Polyimide resin precursor, and photosensitive composition

Abstract

To provide a polyimide resin precursor for giving a polyimide resin film excellent in chemical resistance and a photosensitive composition excellent in resolution, a photosensitive composition containing the polyimide resin precursor, a method for producing a polyimide resin film using the photosensitive composition, and a method for producing a patterned polyimide resin film.SOLUTION: A polyimide resin precursor containing a constitutional unit having a specific structure having a phenolic hydroxyl group at its side chain, is added to a photosensitive composition together with a photosensitive agent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyimide resin precursor, a photosensitive composition containing the polyimide resin precursor, a method for producing a polyimide resin film using the photosensitive composition, and a method for producing a patterned polyimide resin film.

Background Art

[0002] Polyimide resins and polyamide resins have excellent heat resistance, mechanical strength, insulation properties, and characteristics such as a low dielectric constant, and are therefore widely used as insulating materials and protective materials in various elements and electrical and electronic components such as electronic substrates such as multilayer wiring boards.

[0003] In recent years, communication devices such as mobile phones have been operating at higher frequencies. Therefore, insulation portions that insulate metal wirings of communication devices are also required to cope with higher frequencies. Here, the higher the frequency, the greater the transmission loss, and when the transmission loss increases, the electrical signal attenuates. Therefore, in order to further reduce the transmission loss as a countermeasure against higher frequencies for resins such as polyimide resins and polyamide resins, further reduction of the dielectric tangent and further reduction of the dielectric constant in the high-frequency band are required.

[0004] In addition, when manufacturing various elements and electronic substrates, etc., it is often necessary to form an insulating material or a protective material only at a desired position. For this reason, it is also required that the photolithography method can be applied.

[0005] From the above requirements, a photosensitive resin composition that can form a patterned resin film with a low dielectric tangent by applying the photolithography method includes a resin and a photosensitizer, and as the resin, a polyimide resin, a polyamic acid, a polyamide resin, a polybenzoxazole resin, and a polybenzoxazole resin precursor containing a structural unit derived from a diamine compound having a specific structure having an aromatic group are used. At least one selected from the group consisting of (Patent Document 1) has been proposed.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] When using the photosensitive resin composition described in Patent Document 1, a patterned resin film with a low dielectric tangent can be formed by applying the photolithography method. On the other hand, further improvement in chemical resistance and resolution is required for the photosensitive resin composition described in Patent Document 1.

[0008] The present invention has been made in view of the above problems, and provides a polyimide resin precursor that gives a polyimide resin film excellent in chemical resistance and a photosensitive composition excellent in resolution, a photosensitive composition containing the polyimide resin precursor, a method for producing a polyimide resin film using the photosensitive composition, and a method for producing a patterned polyimide resin film.

Means for Solving the Problems

[0009] The present inventors have found that the above problems can be solved by adding a polyimide resin precursor containing a structural unit having a phenolic hydroxyl group in the side chain to a photosensitive composition together with a photosensitizer, and have completed the present invention. More specifically, the present invention provides the following.

[0010] [1] A polyimide resin precursor containing a structural unit (1) represented by the following formula (1), and containing or not containing a structural unit (2) represented by the following formula (2), wherein the structural unit (2) is a structural unit that does not correspond to the structural unit (1).

Chemical Formula

[10] A photosensitive composition comprising a polyimide resin precursor (A), a photosensitizer (B), and a crosslinking agent (C), The photosensitizer (B) is a quinonediazide group-containing compound (B2), The photosensitive composition according to [7], wherein the crosslinking agent (C) is a compound capable of forming a crosslink by reaction with a phenolic hydroxyl group or an aromatic group having a phenolic hydroxyl group.

[11] The crosslinking agent (C) is a methylol type crosslinking agent (C1), The photosensitive composition according to

[10] , wherein the methylol type crosslinking agent (C1) has two or more crosslinkable groups selected from a methylol group and an alkoxymethyl group.

[12] A method for producing a polyimide resin film, comprising coating the photosensitive composition according to any one of [7] to

[11] on a substrate to form a coating film, and heating the coating film to imidize the polyimide resin precursor (A) contained in the coating film.

[13] Coating a photosensitive composition according to any one of [7] to

[11] on a substrate to form a coating film; Selectively exposing the coating film; Developing the exposed coating film with a developer; A method for producing a patterned polyimide resin film, comprising heating the developed coating film to imidize the polyimide resin precursor (A) contained in the coating film.

Advantages of the Invention

[0011] According to the present invention, there can be provided a polyimide resin precursor that provides a polyimide resin film excellent in chemical resistance and a photosensitive composition excellent in resolution, a photosensitive composition containing the polyimide resin precursor, a method for producing a polyimide resin film using the photosensitive composition, and a method for producing a patterned polyimide resin film.

Embodiments for Carrying Out the Invention

[0012] ≪Polyimide Resin Precursor≫ The polyimide resin precursor contains a structural unit (1) represented by the following formula (1) and may or may not contain a structural unit (2) represented by the following formula (2). The structural unit (2) is a structural unit that does not correspond to the structural unit (1).

[0013]

Chemical Formula

[0014]

Chemical formula

[0015] In formula (1), the two Rs A1 , the two Rs A2 , and the two a's may each be the same or different.)

[0016] In terms of easily obtaining a polyimide resin precursor that provides a polyimide resin film excellent in chemical resistance and a photosensitive composition excellent in resolution, the ratio of the constitutional unit (1) to the total number of moles of all constitutional units constituting the polyimide resin precursor is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, even more preferably 95 mol% or more, and particularly preferably 100 mol%.)

[0017] The polyimide resin precursor is typically a polymer of a diamine compound, a dicarboxylic acid which is a reaction product of a tetracarboxylic dianhydride and alcohols.) However, the diamine compound, the dicarboxylic acid, the tetracarboxylic dianhydride, and the alcohols are selected such that the polyimide resin precursor satisfies the above-mentioned predetermined requirements.)

[0018] [Constitutional unit (1)] As described above, the constitutional unit (1) is the constitutional unit represented by the above formula (1). Hereinafter, the diamine compound and the dicarboxylic acid that give the constitutional unit (1) will be described.

[0019] (Diamine compound) The diamine compound that gives the constitutional unit (1) represented by the formula (1) is represented by the following formula (A2a). H2N-Y A1 -NH2 ··· (A2a) (In the formula (A2a), Y A1 represents a divalent organic group having 4 or more and 40 or less carbon atoms.)

[0020] Y A1 is a divalent organic group having 4 or more and 40 or less carbon atoms. Y A1 may have one or more substituents in addition to the two amino groups. Preferable examples of the substituent include a fluorine atom, an alkyl group having 1 or more and 6 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, a fluorinated alkyl group having 1 or more and 6 or less carbon atoms, a fluorinated alkoxy group having 1 or more and 6 or less carbon atoms, a carboxy group, or a hydroxy group. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.

