-acetic acid, 1H-tetrazole-5-propionic acid, 2-[4-(1H-1,2,3,4-tetrazol-5-yl)phenyl]acetic acid, 2-(2H-tetrazol-5-yl)succinic acid, 2,2-bis(2-2H-tetrazol-5-yl)ethyl)malonic acid, 4-(1H-tetrazol-5-yl)benzoic acid, and 1H-tetrazole-5-butyric acid, but are not limited thereto. Among these, from the viewpoints of copper adhesion and copper migration, 1H-tetrazole-5-carboxylic acid, 1H-tetrazole-5-acetic acid, and 4-(1H-tetrazol-5-yl)benzoic acid are preferred, and 1H-tetrazole-5-acetic acid is more preferred. It should be noted that when these compounds are added to the resin composition, they may be in the form of hydrates.

[0215] The compounding amount of the (B) tetrazole compound is preferably 0.001 parts by mass or more and 20 parts by mass or less, more preferably 0.01 parts by mass or more and 10 parts by mass or less, and still more preferably 0.01 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor or polyimide resin. Regarding the above compounding amount, considering that it exerts a sufficient effect from the viewpoints of copper adhesion and copper migration inhibition, it is preferably 0.01 parts by mass or more, and from the viewpoints of copper adhesion, copper migration inhibition, and solubility in the composition, it is preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less. By setting it to 10 parts by mass or less, the reason is not certain. Although not limited to theory, it is speculated that a fragile layer is less likely to be generated between the copper layer and the resin layer, so the copper adhesion becomes good, and the ionic components in the resin layer do not increase above the required level, and the copper migration also becomes good.

[0216] (C) Photoinitiator

[0217] The (C) photoinitiator is described. As the photoinitiator, a photo radical polymerization initiator is preferred, and examples thereof include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone and other acetophenone derivatives, thioxanthone, 2-methyl-thioxanthone, 2-isopropyl-thioxanthone, diethyl-thioxanthone and other thioxanthone derivatives, benzil, benzil dimethyl ketal, benzil-β-methoxyethyl acetal and other benzil derivatives, benzoin, benzoin methyl ether and other benzoin derivatives, 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl) oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl) oxime and other oxime compounds, N-phenylglycine and other N-aryl glycine compounds, peroxides such as benzoyl peroxide, aromatic benzimidazoles, titanocenes, photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide, etc., but are not limited thereto. Among the above photoinitiators, oxime compounds are more preferred especially in terms of sensitivity.

[0218] With respect to 100 parts by mass of the (A) polyimide precursor or polyimide resin, the compounding amount of the (C) photoinitiator is preferably 0.1 part by mass or more and 20 parts by mass, more preferably 1 part by mass or more and 8 parts by mass or less, and still more preferably 1 part by mass or more and 5 parts by mass or less. The above compounding amount is 0.1 part by mass or more from the viewpoint of sensitivity or patterning property, and is preferably 20 parts by mass or less from the viewpoint of the physical properties of the cured photosensitive resin layer of the photosensitive resin composition.

[0219] (D) Solvent

[0220] The solvent (D) is described. Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenylethylene glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, 1,3,5-trimethylbenzene, etc. Among them, from the viewpoints of the solubility of the resin, the stability of the resin composition, and the adhesiveness to the substrate, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenylethylene glycol, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, and tetrahydrofurfuryl alcohol are preferred.

[0221] Among such solvents, in particular, solvents that can completely dissolve the polyimide precursor are preferred. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, etc. are exemplified. In particular, from the viewpoint of in-plane uniformity when the photosensitive resin composition is coated on the substrate, γ-butyrolactone and 3-methoxy-N,N-dimethylpropionamide are preferred.

[0222] The solvent can be one kind or two or more kinds of solvents can be mixed and used. From the viewpoint of appropriately adjusting the stability of the resin composition, two or more kinds are preferred. When two or more kinds of solvents are contained, from the viewpoint of in-plane uniformity, 50% by weight or more of the solvent is preferably any one of γ-butyrolactone and 3-methoxy-N,N-dimethylpropionamide, and more preferably γ-butyrolactone.

[0223] In the photosensitive resin composition, the amount of the solvent used is preferably in the range of 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and further preferably 125 to 500 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor or polyimide resin.

[0224] (E) Free-radical polymerizable compound

[0225] The photosensitive resin composition may further contain (E) a radically polymerizable compound. When the (E) radically polymerizable compound is used, the photosensitive resin composition undergoes crosslinking, and the moisture permeability of the cured film decreases, thereby obtaining a copper migration inhibition effect. With respect to 100 parts by mass of the (A) polyimide precursor or polyimide resin, the photosensitive resin composition preferably contains 5 parts by mass or more and 150 parts by mass or less of the radically polymerizable compound. To obtain good chemical resistance, the photosensitive resin composition preferably contains 5 parts by mass or more of the radically polymerizable compound, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more. If too much of the radically polymerizable compound is contained, the copper adhesion may sometimes decrease. However, it is known that the photosensitive resin composition of the present invention can obtain high copper adhesion even when a large amount of the radically polymerizable compound is contained by containing the above-mentioned specific tetrazole compound. From the viewpoint of patterning characteristics, the upper limit value that can be arbitrarily combined with the above lower limit value is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 80 parts by mass or less.

[0226] The so-called radically polymerizable compound is not particularly limited as long as it is a compound that undergoes a radical polymerization reaction by a photopolymerization initiator and a thermal polymerization initiator, and is preferably a (meth)acrylic acid-based compound, for example, represented by the following general formula (43).

[0227]

[0228] {In formula (43), X 11 is an organic group, and L 11 , L 12 and L 13 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms; n 11 is an integer of 1 to 10.}

[0229] The radically polymerizable compound is not particularly limited to the following, but examples thereof include mono- or di-acrylates and methacrylates of ethylene glycol or polyethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate; mono- or di-acrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or tri-acrylates and methacrylates of glycerin, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol diacrylate and dimethacrylate, 1,6-hexanediol diacrylate and dimethacrylate, neopentyl glycol diacrylate and dimethacrylate, mono- or di-acrylates and methacrylates of bisphenol A, benzenetricrylate, isobornyl acrylate and isobornyl methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or tri-acrylates and methacrylates of glycerin, di-, tri- or tetra-acrylates and methacrylates of pentaerythritol, and adducts of these compounds with ethylene oxide or propylene oxide. More specifically, compounds represented by the following formulas (44) and (45) are exemplified, but are not limited thereto.

[0230]

[0231]

[0232] In the present invention, when the number of radically polymerizable groups of the radically polymerizable compound is one, it is referred to as monofunctional, and when it is two or more, it is referred to as x-functional according to the number x of radically polymerizable groups, but sometimes bifunctional or more is collectively referred to as polyfunctional. The radically polymerizable compound may be monofunctional or bifunctional or more. From the viewpoint of chemical resistance, the radically polymerizable compound is preferably trifunctional or more, more preferably tetrafunctional or more, and still more preferably hexafunctional or more. On the other hand, from the viewpoint of elongation at break, it is preferably decafunctional or less.

[0233] The molecular weight of the radically polymerizable compound is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more. As the upper limit value, it is preferably 1000 or less, more preferably 800 or less. By setting it within the above range, chemical resistance and patterning properties are improved.

[0234] Preferably, at least one of the radically polymerizable compounds is a radically polymerizable compound having at least one group selected from a hydroxyl group and a ureido group.

[0235] As the radically polymerizable compound having a hydroxyl group in the molecule, a structure represented by the following general formula (46) can be exemplified.