[0021] Y A1 The lower limit of the number of carbon atoms of the organic group as Y is 4, preferably 6, the upper limit is 40, and preferably 30. Y A1 may be an aliphatic group, but is preferably an organic group containing one or more aromatic rings. Y A1 The divalent organic group as Y is preferably a residue obtained by removing two amino groups from an aromatic diamine.

[0022] Y A1When the organic group contains an aromatic ring with 1 or more, the organic group may be an aromatic group itself, or may be a group in which 2 or more aromatic groups are bonded via a bond containing an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, or a heteroatom such as an oxygen atom, a sulfur atom, and a nitrogen atom. Y A1 Examples of the bond containing a heteroatom such as an oxygen atom, a sulfur atom, and a nitrogen atom contained in A1 include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -S-S-, etc., and -COO-, -O-, -CO-, and -S- are preferable.

[0023] Y A1 The aromatic ring that binds to the amino group in A1 is preferably a benzene ring. Y A1 When the ring that binds to the amino group in A1 is a condensed ring containing 2 or more rings, the ring that binds to the amino group in the condensed ring is preferably a benzene ring. Also, Y A1 The aromatic ring contained in A1 may be an aromatic heterocyclic ring.

[0024] Y A1 When Y is an organic group containing an aromatic ring, from the viewpoint of improving the electrical properties and mechanical properties of the polyimide resin formed using the polyimide resin precursor, the organic group is preferably at least one of the groups represented by the following formulas (21) to (24).

Chemical formula

[0025] In formulas (21) to (24), R 111 represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a carboxy group, a sulfonic acid group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, and a halogenated alkyl group having 1 to 4 carbon atoms. In formula (24), Q 1is one selected from the group consisting of a 9,9'-fluorenylidene group, or a group represented by the formula: -C6H4-, -C6H4-C6H4-, -O-C6H4-C6H4-O-, -O-C6H4-CO-C6H4-O-, -O-C6H4-C(CH3)2-C6H4-O-, -OCO-C6H4-COO-, -OCO-C6H4-C6H4-COO-, -OCO-, -O-, -CO-, -C(CF3)2-, -C(CH3)2-, -CH2-, -O-C6H4-SO2-C6H4-O-, -C(CH3)2-C6H4-C(CH3)2-, -O-C 10 H6-O-, -O-C6H4-O-, -O-CH2-O-, and -O-(CH2) n -O-.

[0026] Q 1 In the exemplification of -C6H4-, it is a phenylene group, preferably an m-phenylene group and a p-phenylene group, more preferably a p-phenylene group. Also, -C 10 H6- is a naphthalenediyl group, preferably a naphthalene-1,2-diyl group, a naphthalene-1,4-diyl group, a naphthalene-2,3-diyl group, a naphthalene-2,6-diyl group, and a naphthalene-2,7-diyl group, more preferably a naphthalene-1,4-diyl group and a naphthalene-2,6-diyl group. Q 1 In the exemplification of Q, n is an integer of 1 or more, preferably an integer of 1 or more and 20 or less, more preferably an integer of 1 or more and 12 or less, still more preferably an integer of 1 or more and 6 or less.

[0027] Y A1 As, among the diamine compounds containing a group represented by the formula (24), the compound represented by the following formula (a2) is preferred. Regarding n in the formula (a2), it is as described for Q 1 in the formula (24).

Chemical formula

[0028] R in the formulas (21) to (24) 111From the viewpoint of improving the electrical properties of the formed resin film, a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group is more preferable, and a hydrogen atom or a trifluoromethyl group is particularly preferable.

[0029] Q in formula (24) 1 From the viewpoints of the electrical properties and mechanical properties of the formed resin film, -C6H4-C6H4-, -O-C6H4-C6H4-O-, -O-C6H4-CO-C6H4-O-, -O-C6H4-C(CH3)2-C6H4-O-, -OCO-C6H4-COO-, -OCO-C6H4-C6H4-COO-, -OCO-, -O-, -CO-, -C(CF3)2-, -C(CH3)2-, -CH2-, -O-C6H4-SO2-C6H4-O-, -C(CH3)2-C6H4-C(CH3)2-, -O-C 10 H6-O-, -O-C6H4-O-, -O-CH2-O-, -O-(CH2)2-O-, -O-(CH2)3-O-, -O-(CH2)4-O-, -O-(CH2)5-O-, and -O-(CH2)6-O- are preferable. From the viewpoints of improving the electrical properties and mechanical properties of the polyimide resin formed using the polyimide resin precursor, Q in formula (24) 1 As for it, -O-C6H4-C6H4-O- and -O-C6H4-C(CH3)2-C6H4-O- are more preferable, and a group represented by -O-C6H4-C6H4-O- and in which -C6H4- is a p-phenylene group in both cases is particularly preferable.

[0030] When an aromatic diamine compound is used as the diamine compound represented by formula (A2a), for example, the following aromatic diamine compounds can be preferably used. That is, examples of the aromatic diamine compound include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 9,10-diaminoanthracene, 9,10-bis(4-aminophenyl)anthracene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfo-4,4'-diaminodiphenyl ether, 4,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, bis(3-amino-4-hydroxyphenyl)ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 4,4'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(4-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]ketone, 2,2-bis[4-{4-amino-2-(trifluoromethyl)phenoxy}phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-amino-3-methylphenyl)fluorene, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 9,9-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 9,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 2,7-diaminofluorene, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(3-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-6-aminobenzoxazole, 2-(3-aminophenyl)-6-aminobenzoxazole, 1,4-bis(5-amino-2-benzoxazolyl)benzene, 1,4-bis(6-amino-2-benzoxazolyl)benzene, 1,3-bis(5-amino-2-benzoxazolyl)benzene, 1,3-bis(6-amino-2-benzoxazolyl)benzene, 2,6-bis(4-aminophenyl)benzobisoxazole, 2,6-bis(3-aminophenyl)benzobisoxazole, bis[(3-aminophenyl)-5-benzoxazolyl], bis[(4-aminophenyl)-5-benzoxazolyl], bis[(3-aminophenyl)-6-benzoxazolyl], bis[(4-aminophenyl)-6-benzoxazolyl], N,N'-bis(3-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'-[1,4-phenylenebis(1-methylethane-1,1-diyl)]dianiline, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 4-aminobenzoic acid 4-aminophenyl ester, 1,3-bis(4-anilino)tetramethyldisiloxane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone and the like can be mentioned. Among these, from the viewpoint of improving electrical properties and mechanical properties, 4,4'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(4-aminophenoxy)biphenyl, and 3,3'-bis(4-aminophenoxy)biphenyl are preferable.,

[0031] Also, Y A1 As this, a silicon atom-containing group which may have a chain-like aliphatic group and / or an aromatic ring can be adopted. As such a silicon atom-containing group, typically, the groups shown below can be used.

Chemical formula

[0032] Specific examples of the compound having amino groups at both ends and a silicon atom-containing group include amino group-terminated methylphenyl silicone (e.g., X-22-1660B-3 (number average molecular weight of about 4,400) and X-22-9409 (number average molecular weight of about 1,300) manufactured by Shin-Etsu Chemical Co., Ltd.), amino group-terminated dimethyl silicone (e.g., X-22-161A (number average molecular weight of about 1,600), X-22-161B (number average molecular weight of about 3,000), and KF8012 (number average molecular weight of about 4,400) manufactured by Shin-Etsu Chemical Co., Ltd.; BY16-835U (number average molecular weight of about 900) manufactured by Toray Dow Corning; and Silaplane FM3311 (number average molecular weight of about 1,000) manufactured by JNC), etc.

[0033] In addition, as the diamine compound represented by the formula (A2a), a diamine having an oxyalkylene group can also be preferably used. Preferred examples of the oxyalkylene group include an ethyleneoxy group and a propyleneoxy group (-C(CH3)-CH2-O-, -CH2-C(CH3)-O-, or -CH2CH2CH2-O-). The diamine having an oxyalkylene group may contain a combination of two or more oxyalkylene groups. When the diamine having an oxyalkylene group contains two or more oxyalkylene groups, the two or more oxyalkylene groups may be contained in the diamine in a block manner or in a random manner. The diamine having an oxyalkylene group preferably does not contain a cyclic group, and more preferably does not contain an aromatic group. Specific examples of the diamine having an oxyalkylene group include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) EDR-148, Jeffamine (registered trademark) EDR-176, Jeffamine (registered trademark) D-200, Jeffamine (registered trademark) D-400, Jeffamine (registered trademark) D-2000, and Jeffamine (registered trademark) D-4000, all manufactured by Huntsman Corporation, as well as 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc.

[0034] Since the diamine compound is represented by the formula (A2a) and the polyimide resin precursor has excellent solubility in an organic solvent and the dielectric properties of the polyimide resin formed using the polyimide resin precursor in a high-frequency band A1 is a diamine compound (A-1) in which Y is a group represented by the following formula (A1-1), represented by the formula (A2a) and Y A1 has a partial structure represented by the formula (A2-1) described later and does not correspond to the diamine compound (A-1), a diamine compound (A-2), a partial structure represented by the formula (A3) described later, and does not correspond to the diamine compound (A-1) and the diamine compound (A-2). It is preferably selected from the group consisting of a diamine compound (A-3) and a dimer diamine compound (A-4). Among these, the diamine compound (A-1) and the diamine compound (A-2) are preferred.

[0035] (Diamine compound (A-1)) The diamine compound (A-1) is a diamine compound represented by the formula (A1-1) and Y A1 is a group represented by the following formula (A1-1).

Chemical formula

[0036] In formula (A1-1), Ar is a phenyl group optionally substituted with R a2 or a naphthyl group optionally substituted with R a2 Ar is preferably a phenyl group or a naphthyl group. That is, in formula (A1-1), ma2 is preferably 0.)

[0037] In formula (A1-1), R a2 is an aliphatic group having 1 to 20 carbon atoms, a hydroxy group, a carboxy group, a sulfonic acid group, or a halogen atom. The organic group as R a2 may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms.) R a2 The aliphatic group as preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.)

[0038] R a2Examples of the aliphatic group as such include linear alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group; linear alkenyl groups such as vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n-butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group; halogenated linear alkyl groups such as chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and perfluorodecyl group; halogenated cycloalkyl groups such as 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group, and 4-bromocyclohexyl group; hydroxy linear alkyl groups such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, and 4-hydroxy-n-butyl group; hydroxy cycloalkyl groups such as 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group, and 4-hydroxycyclohexyl group;Chain-like alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, and n-icosyloxy group; chain-like alkenyloxy groups such as vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group, and 3-n-butenyloxy group; alkoxyalkyl groups such as methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n-propyl group, 3-n-propoxy-n-propyl group, 4-methoxy-n-butyl group, 4-ethoxy-n-butyl group, and 4-n-propoxy-n-butyl group; alkoxyalkoxy groups such as methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 3-methoxy-n-propoxy group, 3-ethoxy-n-propoxy group, 3-n-propoxy-n-propoxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n-propoxy-n-butyloxy group; aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, and decanoyl group; chain-like alkyloxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyloxycarbonyl group;They are aliphatic acyloxy groups such as formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group, nonanoyloxy group, and decanoyloxy group, etc.;

[0039] In formula (A1-1), ma3 is an integer of 1 or more and 10 or less. The value of ma3 is not particularly limited as long as it is 1 or more and 10 or less, and is appropriately selected according to the structure of X. The value of ma3 is preferably 1 or more and 4 or less, and more preferably 1 or 2.

[0040] In formula (A1-1), X is an organic group having 1 or more and 100 or less carbon atoms. The number of carbon atoms of the organic group as X is preferably 2 or more and 80 or less, and more preferably 6 or more and 50 or less. The organic group as X may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms. In the compound represented by formula (A1-1), the two amino groups are each bonded to a carbon atom in the organic group as X.

[0041] The organic group as X may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group. The organic group as X may be a group bonded through a bond containing heteroatoms such as an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the bond containing heteroatoms such as an oxygen atom, a sulfur atom, and a nitrogen atom contained in the organic group as X include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -S-S-, etc., and -O-, -CO-, and -S- are preferred.

[0042] When the organic group as X is an aliphatic group, the aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. When the organic group as X is an aliphatic group, the aliphatic group is preferably an aliphatic hydrocarbon group. When the organic group as X is an aliphatic group, the aliphatic group may be linear, cyclic, or a combination of a linear aliphatic group and a cyclic aliphatic group. The linear aliphatic group may have a branch.

[0043] When the organic group as X is an aliphatic group, the aliphatic group is preferably a group obtained by removing (ma1 + ma3 + 2) hydrogen atoms from an alkylene group having 1 to 20 carbon atoms, more preferably a group obtained by removing (ma1 + ma3 + 2) hydrogen atoms from an alkylene group having 1 to 16 carbon atoms, and even more preferably a group obtained by removing (ma1 + ma3 + 2) hydrogen atoms from an alkylene group having 1 to 12 carbon atoms.

[0044] When the organic group as X is a group containing an aromatic group, X, Ar, and R in formula (A1-1) a1 and R a2 The groups composed of are groups represented by the following formulas (11) to (15).

Chemical formula

[0045] In formulas (11) to (15), Ar, R a1 R a2, ma1, ma2, and ma3 are the same as these in formula (A1-1). In formula (13), ma4 and ma5 are each independently an integer of 0 or more and 4 or less. ma6 and ma7 are each independently an integer of 0 or more and 4 or less, and the sum of ma6 and ma7 is 1 or more and 8 or less. In formula (14), ma8, ma9, and ma10 are each independently an integer of 0 or more and 4 or less. The sum of ma8, ma9, and ma10 is 0 or more and 10 or less. ma11, ma12, and ma13 are each independently an integer of 0 or more and 4 or less. The sum of ma11, ma12, and ma13 is 1 or more and 10 or less. In formula (15), ma14 is an integer of 0 or more and 3 or less. ma15 is an integer of 0 or more and 5 or less. The sum of ma14 and ma15 is 0 or more and 8 or less. ma16 is an integer of 0 or more and 3 or less. ma17 is an integer of 0 or more and 5 or less. The sum of ma16 and ma17 is 1 or more and 8 or less.