[0236]

[0237] {In formula (46), X 11 is an organic group, and L 11 , L 12 and L 13 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms; n 11 is an integer from 1 to 10, and n 12 is an integer from 1 to 10.}

[0238] In the above formula (46), from the viewpoint of free radical reactivity, it is preferable that L 11 is a hydrogen atom or a methyl group, and L 12 , L 13 is a hydrogen atom. More specifically, compounds represented by the following formula (47) can be cited, but are not limited thereto.

[0239]

[0240] By having a hydroxyl group in the molecular structure, the chemical resistance becomes particularly good. The number of hydroxyl groups in the molecular structure is preferably 1 or more, more preferably 2 or more. As the upper limit value, it is preferably 10 or less, more preferably 6 or less, and further preferably 3 or less. By setting it within the above range, the chemical resistance and the adhesiveness to the substrate become good.

[0241] The radical polymerizable compound having a ureido group in the molecule can be represented by the following general formula (48).

[0242]

[0243] {In formula (48), X 20 , X 21 , X 22 , X 23 are each independently a hydrogen atom, a monovalent organic group having a group represented by the following general formula (49), or a monovalent organic group having 1 to 20 carbon atoms optionally containing a heteroatom, and at least one of X 20 , X 21 , X 22 , X 23 is a monovalent organic group having a group represented by the following general formula (49).}

[0244]

[0245] {In formula (49), L 11 , L 12 and L 13 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.}

[0246] In the above formula (49), L 11is a hydrogen atom or a methyl group, and from the viewpoint of free radical reactivity, L is preferably 12 and L 13 is a hydrogen atom.

[0247] Examples of the hetero atom include an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom, and the like.

[0248] In the formula (48), when X 20 , X 21 , X 22 , X 23 is a monovalent organic group having 1 to 20 carbon atoms optionally containing a hetero atom, from the viewpoint of developability, it is more preferably contains an oxygen atom. The carbon number is not limited as long as it is 1 to 20, and from the viewpoint of heat resistance, the carbon number is preferably 1 to 10, more preferably 3 to 10. X 20 , X 21 , X 22 , X 23 optionally bond to each other to have a cyclic structure, but from the viewpoint of chemical resistance, it is preferably does not have a cyclic structure. By making X 20 , X 21 , X 22 , X 23 bond to each other to have a cyclic structure, the degree of freedom of the bond angle of the urea group is lost, and it becomes difficult to form a strong hydrogen bond. From the viewpoint of forming a hydrogen bond with other molecules, it is preferred that at least one of X 20 , X 21 , X 22 , X 23 is a hydrogen atom. On the other hand, from the viewpoint of solubility, it is preferred that the number of hydrogen atoms in X 20 , X 21 , X 22 , X 23 is 2 or less. Specific examples of the compound represented by the following formula can be exemplified.

[0249]

[0250] The radically polymerizable compound preferably has at least one or more hydroxyl groups and one or more urea groups in the molecule. The radically polymerizable compound having at least one or more hydroxyl groups and at least one or more urea groups in the molecule can be represented by the following general formula (50), for example.

[0251]

[0252] {In the formula (50), X 30 , X 31 , X 32 , X 33Each independently is a hydrogen atom, a monovalent organic group having a group represented by the following general formula (51), or a monovalent organic group having 1 to 20 carbon atoms optionally containing a heteroatom, X 30 、X 31 、X 32 、X 33 At least one of them is a monovalent organic group having a group represented by the following general formula (51), and at least one is a hydroxyl group.}

[0253]

[0254] {In formula (51), L 11 、L 12 and L 13 Each independently is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms}. From the viewpoint of radical reactivity, in the above formula (51), it is preferable that L 11 is a hydrogen atom or a methyl group, and L 12 、L 13 are hydrogen atoms.

[0255] In formula (50), when X 30 、X 31 、X 32 、X 33 are monovalent organic groups having 1 to 20 carbon atoms optionally containing a heteroatom, from the viewpoint of developability, it is more preferable to contain an oxygen atom. As long as the carbon number is 1 to 20, there is no limitation. From the viewpoint of heat resistance, the carbon number is preferably 1 to 10, and more preferably 3 to 10. X in formula (51) 30 、X 31 、X 32 、X 33 Optionally bond to each other to have a cyclic structure, but from the viewpoint of chemical resistance, it is preferably not to have a cyclic structure. By making X 30 、X 31 、X 32 、X 33 bond to each other to have a cyclic structure, the degree of freedom of the bond angle of the ureido group is lost, and it becomes difficult to form a strong hydrogen bond. From the viewpoint of forming a hydrogen bond with other molecules, it is preferable that at least one of X 30 、X 31 、X 32 、X 33 is a hydrogen atom. On the other hand, from the viewpoint of solubility, it is preferable that the number of hydrogen atoms in X 30 、X 31 、X 32 、X 33 is 2 or less. Compounds represented by the following formulas can be specifically exemplified.

[0256]

[0257] In the radical polymerizable compound, the method for producing a radical polymerizable compound having a ureido group is not particularly limited. For example, it can be obtained by reacting an isocyanate compound having a radical polymerizable group with an amine-containing compound. When the amine-containing compound contains a functional group such as a hydroxyl group that can react with the isocyanate, a part of the isocyanate compound may contain a compound that reacts with the functional group such as a hydroxyl group.

[0258] The radical polymerizable compound can be used alone, but it is preferably used in combination of two or more. By using two or more in combination, the chemical resistance and in-plane uniformity become good. Although the reason for the improvement of the in-plane uniformity is only speculation, it is considered that when only one radical polymerizable compound is added in a large amount, microphase separation occurs with the polyimide precursor component in the varnish. For the above reasons, when the radical polymerizable compound is used alone, it is preferably 60 parts by mass or less, more preferably 40 parts by mass or less, based on 100 parts by mass of the polyimide precursor.

[0259] When two or more radical polymerizable compounds are used in combination, from the viewpoint of controlling the crosslinking density, it is preferably six or less, more preferably four or less.

[0260] When a plurality of radical polymerizable compounds are used in combination, it is preferable that the number of functional groups of at least one radical polymerizable compound among the plurality of radical polymerizable compounds is different. When three or more radical polymerizable compounds are used, it is sufficient that at least one of them has a different number of functional groups, but it is preferable that all the radical polymerizable compounds have different numbers of functional groups. When a plurality of radical polymerizable compounds are used, from the viewpoint of the elongation at break, it is preferable to contain at least one monofunctional radical polymerizable compound.

[0261] When two or more radical polymerizable compounds are used in combination, it is preferable to contain at least one radical polymerizable compound containing a nitrogen atom and at least one radical polymerizable compound not containing a nitrogen atom. The radical polymerizable compound containing a nitrogen atom is preferably a radical polymerizable compound containing a ureido group. The radical polymerizable compound containing a nitrogen atom can form a strong hydrogen bond, so the chemical resistance is excellent. However, if a plurality of radical polymerizable compounds containing a nitrogen atom are added, a complex hydrogen bond network structure is formed, resulting in insufficient solubility.

[0262] The photosensitive resin composition may further contain components other than the above components (A) to (E). Examples of components other than components (A) to (E) are not limited, and may include: (F) a thermal crosslinking agent, (G) a heterocyclic compound, (H) a thermal base generator, (I) a hindered phenol compound, (J) an organotitanium compound, (K) an adhesion aid, (L) a sensitizer, (M) a polymerization inhibitor, etc.

[0263] (F) Thermal crosslinking agent

[0264] In order to suppress the copper adhesion or copper migration of the polyimide film, the photosensitive resin composition may optionally contain a thermal crosslinking agent.

[0265] A thermal crosslinking agent refers to a compound that undergoes an addition reaction or a polycondensation reaction by heat. These reactions occur through the combination of (A) a polyimide resin and (F) a thermal crosslinking agent, (F) thermal crosslinking agents with each other, and (F) a thermal crosslinking agent and other components described below. As the reaction temperature, it is preferably 150 °C or higher.

[0266] Examples of the thermal crosslinking agent may include: alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds, etc. From the viewpoint of suppressing curing shrinkage, (F) the thermal crosslinking agent preferably contains a nitrogen atom.

[0267] Examples of the alkoxymethyl compound may include compounds of the following formula, but are not limited to these.

[0268]

[0269] In addition, examples of commercially available alkoxymethyl compounds may include: alkylated urea resin (product name MX290, manufactured by NIKALAC Corporation) or 1,3,4,6 - tetra(methoxymethyl)glycoluril (product name MX270, manufactured by NIKALAC Corporation), etc.

[0270] Examples of the epoxy compound may include: 4 - hydroxybutyl acrylate glycidyl ether, an epoxy compound containing a bisphenol A group, and hydrogenated bisphenol A diglycidyl ether, etc. For example, Epolight 4000 (product name, manufactured by Kyoeisha Chemical Co., Ltd.) can be preferably used.

[0271] Examples of the oxetane compound include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, bisphenol acid bis(3-ethyl-3-oxetanylmethyl) ester, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetra(3-ethyl-3-oxetanylmethyl) ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silsesquioxane] derivative, oxetanyl silicate, novolak type oxetane, 1,3-bis[(3-ethyloxetane-3-yl)methoxy]benzene, etc. For example, OXT121 (product name, manufactured by Toagosei Co., Ltd.), OXT221 (product name, manufactured by Toagosei Co., Ltd.), etc. can be preferably used.

[0272] Examples of the bismaleimide compound include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1,3-phenylenebis(maleimide), N,N'-1,4-phenylenebis(maleimide), 3-methyl-N,N'-1,4-phenylenebis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, etc.

[0273] Examples of the allyl compound include allyl alcohol, allyl phenyl ether, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allyl phenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, triallyl citrate, etc.

[0274] Examples of the blocking isocyanate compound include hexamethylene diisocyanate-based blocking isocyanates (e.g., manufactured by Asahi Kasei Corporation, trade names below: Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G; manufactured by Mitsui Chemicals, Inc., trade name: Takenate B-882N; manufactured by Baxenden Company, trade names below: 7960, 7961, 7982, 7991, and 7992, etc.); toluene diisocyanate-based blocking isocyanates (e.g., manufactured by Mitsui Chemicals, Inc., trade name: Takenate B-830, etc.); 4,4'-diphenylmethane diisocyanate-based blocking isocyanates (e.g., manufactured by Mitsui Chemicals, Inc., trade name: Takenate B-815N; manufactured by Daiei Sangyo Co., Ltd., trade names: Blonate PMD-OA01 and PMD-MA01, etc.); 1,3-bis(isocyanatomethyl)cyclohexane-based blocking isocyanates (e.g., manufactured by Mitsui Chemicals, Inc., trade name: Takenate B-846N; manufactured by Tosoh Corporation, trade names below: Coronate BI-301, 2507, and 2554, etc.); and isophorone diisocyanate-based blocking isocyanates (e.g., manufactured by Baxenden Company, trade names below: 7950, 7951, and 7990, etc.).

[0275] Among these, from the viewpoint of storage stability, a blocking isocyanate compound or a bismaleimide compound is preferred. (F) The thermal crosslinking agent can be used alone or in combination of two or more kinds.

[0276] With respect to 100 parts by mass of the (A) polyimide precursor or polyimide resin, the content of the (F) thermal crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.2 parts by mass to 40 parts by mass. From the viewpoint of chemical resistance, the lower limit value of the thermal crosslinking agent is more preferably 1 part by mass or more, and further preferably 5 parts by mass or more. From the viewpoint of the storage stability of the photosensitive resin composition of the present invention, the upper limit value of the thermal crosslinking agent is more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less.

[0277] (G) Heterocyclic compound

[0278] As the photosensitive resin composition of the present invention, in addition to the (B) tetrazole compound, for the purpose of improving copper adhesion, developability, copper migration inhibition ability, etc., a heterocyclic compound may also be contained. Examples of the heterocyclic compound include imidazole derivatives, triazole derivatives, tetrazole derivatives other than (B), and purine derivatives, etc.

[0279] As specific examples of the purine derivatives, the following can be cited: purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine and the like, and their derivatives. These heterocyclic compounds may be used singly or as a mixture of two or more.

[0280] When the photosensitive resin composition contains a heterocyclic compound, the compounding amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of (A) the polyimide precursor or the polyimide resin, from the viewpoint of copper adhesion. When the compounding amount is 0.1 part by mass or more, discoloration of copper is suppressed when the photosensitive resin composition is formed on copper. On the other hand, when the compounding amount is 10 parts by mass or less, the copper adhesion is excellent.

[0281] (H) Thermal base generator

[0282] The photosensitive resin composition may contain a base generator. The base generator refers to a compound that generates a base upon heating. By containing a thermal base generator, the imidization of the photosensitive resin composition can be further promoted.

[0283] The type of the thermal base generator is not particularly specified, but examples thereof include amine compounds protected by tert-butoxycarbonyl, or the thermal base generators disclosed in International Publication No. 2017 / 038598. However, it is not limited to these, and other known thermal base generators may also be used.

[0284] Examples of the amine compound protected with a tert-butoxycarbonyl group include, but are not limited to, ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanediol bis(3-aminopropyl)ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl)ether, 1,11-diamino-3,6,9-trioxaundecane, and compounds obtained by protecting the amino group of an amino acid and its derivatives with a tert-butoxycarbonyl group.

[0285] With respect to 100 parts by mass of the (A) polyimide precursor or polyimide resin, the compounding amount of the thermal base generator is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less. As the above compounding amount, it is 0.1 part by mass or more from the viewpoint of the imidization promotion effect, and preferably 20 parts by mass or less from the viewpoint of the physical properties of the cured photosensitive resin layer of the photosensitive resin composition.

[0286] (I) hindered phenol compound

[0287] To inhibit discoloration on the copper surface, the photosensitive resin composition may optionally contain a hindered phenol compound. Examples of the hindered phenol compound are not limited, and include, for example: 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-benzamide), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), pentaerythrityl-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, etc.

[0288] In addition, examples of the hindered phenol compound include, but are not limited to: 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-trimethylethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, etc.

[0289] Among these, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, etc. are particularly preferred.

[0290] With respect to 100 parts by mass of the polyimide precursor or polyimide resin (A), the compounding amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass from the viewpoint of the photosensitivity characteristics. When the compounding amount is 0.1 part by mass or more, for example, when forming a photosensitive resin composition on copper or a copper alloy, discoloration and corrosion of copper or a copper alloy are prevented. On the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent.

[0291] (J) Organotitanium compound

[0292] The photosensitive resin composition may contain an organotitanium compound. By containing an organotitanium compound, a photosensitive resin layer excellent in chemical resistance can be formed even when cured at a low temperature.

[0293] Examples of the organotitanium compound that can be used include substances in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

[0294] Specific examples of the organotitanium compound are shown in the following I) to VII):

[0295] I) Titanium chelate: Among them, from the aspect of obtaining the storage stability of the photosensitive resin composition and a good pattern, a titanium chelate having two or more alkoxy groups is more preferable. Specific examples are: bis(triethanolamine)diisopropoxytitanium, bis(2,4-pentanedionato)di(n-butyl)titanium, bis(2,4-pentanedionato)diisopropoxytitanium, bis(tetramethylheptanedionato)diisopropoxytitanium, bis(ethyl acetoacetate)diisopropoxytitanate, etc.