[0046] In formula (11), it is preferable that ma1 is 0, ma2 is preferably 0, and ma3 is preferably 1 or 2. In formula (12), it is preferable that ma1 is 0, ma2 is preferably 0, and ma3 is preferably 1 or 2. In formula (13), it is preferable that ma2 is 0, ma4 and ma5 are each preferably 0, ma6 and ma7 are each preferably 0, 1, or 2, and the sum of ma6 and ma7 is 1 or more and preferably 4 or less. In formula (14), it is preferable that ma2 is 0, ma8, ma9, and ma10 are each preferably 0, ma11, ma12, and ma13 are each preferably 0, 1, or 2, and the sum of ma11, ma12, and ma13 is 1 or more and preferably 6 or less. In formula (15), it is preferable that ma2 is 0, ma14 and ma15 are each preferably 0, ma16 and ma17 are each preferably 0, 1, or 2, and the sum of ma16 and ma17 is 1 or more and preferably 4 or less.

[0047] In formulas (11) to (15), R a3is a single bond or a divalent linking group, provided that the divalent linking group is not a group containing an aromatic group. Examples of the divalent linking group include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -S-S-, and groups formed by combining two or more of these groups. The number of carbon atoms of the linking group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. The aliphatic hydrocarbon group as the linking group may have one or more unsaturated bonds, may have a branch, and may contain a ring structure. Specific examples of the aliphatic hydrocarbon group as the linking group include methylene group, ethane-1,2-diyl group (ethylene group), ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, octadecane-1,18-diyl group, nonadecane-1,19-diyl group, icosane-1,20-diyl group, ethene-1,2-diyl group (vinylene group), propene-1,3-diyl group, ethyne-1,2-diyl group, and propyne-1,3-diyl group, etc.

[0048] Preferable examples of the linking group include an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, an alkynylene group having 2 to 6 carbon atoms, an alkyleneoxy group having 1 to 6 carbon atoms, an alkenyleneoxy group having 2 to 6 carbon atoms, an alkynyleneoxy group having 2 to 6 carbon atoms, an alkylenethio group having 1 to 6 carbon atoms, an alkenylenethio group having 2 to 6 carbon atoms, an alkynylenethio group having 2 to 6 carbon atoms, an alkyleneamino group having 1 to 6 carbon atoms, an alkenyleneamino group having 2 to 6 carbon atoms, an alkynyleneamino group having 2 to 6 carbon atoms, -CONH-, -NH-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, -OCONH-, and -OCOO-, etc.

[0049] Among the divalent groups represented by the formula (A1-1), the divalent group represented by the following formula (A1-2) is preferable because the polyimide resin formed using the polyimide resin precursor exhibits a low dielectric tangent and good mechanical properties.

Chemical formula

[0050] In the formula (A1-2), the organic group as Y a1 may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms. The organic group as Y a1 is preferably a hydrocarbon group. The hydrocarbon group as Y a1 may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Y a1As the hydrocarbon group, an aromatic hydrocarbon group is preferable, and a phenylene group and a naphthalenediyl group are more preferable. Y a1 Preferable specific examples of the aromatic hydrocarbon group include a p-phenylene group, an m-phenylene group, an o-phenylene group, a naphthalene-1,4-diyl group, a naphthalene-1,2-diyl group, a naphthalene-1,3-diyl group, a naphthalene-1,5-diyl group, a naphthalene-1,6-diyl group, a naphthalene-1,7-diyl group, a naphthalene-1,8-diyl group, a naphthalene-2,6-diyl group, a naphthalene-2,7-diyl group, and a naphthalene-2,3-diyl group. Among these aromatic hydrocarbon groups, a p-phenylene group and an m-phenylene group are preferable, and a p-phenylene group is more preferable.

[0051] In formula (A1-2), it is preferable that na2 is 1, and it is more preferable that both na1 and na2 are 1, and Y a1 is an organic group. In this case, due to the high steric freedom of the ether bond, the structural unit derived from the diamine compound (A-1) having a divalent group represented by formula (A1-2) is likely to be packed well, and it is considered easy to obtain a polyimide resin precursor that gives a polyimide resin excellent in mechanical properties, thermal properties, electrical properties, etc.

[0052] In formula (A1-2), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2.

[0053] Specific examples of the diamine compound (A-1) described above include the following compounds.

Chemical formula

[0054]

Chemical formula

[0055]

Chemical formula

[0056]

Chem.

[0057]

Chem.

[0058]

Chem.

[0059]

Chem.

[0060]

Chem.

[0061] (Diamine compound (A-2)) The diamine compound (A-2) has a partial structure represented by the following formula (A2-1) and is a diamine compound that does not correspond to the diamine compound (A-1).

Chem.

[0062] In formula (A2-1), R a3 and R a4Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these alkyl groups, a methyl group and an ethyl group are preferred, and a methyl group is more preferred. In formula (A2-1), R a3 and R a4 Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred. In formula (A2-1), R a3 and R a4 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, a chlorine atom and a bromine atom are preferred.

[0063] In formula (A2-1), ma4 and ma5 are each independently an integer of 0 or more and 4 or less. Since the diamine compound (A-2) is easily available, etc., ma4 and ma5 are each preferably an integer of 0 or more and 2 or less, and more preferably 0.

[0064] Examples of the suitable divalent group having the partial structure represented by formula (A2-1) include the divalent group represented by the following formula (A2-2). [Chemical formula] (In formula (A2-2), X 1 and X 2 are each independently an aromatic hydrocarbon group which may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. R a3 , R a4, ma4, and ma5 are the same as these in formula (A2-1). However, the upper limit of the number of carbon atoms of the divalent group represented by formula (A2-2) is 40.)

[0065] X in formula (A2-2) 1 and X 2 are each independently a divalent aromatic hydrocarbon group which may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom.) Examples of the alkyl group having 1 to 4 carbon atoms as a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these alkyl groups, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.) Examples of the alkoxy group having 1 to 4 carbon atoms as a substituent include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.) Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, a chlorine atom and a bromine atom are preferred.)

[0066] X 1 and X 2 The number of carbon atoms of the aromatic hydrocarbon group as X and X is not particularly limited as long as the number of carbon atoms of the divalent group represented by formula (A2-2) is 40 or less. Note that the number of carbon atoms of the aforementioned aromatic hydrocarbon group does not include the number of carbon atoms of the substituent.) X 1 , and X 2Examples of the aromatic hydrocarbon group as such include phenylene groups such as o-phenylene group, m-phenylene group, and p-phenylene group; naphthalenediyl groups such as naphthalene-1,4-diyl group, naphthalene-1,3-diyl group, naphthalene-2,6-diyl group, and naphthalene-2,7-diyl group; and biphenyldiyl groups such as biphenyl-4,4'-diyl group, biphenyl-3,4'-diyl group, and biphenyl-3,3'-diyl group.