[0296] II) Tetraalkoxytitanium compound: For example, tetra(n-butyl)titanium, tetraethanoltitanium, tetra(2-ethylhexyl)titanium, tetra(isobutyl)titanium, tetraisopropoxytitanium, tetramethanoltitanium, tetramethoxypropanoltitanium, tetramethylphenoltitanium, tetra(n-nonyl)titanium, tetra(n-propyl)titanium, tetrastearyl alcohol titanium, tetra[bis{2,2-(allyloxymethyl)butanol}]titanium, etc.

[0297] III) Metallocene titanium compound: For example, pentamethylcyclopentadienyltrimethanol titanium, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc.

[0298] IV) Monoalkoxytitanium compound: For example, tri(dioctyl phosphate)isopropoxytitanium, tri(dodecylbenzenesulfonic acid)isopropoxytitanium, etc.

[0299] V) Titanium oxide compound: For example, bis(pentanedionato)titanium oxide, bis(tetramethylheptanedionato)titanium oxide, phthalocyanine titanium oxide, etc.

[0300] VI) Titanium tetraacetylacetonate compounds: such as titanium tetraacetylacetonate and the like.

[0301] VII) Titanate coupling agents: such as isopropyl tri(dodecylbenzenesulfonyl) titanate and the like.

[0302] Among them, when the organotitanium compound is at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, it is preferable from the viewpoint of exhibiting better chemical resistance. Particularly preferred are diisopropyl bis(ethyl acetoacetate) titanate, tetra(n-butyl)titanium, and bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

[0303] When compounding an organotitanium compound with respect to 100 parts by mass of (A) polyimide precursor or polyimide, the compounding amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass. When the above compounding amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited. On the other hand, when it is 10 parts by mass or less, the storage stability is excellent.

[0304] (K) Adhesion aids

[0305] In order to improve the adhesion between the film formed using the photosensitive resin composition and the substrate, the photosensitive resin composition may optionally contain an adhesion aid. Examples of the adhesion aid include: silane coupling agents such as γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyldimethoxysilane, γ-glycidoxypropyl methyldimethoxysilane, γ-mercaptopropyl methyldimethoxysilane, 3-methacryloxypropyl dimethoxymethylsilane, 3-methacryloxypropyl trimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalic acid amide, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyl trimethoxysilane, 3-ureidopropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride, etc., and aluminum-based adhesion aids such as tris(ethyl acetoacetate)aluminum, tris(acetylacetone)aluminum, and ethyl acetoacetate aluminum diisopropyl ester.

[0306] Among these adhesion aids, in terms of adhesion force, a silane coupling agent is more preferably used. When the photosensitive resin composition contains an adhesion aid, the compounding amount of the adhesion aid is preferably in the range of 0.5 to 25 parts by mass relative to 100 parts by mass of the (A) polyimide precursor.

[0307] As the silane coupling agent, there is no limitation. For example, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Corporation: trade name Sila-Ace S810), N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM573), 3-mercaptopropyltriethoxysilane (manufactured by AZmax Corporation: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by AZmax Corporation: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by AZmax Corporation: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by AZmax Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyl diethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyl dimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyl dimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, tert-butyl carbamate (3-triethoxysilylpropyl), 4,4'-carbonylbis(2-(((3-triethoxysilyl)propyl)amino)carbonyl)benzoic acid, 2-(3-triethoxysilylpropylcarbamoyl)benzoic acid, etc.

[0308] In addition, as the silane coupling agent, without limitation, for example, the following can be cited: N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by AZmax Co., Ltd.: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by AZmax Co., Ltd.: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by AZmax Co., Ltd.: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by AZmax Co., Ltd.: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by AZmax Co., Ltd.: trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by AZmax Co., Ltd.: trade name SLA0599.2), etc.

[0309] In addition, examples of the silane coupling agent include: 2-(trimethoxysilylethyl)pyridine (manufactured by AZmax Co., Ltd.: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, tert-butyl (3-triethoxysilylpropyl)carbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-isobutoxysilane, tetra-tert-butoxysilane, tetra(methoxyethoxysilane), tetra(methoxy-n-propoxysilane), tetra(ethoxyethoxysilane), tetra(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, di-tert-butoxydiacetoxysilane, di-isobutoxyaluminoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butyldiphenylsilanediol, isobutyldiphenylsilanediol, tert-butyldiphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxy-di-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl-n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, etc., but are not limited thereto.

[0310] The silane coupling agents listed above can be used alone or in combination of multiple types. Among the silane coupling agents listed above, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxy-di-p-tolylsilane, triphenylsilanol, and silane coupling agents having a structure represented by the following formula are preferred.

[0311]

[0312] As the compounding amount in the case of using a silane coupling agent, it is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of (A) a polyimide precursor or a polyimide resin.

[0313] (L) Sensitizer

[0314] To improve the photosensitivity, the photosensitive resin composition may optionally contain a sensitizer. Examples of such sensitizers include: Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylstilbene)-benzothiazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)isoindolothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, 2,2'-(phenylimino)diethanol, etc. These can be used alone or in combinations of, for example, 2 to 5 kinds.

[0315] When the photosensitive resin composition contains a sensitizer, the compounding amount is preferably 0.1 to 25 parts by mass relative to 100 parts by mass of (A) a polyimide precursor or a polyimide resin.

[0316] (M) Polymerization inhibitor

[0317] In order to improve the viscosity and the stability of the photosensitivity of the photosensitive resin composition especially when stored in a solution containing a solvent, the photosensitive resin composition may optionally contain a polymerization inhibitor. As the polymerization inhibitor, the following can be used: hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, diethylene glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, ammonium salt of N-nitroso-N-phenylhydroxylamine, ammonium salt of N-nitroso-N(1-naphthyl)hydroxylamine, etc.

[0318] <Manufacturing Method of Cured Relief Pattern and Semiconductor Device>

[0319] The manufacturing method of the cured relief pattern of the present invention includes the following steps: (1) a step of coating the photosensitive resin composition of the present invention on a substrate to form a photosensitive resin layer on the substrate; (2) a step of exposing the resin layer; (3) a step of developing the exposed resin layer to form a relief pattern; (4) a step of heat-treating the relief pattern to form a cured relief pattern.

[0320] (1) Resin layer forming step

[0321] In this step, the photosensitive resin composition is coated on a substrate and, if necessary, dried thereafter to form a photosensitive resin layer. As the coating method, the methods conventionally used for coating photosensitive resin compositions can be used. For example, the methods of coating by a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., and the method of spray coating by a spray coater can be used.

[0322] (2) Exposure step

[0323] In this step, an exposure device such as a contact aligner, a mirror projection, a stepper, etc. is used to expose the formed resin layer via a photomask or reticle having a pattern or directly through an ultraviolet light source, etc.

[0324] (3) Relief pattern forming step

[0325] In this step, the unexposed portion in the photosensitive resin layer after exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected from the known developing methods for photoresists, such as spin spray method, paddle method, dipping method with ultrasonic treatment, etc. and used. In addition, after development, for the purpose of adjusting the shape of the relief pattern, etc., post-development baking can be carried out according to need with any combination of temperature and time.

[0326] As the developer used in development, for example, a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent is preferably used. As the good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferably used. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol monomethyl ether acetate, and water, etc. are preferably used. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the photosensitive resin composition. In addition, two or more of each solvent can also be used, for example, several kinds can be combined and used.

[0327] (4) Curing Relief Pattern Formation Step

[0328] In this step, the relief pattern obtained by the above development is heat-treated to volatilize the photosensitive component and imidize the (A) polyimide precursor, thereby converting it into a cured relief pattern (cured film) containing polyimide. As the method of heat treatment, for example, various methods such as the method using a hot plate, the method using an oven, and the method using a temperature-programmable oven can be selected. The heat treatment can be carried out, for example, under the conditions of 160°C to 350°C for 30 minutes to 5 hours. As the temperature of the heat treatment, in order to further improve the copper adhesion, it is preferably 350°C or lower, more preferably 230°C or lower, further preferably 200°C or lower, and still more preferably 180°C or lower. In addition, in order to further suppress copper migration, the temperature is preferably 200°C or higher, more preferably 230°C or higher. As the atmosphere gas during heat curing, air can be used, or inert gases such as nitrogen and argon can be used.

[0329] <Polyimide Film>

[0330] The polyimide film (cured film) of the present invention can be produced by curing the photosensitive resin composition of the present invention, and the present invention also provides a cured film formed from the cured product of the photosensitive resin composition of the present invention. For example, the photosensitive resin composition containing (A) polyimide resin of the present invention can produce a polyimide film based on the above-described method for manufacturing a cured relief pattern. Further, for example, the photosensitive resin composition containing (A) polyimide precursor of the present invention can be imidized to form a polyimide cured product with an imidization rate of 80 to 100%, thereby producing a polyimide film. In this case, the polyimide film can also be produced based on the above-described method for manufacturing a cured relief pattern. The structure of the polyimide contained in the cured relief pattern formed from the above polyimide precursor composition is represented by the following general formula.

[0331]

[0332] Preferred X in General Formulas (4) and (4') 1 , Y 1 For the same reason, it is also preferred in the polyimide having the structure represented by the above general formula. In the above general formula, the number of repeating units m is not particularly limited and may be an integer of 2 to 150.

[0333] <Semiconductor Device>

[0334] The semiconductor device preferably has a cured relief pattern obtained by the above-described method for manufacturing a cured relief pattern. The semiconductor device preferably has a substrate for a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-described method for manufacturing a cured relief pattern. The semiconductor device can use a semiconductor element as a substrate and be produced by using the method for manufacturing a cured relief pattern of the present invention as part of the process. More specifically, the semiconductor device can be produced by the following method for manufacturing a semiconductor device, which includes forming a cured relief pattern formed by the method for manufacturing a cured relief pattern of the present invention into a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure.

[0335] <Display Device>

[0336] The display device preferably includes a display element and a display device having a cured film provided on the upper part of the display element, and the cured film is the above-described cured relief pattern. Here, the cured relief pattern can be directly laminated in contact with the display element or can be laminated with other layers interposed therebetween. For example, as the cured film, there can be mentioned: a surface protective film, an insulating film, and a planarizing film for a TFT liquid crystal display element and a color filter element, a protrusion for an MVA type liquid crystal display device, and a partition wall for a cathode of an organic EL element.

[0337] The photosensitive resin composition of the present invention is preferably a photosensitive resin composition for forming an insulating member or an interlayer insulating film. In addition, the photosensitive resin composition can be used to form a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure. The photosensitive resin composition of the present invention can be used not only for semiconductor devices as described above, but also for interlayer insulating films of multilayer circuits, covering coatings of flexible copper clad laminates, solder resist films, and liquid crystal alignment films, etc.

[0338] Examples

[0339] Hereinafter, examples of the present invention will be specifically described, but the embodiments are not limited to these. In the examples, comparative examples, and production examples, the physical properties of the polyimide precursor or the photosensitive resin composition were measured and evaluated according to the following methods.

[0340] <Measurement and evaluation methods>

[0341] (1) Weight-average molecular weight

[0342] The weight-average molecular weight (Mw) of each resin was measured using gel permeation chromatography (standard polystyrene conversion) under the following conditions.

[0343] Pump: JASCO PU-980

[0344] Detector: JASCO RI-930

[0345] Column oven: JASCO CO-965 40 °C

[0346] Columns: Two Shodex KD-806M manufactured by Showa Denko K.K. in series, or

[0347] Shodex 805M / 806M manufactured by Showa Denko K.K. in series

[0348] Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko K.K.

[0349] Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP)

[0350] Flow rate: 1 mL / min.

[0351] (2) Fabrication of a cured relief pattern for copper void evaluation

[0352] On a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625 ± 25 μm), using a sputtering device (type L-440S-FHL, manufactured by CANON ANELVA Corporation), titanium (Ti) with a thickness of 200 nm and copper (Cu) with a thickness of 400 nm were sequentially sputtered. Then, using a spin coater / developer (type D-Spin60A, manufactured by SOKUDO Corporation), the photosensitive resin composition prepared by the following method was spin-coated on the wafer, and pre-baked on a hot plate at 110 °C for 180 seconds to form a film with a thickness of approximately 10 μm. Using a mask with test patterns for this film, irradiated with i-ray at an energy of 650 mJ / cm 2 of the energy. Subsequently, using cyclopentanone as the developer, after a time obtained by multiplying the time until the unexposed portion was completely dissolved and disappeared by 1.4, the film was spray-developed using a spin coater / developer (type D-Spin60A, manufactured by SOKUDO Corporation), and spin-spray rinsed with propylene glycol monomethyl ether acetate for 10 seconds, thereby obtaining a relief pattern on Cu.

[0353] Using a temperature-programmed curing furnace (type VF-2000, manufactured by Koyo Lindberg Corporation), in a nitrogen atmosphere, the wafer with the relief pattern formed on Cu was heat-treated at 230 °C for 2 hours, thereby obtaining a cured relief pattern containing resin with a thickness of approximately 6 - 9 μm on Cu.

[0354] (3) High temperature storage test of the cured relief pattern on Cu and subsequent void area evaluation

[0355] Using a temperature-programmed curing furnace (type VF-2000, manufactured by Koyo Lindberg Corporation), in air, the wafer with the cured relief pattern formed on Cu was heated at 150 °C for 168 hours. Then, using a plasma surface treatment device (type EXAM, manufactured by Shinko Seiki Co., Ltd.), all the resin layers on Cu were removed by plasma etching, and the portion where the resin originally existed was observed under the following conditions to evaluate the copper voids. The plasma etching conditions are as follows.

[0356] Output power: 133 W

[0357] Gas type, flow rate: O 2 : 40 mL / min + CF4: 1 mL / min

[0358] Air pressure: 50 Pa

[0359] Mode: hard mode

[0360] Etching time: 4200 seconds

[0361] The surface of Cu after completely removing the resin layer was observed under the following conditions using FE-SEM (model S-4800, manufactured by Hitachi High-Technologies Corporation), and the area occupied by voids on the surface of the Cu layer was calculated using image analysis software (A Image King, manufactured by Asahi Kasei Corporation).

[0362] <Observation adjustment>

[0363] ·Acceleration voltage: 20 kV

[0364] ·SE detector: Mixed, BSE-L (L.A.5)

[0365] ·Probe current: High

[0366] ·Working Distance: 8 mm

[0367] ·Tilt: 0°

[0368] ·Observation magnification: 1000 times

[0369] When the total area of voids when evaluating the photosensitive resin composition described in Comparative Example 1 is set to 100%, those with a total area ratio of voids less than 50% are judged as "A", those with 50% or more and less than 70% are judged as "B", those with 70% or more and less than 100% are judged as "C", and those with 100% or more are judged as "D". If the evaluation is B or above, it can be preferably used as a cured relief pattern suitable for semiconductors.