[0067] X 1 、and X 2 Examples of X include p-phenylene group, m-phenylene group, naphthalene-1,4-diyl group, and biphenyl-4,4'-diyl group, with p-phenylene group and biphenyl-4,4'-diyl group being more preferred, and p-phenylene group being even more preferred.

[0068] Specific examples of the diamine compound (A-2) having a divalent group having the partial structure represented by the formula (A2-1) described above include the following compounds. [Chemical formula]

[0069] (Diamine compound (A-3)) The diamine compound (A-3) has a partial structure represented by the following formula (A3) and is a diamine compound that does not fall under the diamine compound (A-1) and the diamine compound (A-2). [Chemical formula] (In the formula (A3), R a5 and R a6 are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, ma6 and ma7 are each independently an integer of 0 to 4, R a7 and R a8 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or a phenyl group, R a7 and Ra8 They may combine with each other to form a ring. )

[0070] In formula (A3), R a5 and R a6 Examples of the alkyl group having 1 to 4 carbon atoms as R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these alkyl groups, a methyl group and an ethyl group are preferable, and a methyl group is more preferable. In formula (A3), R a5 and R a6 Examples of the alkoxy group having 1 to 4 carbon atoms as R include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Among these alkoxy groups, a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable. In formula (A3), R a5 and R a6 Examples of the halogen atom as R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, a chlorine atom and a bromine atom are preferable.

[0071] In formula (A3), ma6 and ma7 are each independently an integer of 0 or more and 4 or less. From the ease of obtaining the diamine compound (A-3) and the like, ma6 and ma7 are each preferably an integer of 0 or more and 2 or less, and more preferably 0.

[0072] In formula (A3), R a7 and R a8 Examples of the alkyl group having 1 to 4 carbon atoms as R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. In formula (A3), R a7 and R a8Examples of the alkyl halide group having 1 to 4 carbon atoms include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, and 1,1,2,2,2-pentafluoroethyl group. R in formula (A3) a7 and R a8 are preferably a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group, and a phenyl group because of good solubility of the polyimide resin precursor in an organic solvent and easy availability of the diamine compound (A-3). Also, it is also preferable that R a7 and R a8 are bonded to each other to form a cycloalkylidene group having 5 to 8 carbon atoms such as a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, and a cyclooctylidene group.

[0073] Preferable specific examples of the partial structure represented by formula (A3) include the following structures.

Chemical formula

[0074] Preferable compounds as the diamine compound (A-3) include compounds represented by the following formula (A3-1).

Chemical formula

[0075] X in formula (A3-1) 3 and X 4 are each independently a divalent aromatic hydrocarbon group which may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. Examples of the alkyl group having 1 to 4 carbon atoms as a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these alkyl groups, a methyl group and an ethyl group are preferable, and a methyl group is more preferable. Examples of the alkoxy group having 1 to 4 carbon atoms as a substituent include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Among these alkoxy groups, a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable. Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, a chlorine atom and a bromine atom are preferable.

[0076] X 3 and X 4 The number of carbon atoms of the aromatic hydrocarbon group as X and X is not particularly limited, and for example, 6 or more and 50 or less is preferable, and 6 or more and 20 or less is more preferable. Note that the number of carbon atoms of the aforementioned aromatic hydrocarbon group does not include the number of carbon atoms of the substituent. X 3 and X 4 Examples of the aromatic hydrocarbon group as X and X include phenylene groups such as an o-phenylene group, an m-phenylene group, and a p-phenylene group, naphthalenediyl groups such as a naphthalene-1,4-diyl group, a naphthalene-1,3-diyl group, a naphthalene-2,6-diyl group, and a naphthalene-2,7-diyl group, and biphenyldiyl groups such as a biphenyl-4,4'-diyl group, a biphenyl-3,4'-diyl group, and a biphenyl-3,3'-diyl group are preferable.

[0077] X 3 and X 4 Examples of the diamine compound (A-3) represented by the formula (A3) described above include, as the group X, a p-phenylene group, an m-phenylene group, a naphthalene-1,4-diyl group, and a biphenyl-4,4'-diyl group. Among them, a p-phenylene group and a biphenyl-4,4'-diyl group are more preferable, and a p-phenylene group is even more preferable.

[0078] Specific examples of the diamine compound (A-3) represented by the formula (A3) described above include the following compounds.

Chemical formula

[0079]

Chemical formula

[0080] (Dimer diamine compound (A-4)) Since it is easy to obtain a polyimide resin precursor that gives a polyimide resin having a low dielectric constant and a low dielectric loss tangent in a high frequency band, the dimer diamine compound (A-4) is also preferable as the diamine compound. The dimer diamine compound (A-4) is a diamine compound in which two terminal carboxy groups of the dimer acid are substituted with an aminomethyl group or an amino group. The dimer acid is a known dibasic acid obtained by an intermolecular polymerization reaction of an unsaturated fatty acid. The industrial production process for producing the dimer acid is almost standardized. Typically, the dimer acid is obtained by dimerizing an unsaturated fatty acid having 11 or more and 22 or less carbon atoms in the presence of a clay catalyst or the like. Industrially obtained dimer acid mainly consists of a dibasic acid having 36 carbon atoms obtained by dimerizing unsaturated fatty acids having 18 carbon atoms such as oleic acid, linoleic acid, and linolenic acid. Industrially obtained dimer acid may contain, in arbitrary amounts, monomer acids having 18 carbon atoms, trimer acids having 54 carbon atoms, and other polymerized fatty acids having 20 or more and 54 or less carbon atoms, depending on the degree of purification.

[0081] As the dimer diamine compound (A-4), known dimer diamine compounds can be used without particular limitation. Regarding the dimer diamine, for example, it is described in JP-A-9-12712.

[0082] Preferable examples of the dimer diamine compound (A-4) include compounds represented by the following formula. In the following formula, m, n, p, and q are each an integer of 1 or more. m + n is preferably 6 or more and 17 or less. p + q is preferably 8 or more and 19 or less. [Chemical formula]

[0083] As the dimer diamine compound (A-4), commercially available dimer diamine compounds can be used. Examples of commercially available dimer diamine compounds include Versamine 551 (manufactured by Cognis Japan Co., Ltd.), Versamine 552 (a hydrogenated product of Versamine 551, manufactured by Cognis Japan Co., Ltd.), PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.), and PRIAMINE 1074 (manufactured by Croda Japan Co., Ltd.).