[0370] (4) Copper adhesion evaluation

[0371] On a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625 ± 25 μm), using a sputtering device (model L-440S-FHL, manufactured by CANON ANELVA Corporation), titanium (Ti) with a thickness of 200 nm and copper (Cu) with a thickness of 400 nm were sequentially sputtered. Then, the photosensitive resin composition was spin-coated on the wafer so that the cured film thickness became approximately 9 μm and dried, and then through a parallel light mask aligner (model PLA-501FA, manufactured by Canon Inc.) at 800 mJ / cm 2Expose the entire surface. Using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg), heat for 2 hours at the temperatures described in Tables 1 to 4 under a nitrogen atmosphere to obtain a cured relief pattern (a film of thermally cured polyimide). For the film after the heat treatment, evaluate the adhesion characteristics between the copper substrate and the cured resin film based on the cross-cut method of JIS K 5600-5-6 according to the following criteria. If the evaluation is B or above, it can preferably be used as a cured relief pattern suitable for semiconductors.

[0372] A: The number of grids of the cured resin film adhered to the substrate is 100

[0373] B: The number of grids of the cured resin film adhered to the substrate is 80 or more and less than 100

[0374] C: The number of grids of the cured resin film adhered to the substrate is 40 or more and less than 80

[0375] D: The number of grids of the cured resin film adhered to the substrate is less than 40

[0376] (5) b-Hast test

[0377] Prepare a TEG (Test Element Group) wafer with a comb-shaped Cu wiring of line / space = 10 μm / 10 μm and a height of 5 μm formed on a silicon wafer. Immerse this TEG wafer in a 1% aqueous acetic acid solution for 1 minute, then rinse it with running deionized water and dry it with an air gun. And, apply oxygen plasma for 20 seconds at 40 mL / minute, 133 W, and 50 Pa by low-pressure plasma (manufactured by Shinko Seiki Co., Ltd., EXAM). After that, use a spin coater (D-Spin60A type, manufactured by SOKUDO Co., Ltd.) to spin coat the photosensitive resin composition so that the film thickness becomes 10 μm, and perform pre-baking on a hot plate at 110 °C for 180 seconds to form a film on the TEG wafer. And, through a parallel light mask aligner (PLA-501FA type, manufactured by Canon Inc.), at 800 mJ / cm 2Exposure. At this time, in order to form conduction during the b-HAST test, exposure is performed in a state where the Cu electrode portion is masked so as not to be irradiated with light, and the unexposed portion is removed by subsequent development. After exposure, after 30 minutes or more, using a spin coater (D-Spin60A type, manufactured by SOKUDO Co., Ltd.), cyclopentanone is used as the developer at 23°C, and spin spray development is performed for 1.4 times the time until the unexposed portion is completely dissolved and disappeared, and then spin spray rinsing is performed with propylene glycol monomethyl ether acetate for 10 seconds. After that, using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.), heating is performed at the temperatures shown in Tables 2 to 4 for 2 hours in a nitrogen atmosphere to obtain a cured relief pattern.

[0378] Using a high-temperature and high-humidity test chamber (TH-222M, manufactured by ESPEC Corporation) and a highly accelerated life test device HAST Chamber (EHS-222M, manufactured by ESPEC Corporation), a b-HAST test is performed at 130°C and 85% RH with an applied voltage of 50V. The insulation resistance value between the copper wirings is measured at 30-minute intervals. If it becomes 1×10 4 Ω or less, it is insulation breakdown. Calculate the time from the start of the test to insulation breakdown and evaluate based on the following criteria. If the evaluation is D or above, it can preferably be used as a cured relief pattern suitable for semiconductors.

[0379] A: 250 hours or more until insulation breakdown

[0380] B: 200 hours or more and less than 250 hours until insulation breakdown

[0381] C: 150 hours or more and less than 200 hours until insulation breakdown

[0382] D: 100 hours or more and less than 150 hours until insulation breakdown

[0383] E: Less than 100 hours until insulation breakdown

[0384] <Production Example>

[0385] Production Example 1: (A) Synthesis of polyimide precursor A1

[0386] 124.0 g of 4,4'-oxydiphthalic anhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) were charged into a separable flask with a capacity of 2 L. 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone (hereinafter referred to as GBL) were charged, and the mixture was stirred at room temperature. While stirring, 81.5 g of pyridine was added to obtain a reaction mixture. After the heat generation due to the reaction ended, the reaction mixture was naturally cooled to room temperature and left for 16 hours.

[0387] Next, while cooling in an ice bath and stirring, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 200 mL of γ-butyrolactone was added to the reaction mixture over 20 minutes. Then, while stirring, a substance obtained by suspending 93.0 g of 4,4'-oxydianiline (ODA) in 350 mL of γ-butyrolactone was added over 30 minutes. Further, after stirring at room temperature for 4 hours, 30 mL of ethanol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

[0388] The obtained reaction solution was added to 3 L of ethanol to form a precipitate containing a crude polymer. The generated crude polymer was separated by filtration, dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer. After the obtained precipitate was separated by filtration, it was dried under vacuum to obtain a powdery polymer (polyimide precursor A1). The molecular weight of polyimide precursor A1 was measured by gel permeation chromatography (standard polystyrene conversion), and the result showed that the weight average molecular weight (Mw) was 24,000.

[0389] Production Example 2: (A) Synthesis of polyimide precursor A2

[0390] The reaction was carried out in the same manner as described in Production Example 1 above, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 124.0 g of 4,4'-oxydiphthalic anhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), to obtain a polymer (polyimide precursor A2). The molecular weight of polyimide precursor A2 was measured by gel permeation chromatography (standard polystyrene conversion), and the result showed that the weight average molecular weight (Mw) was 24,000.

[0391] Production Example 3: (A) Synthesis of polyimide precursor A3

[0392] Except for using 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) instead of 124.0 g of 4,4'-oxydiphthalic anhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), the reaction was carried out in the same manner as described in Production Example 1 above to obtain a polymer (polyimide precursor A3). The molecular weight of polyimide precursor A3 was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 21,000.

[0393] Production Example 4: (A) Synthesis of polyimide precursor A4

[0394] Except for using 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) instead of 124.0 g of 4,4'-oxydiphthalic anhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and using 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) instead of 93.0 g of 4,4'-oxydianiline (ODA), the reaction was carried out in the same manner as described in Production Example 1 above to obtain a polymer (A4). The molecular weight of polymer (A4) was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 21,000.

[0395] Production Example 5: (A) Synthesis of polyimide precursor A5

[0396] Except for using 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) instead of 124.0 g of 4,4'-oxydiphthalic anhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and using 49.2 g of 1,4-phenylenediamine (pPD) instead of 93.0 g of 4,4'-oxydianiline (ODA), the reaction was carried out in the same manner as described in Production Example 1 above to obtain a polymer (polyimide precursor A5). The molecular weight of polyimide precursor A5 was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 21,000.

[0397] Production Example 6: (A) Synthesis of polyimide precursor A6

[0398] Except for using 62 g of 4,4'-oxydiphthalic anhydride (ODPA) and 88.3 g of pyromellitic dianhydride (PMDA) instead of 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) in Production Example 4, the reaction was carried out in the same manner as described in Production Example 1 above to obtain a polymer (polyimide precursor A6). The molecular weight of polyimide precursor A6 was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight-average molecular weight (Mw) was 28,000.

[0399] Production Example 7: (A) Synthesis of polyimide resin A7

[0400] 200 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 33.1 g (0.012 mol) of 6-(4-aminophenoxy)biphenyl-3-amine (PDPE) were added to a three-necked flask equipped with a Dean-Stark extraction apparatus and purged with nitrogen and dissolved therein. To this, 24.8 g (0.1 mol) of bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD) and 50.0 g of toluene were added, and the mixture was heated to 180°C. After confirming that the theoretical amount of water and the added toluene were extracted in the Dean-Stark extraction apparatus, heating was stopped and the mixture was cooled to room temperature. The obtained reaction solution was dropped into 2000 g of ion-exchanged water to precipitate the polymer, and after filtration and separation, it was dried in vacuo at 40°C to obtain a powdery polymer (polyimide resin A7). The weight-average molecular weight of polyimide resin A7 was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, it was Mw = 14,300.

[0401] Production Example 8: (A) Synthesis of polyimide resin A8

[0402] Except that NMP in Production Example 7 was changed to GBL, the addition amount of PDPE was changed to 23.0 g (0.083 mol), and BCD was changed to 44.4 g (0.1 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), polyimide resin A8 was obtained in the same manner as in Production Example 7. The weight-average molecular weight of polyimide resin A8 was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, it was Mw = 14,000.

[0403] Production Example 9: (A) Synthesis of polyimide resin A9

[0404] Except for changing NMP in Production Example 7 to GBL, changing PDPE to 9,9'-bis(4-aminophenyl)fluorene (BAFL) 30.1 g (0.088 mol), and changing BCD to 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) 19.6 g (0.1 mol), polyimide resin A9 was obtained in the same manner as in Production Example 7. The weight-average molecular weight of polyimide resin A9 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was Mw = 29,000.

[0405] Production Example 10: (A) Synthesis of polyimide resin A10 (MOI-modified BCD-PDPE)

[0406] In a three-necked flask equipped with a Dean-Stark extraction apparatus and purged with nitrogen, 200 g of GBL and 33.1 g (0.12 mol) of PDPE were added and dissolved, and 24.8 g (0.1 mol) of BCD and 50.0 g of toluene were added thereto, and the mixture was heated to 180°C. After confirming that the theoretical amount of water and the added toluene were extracted in the Dean-Stark extraction apparatus, heating was stopped and the mixture was cooled to room temperature.

[0407] Next, at room temperature, 6.2 g of 2-isocyanatoethyl methacrylate (hereinafter referred to as MOI) was added, and the reaction was carried out at room temperature for 12 hours. The obtained reaction solution was dropped into 2000 g of ion-exchanged water to precipitate the polymer, and after filtration and separation, it was vacuum-dried at 40°C to obtain a powdery polymer (polyimide resin A10). The weight-average molecular weight of polyimide resin A10 was measured by gel permeation chromatography (standard polystyrene conversion), and the result was Mw = 15,200.

[0408] <Example 1>

[0409] Using the polyimide precursor A1, a photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. (A) Polyimide precursor A1: 100 g of the polyimide precursor described in Production Example 1, (B) tetrazole compound B1: 3 g of 1H-tetrazole-5-carboxylic acid (manufactured by Advanced ChemBlocks), (C) photopolymerization initiator C1: 3 g of TR-PBG-3057 (manufactured by TRONLY), and (E) radically polymerizable compound E1: 10 g of NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.) were dissolved in a mixed solvent of (D) solvent D1: 80 g of γ-butyrolactone (hereinafter referred to as GBL, manufactured by Mitsubishi Chemical Corporation) and solvent D2: 20 g of dimethyl sulfoxide (hereinafter referred to as DMSO, manufactured by Toray Fine Chemical Co., Ltd.). By adding a solution of GBL:DMSO = 80:20 (mass ratio) in a required amount, the viscosity of the obtained solution was adjusted to about 40 poise to prepare a photosensitive resin composition. The composition was evaluated according to the above method. The results are shown in Table 1.

[0410] <Examples 2 to 51, Comparative Examples 1 to 13>

[0411] Except for the solvent, the blending ratio was adjusted as shown in Tables 1 to 4. In addition, it was dissolved in the solvent in the same manner as in Example 1, and the viscosity was adjusted to prepare a photosensitive resin composition. Furthermore, copper adhesion and copper void evaluation or b-HAST test were carried out to evaluate copper adhesion and copper migration properties. The results are shown in Tables 1 to 4. The compounds described in Tables 1 to 4 are as follows.

[0412] (A) Polyimide precursor or a polymer for comparison thereof

[0413] A1: The polyimide precursor described in Production Example 1

[0414] A2: The polyimide precursor described in Production Example 2

[0415] A3: The polyimide precursor described in Production Example 3

[0416] A4: The polyimide precursor described in Production Example 4

[0417] A5: The polyimide precursor described in Production Example 5

[0418] A6: The polyimide precursor described in Production Example 6

[0419] A7: The polyimide resin described in Production Example 7

[0420] A8: The polyimide resin described in Production Example 8

[0421] A9: The polyimide resin described in Production Example 9

[0422] A10: The polyimide resin described in Production Example 10

[0423] A1': ZCR-1797H (acid-modified product of epoxy acrylate having a biphenyl skeleton, manufactured by Nippon Kayaku Co., Ltd.)

[0424] (B) Tetrazole compound

[0425] B1: 1H-tetrazole-5-carboxylic acid (manufactured by Advanced ChemBlocks)

[0426] B2: Ethyl 1H-tetrazole-5-carboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0427] B3: 1H-tetrazole-5-acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0428] B4: Ethyl 1H-tetrazole-5-acetate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0429] B5: 2-(2H-tetrazol-5-yl)succinic acid (manufactured by Enamine Building Blocks)

[0430] B6: 2,2-bis(2-(2H-tetrazol-5-yl)ethyl)malonic acid (manufactured by Chemieliva pharmaceutical)

[0431] B7: 4-(1H-tetrazol-5-yl)benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0432] B8: 1H-tetrazole-5-propanoic acid (manufactured by Enamine Building Blocks)

[0433] B1': 5-amino-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0434] B2': 5-phenyltetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0435] B3': 1-methyltetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0436] (C) Photoinitiator

[0437] C1: TR-PBG3057 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0438] C2: 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime (product name KZ-941, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0439] C3: Acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime) (Product name: Irgacure OXE02, manufactured by BASF)

[0440] (D) Solvent

[0441] D1: GBL (manufactured by Mitsubishi Chemical)

[0442] D2: DMSO (manufactured by Toray Fine Chemical)

[0443] (E) Radical polymerization initiator

[0444] E1: Tris-(2-acryloyloxyethyl) isocyanurate (Product name: NK Ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0445] E2: Tetraethylene glycol dimethacrylate (Trade name: NK Ester 4G, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0446] E3: Methoxy nonaethylene glycol monomethacrylate (Product name: PME-400, manufactured by Nippon Oil Co., Ltd.)

[0447] E4: Pentaerythritol tetraacrylate (Product name: A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0448] E5: Dipentaerythritol polyacrylate (Product name: A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0449] (F) Thermal crosslinking agent

[0450] F1: Alkylated urea resin (Product name: NIKALAC MX-290, manufactured by Sanwa Chemical Co., Ltd.)

[0451] F2: 1,3,4,6-Tetra(methoxymethyl) glycoluril (Product name: NIKALAC MX-270, manufactured by Sanwa Chemical Co., Ltd.)

[0452] (G) Heterocyclic compound

[0453] G1: Benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0454] G2: 5-Carboxybenzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0455] G3: 8-Azaadenine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0456] (J) Organotitanium compound

[0457] J1: Diisopropanoltitanium bis(ethylacetoacetate) (Product name: ORGATIX TC-750, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0458] (K) Adhesion promoter

[0459] K1: N-Phenyl-3-aminopropyltrimethoxysilane (Product name: KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0460] K2: tert-Butyl (3-triethoxysilylpropyl)carbamate (manufactured by Gelest)

[0461] K3: 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0462] K4: 4,4'-Carbonylbis(2-(((3-triethoxysilyl)propyl)amino)carbonyl)benzoic acid (manufactured by this company)

[0463] K5: 2-(3-Triethoxysilylpropylcarbamoyl)benzoic acid (manufactured by this company)

[0464] (L) Sensitizer

[0465] L1: 2,2'-(Phenylimino)diethanol (manufactured by Kanto Chemical Co., Inc.)