[0084] The ratio of the number of moles of one or more compounds selected from the group consisting of the diamine compound (A-1), the diamine compound (A-2), the diamine compound (A-3), and the dimer diamine compound (A-4) to the total number of moles of the diamine compounds is preferably 10 mol% or more and 100 mol% or less, more preferably 15 mol% or more and 100 mol% or less, and even more preferably 20 mol% or more and 100 mol% or less.

[0085] (Dicarboxylic acid) The dicarboxylic acid is a reaction product of a tetracarboxylic dianhydride and alcohols. The polyimide resin precursor essentially contains the structural unit (1) represented by the aforementioned formula (1). The dicarboxylic acid that provides the structural unit (1) is a reaction product of a tetracarboxylic dianhydride represented by the following formula (A3a) and a polyol represented by the following formula (a3a). In formula (A3a) and formula (a3a), RA1 , R A2 , a, and X A1 in formula (1), R A1 , R A2 , a, and X A1 are the same as

Chemical Formula

[0086] Note that R A1 is a divalent aliphatic group having 2 or more carbon atoms which may be substituted with a hydroxyl group. R A2 is an a + 1-valent aromatic group. Therefore, the hydroxyl group bonded to R A1 is an alcoholic hydroxyl group. Also, the hydroxyl group bonded to R A2 is a phenolic hydroxyl group. When the polyol represented by formula (a3a) and the tetracarboxylic dianhydride represented by formula (A3a) are reacted, the alcoholic hydroxyl group in the polyol reacts with the dicarboxylic anhydride group. As a result, an ester group represented by -CO-O-R A1 -R A2 -(OH) a is formed.

[0087] Hereinafter, the tetracarboxylic dianhydride represented by formula (A3a) and the polyol represented by formula (a3a) will be described.

[0088] · Tetracarboxylic dianhydride As described above, the dicarboxylic acid that gives the structural unit (1) is obtained by reacting the tetracarboxylic dianhydride represented by the above formula (A3a) and the polyol represented by the above formula (a3a).

[0089] In formula (A3a), X A1 is a tetravalent organic group having 4 to 40 carbon atoms, and may have one or more substituents in addition to the two acid anhydride groups represented by -CO-O-CO- in formula (A3a). Preferable examples of the substituent include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and a fluorinated alkoxy group having 1 to 6 carbon atoms. Further, the compound represented by the formula (A3a) may contain a carboxy group and a carboxylic acid ester group in addition to the acid anhydride group. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, a perfluoroalkyl group or a perfluoroalkoxy group is preferable. Regarding the above substituents, the same applies to one or more substituents that the aromatic group described later may have on the aromatic ring.

[0090] X A1 Preferably has 8 or more carbon atoms, more preferably 12 or more carbon atoms. Also, X A1 Preferably has 30 or less carbon atoms. X A1 may be an aliphatic group, an aromatic group, or a group combining these structures. X A1 may contain a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom in addition to carbon atoms and hydrogen atoms. X A1 When contains an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, nitrogen atom, or sulfur atom is a group selected from a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -S-S-, and may be contained in X A1 and is more preferably contained in X A1 as a group selected from -O-, -CO-, -S-, and.

[0091] The tetracarboxylic dianhydride represented by the formula (A3a) may be an aliphatic tetracarboxylic dianhydride having two dicarboxylic anhydride groups bonded to an aliphatic group, or an aromatic tetracarboxylic dianhydride having at least one dicarboxylic anhydride group bonded to an aromatic group. In addition, the aromatic tetracarboxylic dianhydride preferably has two dicarboxylic anhydride groups bonded to the aromatic group. That is, X A1 The tetravalent organic group as is preferably a residue obtained by removing two dicarboxylic anhydride groups from the aromatic tetracarboxylic dianhydride.

[0092] The aliphatic tetracarboxylic dianhydride may contain an alicyclic structure. The alicyclic structure may be polycyclic. Examples of the aliphatic tetracarboxylic dianhydride having no alicyclic structure include 1,2,3,4-tetracarboxylic dianhydride (e.g., Likacid BT-100, manufactured by Shin Nippon Rika Co., Ltd.). Examples of the aliphatic tetracarboxylic dianhydride having an alicyclic structure include cyclobutane tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride (e.g., Enhydride (registered trademark) CpODA, manufactured byENEOS Corporation), 2,2-bis(2,3-dicarboxyphenoxy)hexafluoropropane dianhydride [5,5'-(1,4-phenylene)bisnorbornane]-2,2',3,3'-tetracarboxylic dianhydride (e.g., Enhydride (registered trademark) BzDA, manufactured by ENEOS Corporation), 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione (e.g., Likacid TDA-100, manufactured by Shin Nippon Rika Co., Ltd.).

[0093] Examples of the aromatic tetracarboxylic dianhydride represented by the formula (A3a) and having two dicarboxylic anhydride groups bonded to an aromatic group include, for example, pyromellitic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, trimellitic acid (3,4-dicarboxyphenyl) dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis(2,3-dicarboxyphenoxy)methane dianhydride, 1,1-bis(2,3-dicarboxyphenoxy)ethane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride, 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride, 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (for example, Rica Sid TMEG100, manufactured by Shin Nippon Rika Co., Ltd.), and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (for example, 10BTA, manufactured by Koganei Kasei Co., Ltd.). Among these aromatic tetracarboxylic dianhydrides, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride, and α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride are preferable in terms of easily forming a cured product with excellent electrical properties. α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride is a compound represented by the following formula (a1).

Chemical formula

[0094] In formula (a1), which represents the number of carbon atoms of the linear alkylene group in α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride, n is an integer of 1 or more, preferably 1 or more and 20 or less, and more preferably 2 or more and 12 or less. Preferable specific examples of α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride include 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (for example, Rica Sid TMEG100, manufactured by Shin Nippon Rika Co., Ltd.) and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (for example, 10BTA, manufactured by Koganei Kasei Co., Ltd.).

[0095] Also, in terms of suppressing the warpage of the polyimide resin film formed using the chemically amplified negative photosensitive composition containing the polyimide resin precursor (A) and having good photolithography properties of the chemically amplified negative photosensitive composition, it is also preferable that the aromatic tetracarboxylic dianhydride is biphenyltetracarboxylic dianhydride. Examples of the biphenyltetracarboxylic dianhydride include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyltetracarboxylic dianhydride, with 3,3',4,4'-biphenyltetracarboxylic dianhydride being preferred.

[0096] Examples of the aromatic tetracarboxylic dianhydride may also include, for example, compounds represented by the following general formulas (a3-2) to (a3-4). [Chemical formula]

[0097] In the above formulas (a3-2) and (a3-3), R a01 , R a02 and R a03 each represent a divalent group which is either an aliphatic group optionally substituted with a halogen, an oxygen atom, a sulfur atom, an aromatic group via one or more divalent elements, or a combination thereof. R a02 and R a03 may be the same or different. That is, R a01 , R a02 and R a03 may contain a carbon-carbon single bond, a carbon-oxygen-carbon ether bond, or a halogen element (fluorine, chlorine, bromine, iodine). Examples of the compound represented by the formula (a3-2) include 2,2-bis(3,4-dicarboxyphenoxy)propane dianhydride, bis(3,4-dicarboxyphenoxy)methane dianhydride, 1,1-bis(3,4-dicarboxyphenoxy)ethane dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene, 2,2-bis(3,4-dicarboxyphenoxy)hexafluoropropane dianhydride, and 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, etc.

[0098] Also, in the above formula (a3-4), R a04 , R a05represents a monovalent substituent composed of an aliphatic group which may be substituted with a halogen, an aromatic group via one or more divalent elements, a halogen, or a combination thereof. R a04 , and R a05 may be the same or different from each other. As the compound represented by the formula (a3-4), difluoropyromellitic dianhydride, dichloropyromellitic dianhydride, etc. can also be used.

[0099] · Polyol As described above, the dicarboxylic acid that provides the structural unit (1) is obtained by reacting a tetracarboxylic dianhydride represented by the following formula (A3a) with the polyol represented by the above formula (a3a). Hereinafter, the polyol represented by the formula (a3a) will be described. (HO) a -R A2 -R A1 -OH ··· (a3a)

[0100] R A1 is a divalent aliphatic group having 2 or more carbon atoms which may be substituted with a hydroxyl group. The aliphatic group as R A1 is bonded to the non-carbonyl oxygen atom in the formula (1) via a C-O bond.

[0101] R A1 The structure of the aliphatic group as may be linear, cyclic, or a combination of linear and cyclic. The structure of the aliphatic group as R A1 is preferably linear. When R A1 is a linear aliphatic group, the linear aliphatic group may be a straight-chain aliphatic group or a branched-chain aliphatic group, and a straight-chain aliphatic group is preferred.

[0102] R A1 The aliphatic group as may contain a heteroatom. Examples of the heteroatom include O, N, S, B, P, Si, and halogen atoms. R A1The aliphatic group as such is preferably an aliphatic hydrocarbon group, more preferably an alkylene group, and even more preferably a linear alkylene group.

[0103] R A1 The number of carbon atoms of the aliphatic group as such is 2 or more, preferably 2 or more and 20 or less, more preferably 2 or more and 12 or less, and even more preferably 2 or more and 6 or less.

[0104] R A1 Preferable examples of the aliphatic group when it is an alkylene group include ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, butane-2,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, and dodecane-1,12-diyl group. Among these groups, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, butane-2,3-diyl group, pentane-1,5-diyl group, and hexane-1,6-diyl group are preferable, and ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, and butane-1,4-diyl group are more preferable.

[0105] Also, as the aliphatic group as R A1 a group represented by -O-R A10 -* is also preferable. R A10 is an alkylene group. The bond represented by ** is bonded to R A2 in formula (a3a). R A10 Preferable examples of the alkylene group as R A1 are the same as the preferable examples of the alkylene group as R

[0106] R A1 As the aliphatic group, **-R A12 -O-R A11 The group represented by -* is also preferred. R A11 R is a group obtained by removing two hydroxyl groups from among the plurality of hydroxyl groups possessed by the saccharide. R A12 R is an alkylene group. The bond represented by ** is bonded to R A2 in formula (a3a). R A12 Preferable examples of the alkylene group as R A1 are the same as the preferable examples of the alkylene group as R

[0107] As the above saccharide, pentose and hexose are preferable, and hexose is more preferable. Specific examples of hexose preferably include glucose, mannose, galactose, and fructose, and glucose is more preferable. R A12 Preferable examples of the chain aliphatic hydrocarbon group as R A1 are the same as the preferable examples of the chain aliphatic hydrocarbon group as R

[0108] In formula (a3a), R A2 is an a + 1-valent aromatic group. The aromatic group as R A2 may be an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic group as R A2 is preferably an aromatic hydrocarbon group. That is, the aromatic group as R A2 is preferably a group obtained by removing a hydrogen atoms from a monovalent aromatic hydrocarbon group.

[0109] R A2 As the aromatic hydrocarbon group as R, a group obtained by removing a hydrogen atoms from a phenyl group, a naphthyl group, a 4-phenylphenyl group, a 3-phenylphenyl group, or a 2-phenylphenyl group is preferable.

[0110] -R A2 -(OH) aThe group represented by is preferably a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxynaphthyl group, or a dihydroxynaphthyl group.

[0111] When a is 1, R A2 Preferable specific examples of the aromatic hydrocarbon as include a p-phenylene group, an m-phenylene group, an o-phenylene group, a naphthalene-1,2-diyl group, a naphthalene-1,3-diyl group, a naphthalene-1,4-diyl group, a naphthalene-1,5-diyl group, a naphthalene-1,6-diyl group, a naphthalene-1,7-diyl group, a naphthalene-1,8-diyl group, a naphthalene-2,3-diyl group, a naphthalene-2,6-diyl group, and a naphthalene-2,7-diyl group.

[0112] When a is 2, R A2 Preferable specific examples of the aromatic hydrocarbon as include a benzene-1,2,3-triyl group, a benzene-1,2,4-triyl group, a benzene-1,3,5-triyl group, a naphthalene-1,2,3-triyl group, a naphthalene-1,2,4-triyl group, a naphthalene-1,2,5-triyl group, a naphthalene-1,2,6-triyl group, a naphthalene-1,2,7-triyl group, a naphthalene-1,2,8-triyl group, a naphthalene-1,3,5-triyl group, a naphthalene-1,3,6-triyl group, a naphthalene-1,3,7-triyl group, a naphthalene-1,3,8-triyl group, a naphthalene-1,4,5-triyl group, a naphthalene-1,4,6-triyl group, a naphthalene-1,4,7-triyl group, a naphthalene-1,6,7-triyl group, a naphthalene-1,6,8-triyl group, and a naphthalene-2,3,6-triyl group.

[0113] In formula (a3a), (HO) a -R A2Preferable examples of the group represented by - include 4-hydroxyphenyl group, 3-hydroxyphenyl group, 2-hydroxyphenyl group, 3,4-dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,3-dihydroxyphenyl group, 3,5-dihydroxyphenyl group, 4-hydroxynaphthalen-1-yl group, 2-hydroxynaphthalen-1-yl group, 3-hydroxynaphthalen-1-yl group, 6-hydroxynaphthalen-1-yl group, 7-hydroxynaphthalen-1-yl group, 3-hydroxynaphthalen-2-yl group, 6-hydroxynaphthalen-2-yl group, and 7-hydroxynaphthalen-6-yl group, etc. Among these groups, 4-hydroxyphenyl group, 3-hydroxyphenyl group, 2-hydroxyphenyl group, and 3,4-dihydroxyphenyl group are preferable.