[0466] [Table 1]

[0467]

[0468] [Table 2]

[0469]

[0470] [Table 3]

[0471]

[0472] [Table 4]

[0473]

[0474] As shown in Table 1, in the photosensitive resin compositions of Examples 3, 8, and 11 to 14, the copper adhesion was A and the copper void suppression was also A. In the photosensitive resin compositions of Examples 4 and 9, the copper void suppression was A, but the copper adhesion was B. In the photosensitive resin compositions of Examples 1 to 2, 5 to 7, and 10, both the copper adhesion and the copper void suppression were B. On the other hand, in Comparative Examples 1 to 2, both the copper adhesion and the copper voids were C, and in Comparative Examples 3 to 6, the copper void suppression and the copper adhesion were D.

[0475] From the results in Tables 2 to 4, it was found that Comparative Examples 7 to 13, which do not satisfy the necessary conditions of the present invention, could not achieve good results in both copper adhesion and copper migration performance (results of the b-HAST test). On the other hand, Examples 15 to 51 showed excellent performance in both adhesion and copper migration performance. From the comparison between Comparative Examples 7 to 11, Comparative Example 13 and Example 16, and the comparison between Comparative Example 12 and Example 47, it was found that by using the (B) tetrazole compound of the present invention, copper adhesion and copper migration performance can be improved. Comparative Examples 7 to 10 contain tetrazole compounds but do not have the structure of General Formula (1) or (2), and the pKa and tPSA also do not satisfy the preferred range of the present invention, so sufficient effects cannot be obtained. Comparative Examples 11 to 13 contain heterocyclic compounds with pKa or / and tPSA satisfying the preferred range of the present invention, but these heterocyclic compounds are not tetrazole compounds, so sufficient effects cannot be obtained.

[0476] Next, when observing the examples, it was found that Examples 16 to 20 had compositions with different contents of the (B) tetrazole compound, and Examples 16, 18, and 19 with a content in the range of 0.01 to 10 parts by mass had more excellent copper adhesion and copper migration performance. In addition, when comparing Example 16 with Example 23, or Example 18 with Examples 24 to 28, it was found that by increasing the curing temperature, copper migration can be improved, but for copper adhesion, a temperature of 230 °C or lower, and further 200 °C or lower is good. When comparing Example 31 with Example 30, it was found that by containing the (E) radically polymerizable compound, copper migration can be improved. In addition, when comparing Example 34 with Example 33, it was found that by containing the (F) thermal crosslinking agent, copper migration can be improved. When comparing Example 38 with Example 16, it was found that by containing the (G) adhesion aid, copper adhesion can be improved. Furthermore, when comparing Example 33 with Example 32, it was found that Example 32 with the content of the (E) radically polymerizable compound in the range of 20 to 80 parts by mass had better copper migration.

[0477] Industrial Applicability

[0478] By using the photosensitive resin composition of the present invention, a cured relief pattern with excellent copper adhesion and copper void suppression and less copper migration in the b-HAST test can be obtained. The photosensitive resin composition of the present invention can be preferably used, for example, in the field of photosensitive materials useful for the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, for example, it can be used for the formation of relief patterns of insulating materials for electronic components, passivation films, buffer coating films, and interlayer insulating films of semiconductor devices, etc.

Claims

1. A photosensitive resin composition containing the following components: (A) A polyimide precursor and / or a polyimide resin, (B) A tetrazole compound, (C) A photoinitiator, and (D) A solvent, wherein the pKa of the (B) tetrazole compound is 1.3 to 4.

1.

2. A photosensitive resin composition containing the following components: (A) A polyimide precursor and / or a polyimide resin, (B) A tetrazole compound, (C) A photoinitiator, and (D) A solvent, wherein the (B) tetrazole compound contains a compound represented by the following general formula (1) or the following general formula (2): In formula (1), R 1 is a hydrogen atom, or a monovalent organic group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms; the hydrogen atoms of the alkyl group and the aryl group are each independently optionally substituted or unsubstituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxysilyl group, and an amino group; In formula (2), R 2 is a hydrogen atom, or a monovalent organic group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms; R 3 is an alkylene group having 1 to 10 carbon atoms; and the hydrogen atoms of the alkyl group, the aryl group, and the alkylene group are each independently optionally substituted or unsubstituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxysilyl group, and an amino group.

3. A photosensitive resin composition containing the following components: (A) A polyimide precursor and / or a polyimide resin, (B) A tetrazole compound, (C) A photoinitiator, and (D) A solvent, wherein the polar surface area (tPSA) of the (B) tetrazole compound is 81 to 200.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the content of the (B) component is 0.01 to 10 parts by mass with respect to 100 parts by mass of the (A) component.

5. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (B) tetrazole compound contains a compound represented by the following general formula (3): In formula (3), R 4 is a hydrogen atom, or a monovalent organic group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms; the hydrogen atoms of the alkyl group and the aryl group are each independently optionally substituted or unsubstituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxysilyl group, and an amino group.

6. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (B) tetrazole compound contains a compound represented by the following formula:

7. The photosensitive resin composition according to any one of claims 1 to 3, further containing (E) a radically polymerizable compound.

8. The photosensitive resin composition according to claim 7, wherein the content of the (E) component is 20 to 80 parts by mass with respect to 100 parts by mass of the (A) component.

9. The photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (4): In formula (4), X 1 is a tetravalent organic group, Y 1 is a divalent organic group, n 1 is an integer from 2 to 150, and R 11 and R 12 are each independently a hydrogen atom or a monovalent organic group; and / or the photosensitive resin composition contains the polyimide resin, and the polyimide resin has a structural unit represented by the following general formula (4'): In formula (4'), X 1 is a tetravalent organic group, Y 1 is a divalent organic group, and n is an integer from 1 to 150.

10. The photosensitive resin composition according to claim 9, wherein In the general formula (4), R 11 and R 12 at least one of them has a structural unit represented by the following general formula (5): In formula (5), L 1 , L 2 and L 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m 1 is an integer from 2 to 10.

11. The photosensitive resin composition according to claim 9, wherein X of the general formula (4') 1 is at least one selected from the structures represented by the following general formulas (6) to (14), or Y of the general formula (4') 1 is at least one selected from the structures represented by the following general formulas (15) to (23):

12. The photosensitive resin composition according to any one of claims 1 to 3, further containing (F) a thermal crosslinking agent.

13. The photosensitive resin composition according to any one of claims 1 to 3, further containing (K) an adhesion aid.

14. The photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive resin composition is a photosensitive resin composition for forming a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure.

15. A method for manufacturing a cured relief pattern, comprising the following steps: (1) A step of coating the photosensitive resin composition according to any one of claims 1 to 3 on a substrate to form a photosensitive resin layer on the substrate; (2) The step of exposing the photosensitive resin layer; (3) The step of developing the exposed photosensitive resin layer to form a relief pattern; and (4) The step of heat-treating the relief pattern to form a cured relief pattern.

16. The method for manufacturing a cured relief pattern according to claim 15, wherein, the heat treatment in the step (4) is a heat treatment at 350 °C or lower.

17. A cured film containing a cured product of the photosensitive resin composition according to any one of claims 1 to 3.

18. A method for manufacturing a polyimide film, which comprises curing the photosensitive resin composition according to any one of claims 1 to 3.

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