[0114] Preferable specific examples of the polyol represented by the formula (a3a) include 2-(4-hydroxyphenyl)ethanol, 2-(3-hydroxyphenyl)ethanol, 2-(2-hydroxyphenyl)ethanol, 4-(4-hydroxyphenyl)butan-2-ol (rododenol), 2-(3,4-dihydroxyphenyl)ethanol, 4-hydroxyphenyl β-D-glucopyranoside (arbutin), 2-(4-hydroxyphenyl)ethyl β-D-glycopyranoside (salidroside), 4-(4-hydroxyphenyl)propanol, 3-(4-hydroxyphenyl)propanol, 2-(4-hydroxyphenyl)propanol, 4-(2-hydroxyethoxy)phenol, 3-(2-hydroxyethoxy)phenol, 2-(2-hydroxyethoxy)phenol, 4-(6-hydroxyhexyloxy)phenol, 3-(6-hydroxyhexyloxy)phenol, and 2-(6-hydroxyhexyloxy)phenol, etc.

[0115] (Production of dicarboxylic acid) By reacting the tetracarboxylic dianhydride described above with alcohols, a dicarboxylic acid can be obtained. The alcohols react with the carboxylic anhydride group to form a carboxy group and an ester group.

[0116] A dicarboxylic acid that provides the structural unit (1) is obtained by reacting the above-described tetracarboxylic dianhydride with a polyol represented by the formula (a3a) as alcohols. Hereinafter, the polyol represented by the formula (a3a) will be referred to as R a21 -OH. R a21 is a group represented by -R A1 -R A2 -(OH) a . Such a dicarboxylic acid has two pairs of a carboxy group and a group represented by -CO-O-R a21 located on adjacent carbon atoms in the dicarboxylic acid.

[0117] For the above dicarboxylic acid having two pairs of a carboxy group and a group represented by -CO-O-R a21 , isomers may exist in which the position of the carboxy group is different from the position of the group represented by -CO-O-R a21 . As the above dicarboxylic acid, one of such isomers may be used alone, or two or more thereof may be used in combination. In the specification and claims of the present application, it is assumed that the polyimide resin precursor contains a plurality of types of structural units derived from a plurality of isomers of dicarboxylic acid.

[0118] As an example, regarding the dicarboxylic acid corresponding to pyromellitic dianhydride, as isomers, a compound represented by the following formula (a4-a1) and a compound represented by the following formula (a4-a2) exist. Further, regarding the dicarboxylic acid corresponding to 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, as isomers, a compound represented by the following formula (a4-b1), a compound represented by the following formula (a4-b2), and a compound represented by the following formula (a4-b3) exist. In the following formula (a4-a1), formula (a4-a2), and formula (a4-b1) to formula (a4-b3), R a21 is as described above respectively.

[0119] [Chemical formula]

[0120] Examples of the dicarboxylic acids corresponding to the tetracarboxylic dianhydrides represented by the aforementioned formulas (a3-2) to (a3-4) include compounds represented by the following formulas (a4-2a) to (a4-2c), formulas (a4-3a) to (a4-3c), and formulas (a4-4a) to (a4-4c). In formulas (a4-2a) to (a4-2c), formulas (a4-3a) to (a4-3c), and formulas (a4-4a) to (a4-4c), R a01 ~R a05 are the same as these in formulas (a3-2) to (a3-4). In formulas (a4-2a) to (a4-2c), formulas (a4-3a) to (a4-3c), and formulas (a4-4a) to (a4-4c), R a21 is as described above. [Chemical formula]

[0121] Examples of the dicarboxylic acids corresponding to the tetracarboxylic dianhydrides represented by the aforementioned formulas (a3-5) to (a3-7) include compounds represented by the following formulas (a4-5a) to (a4-5c), formulas (a4-6a) to (a4-6c), formula (a4-7a), and formula (a4-7b). In formulas (a4-5a) to (a4-5c), formulas (a4-6a) to (a4-6c), formula (a4-7a), and formula (a4-7b), R a01 ~R a03 , R a06 , m1, and m2 are the same as these in formulas (a3-5) to (a3-7). In formulas (a4-5a) to (a4-5c), formulas (a4-6a) to (a4-6c), formula (a4-7a), and formula (a4-7b), R a21 is as described above.

[0122] [Chemical formula]

[0123] The reaction between a tetracarboxylic dianhydride and alcohols is usually carried out in an organic solvent. The organic solvent used in the reaction between a tetracarboxylic dianhydride and alcohols is not particularly limited as long as it can dissolve the tetracarboxylic dianhydride and alcohols and does not react with the tetracarboxylic dianhydride and alcohols. The organic solvent can be used alone or in combination of two or more kinds.

[0124] Examples of the organic solvent used in the reaction between a tetracarboxylic dianhydride and alcohols include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyramide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylisobutyric amide, methoxy-N,N-dimethylpropionamide, butoxy-N,N-dimethylpropionamide, N-methylcaprolactam, N,N'-dimethylpropyleneurea, N,N,N',N'-tetramethylurea, and pyridine; dimethyl sulfoxide; sulfolane; lactones such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ-caprolactone; esters such as methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate; carbonates such as ethylene carbonate and propylene carbonate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetonitrile; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, and tetrahydrofuran; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, and o-dichlorobenzene; hexane, heptane, benzene, toluene, and xylene. These organic solvents may be used alone or in combination of two or more kinds.

[0125] Among these organic solvents, nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, and N,N,N’,N’-tetramethylurea are preferred.

[0126] The temperature at which the tetracarboxylic dianhydride and the alcohols are reacted is not particularly limited as long as the reaction proceeds well. Typically, the reaction temperature of the tetracarboxylic dianhydride and the alcohols is preferably -5°C or higher and 120°C or lower, more preferably 0°C or higher and 80°C or lower, and particularly preferably 0°C or higher and 50°C or lower. The reaction time of the tetracarboxylic dianhydride and the alcohols varies depending on the reaction temperature, but typically, it is preferably 30 minutes or longer and 20 hours or shorter, more preferably 1 hour or longer and 8 hours or shorter, and particularly preferably 2 hours or longer and 6 hours or shorter.

[0127] For the purpose of preventing crosslinking between ethylenically unsaturated double bonds during the reaction of the tetracarboxylic dianhydride and the alcohols, a small amount of a polymerization inhibitor may be used. Examples of the polymerization inhibitor include phenols such as hydroquinone, 4-methoxyphenol, tert-butylpyrocatechol, and bis-tert-butylhydroxytoluene, and phenothiazine. The usage amount of the polymerization inhibitor is preferably 0.01 mol% or more and 5 mol% or less, for example, based on the number of moles of the ethylenically unsaturated double bond.

[0128] The reaction of the tetracarboxylic dianhydride and the alcohols may be carried out in the presence of an organic base such as pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, 1,4-diazabicyclo[2,2,2]octane. These bases may be used alone or two or more of them may be used simultaneously.

[0129] The usage amount of the alcohols is preferably 1.8 moles or more and 2.2 moles or less, more preferably 2 moles or more and 2.1 moles or less, per 1 mole of the tetracarboxylic dianhydride.

[0130] In the production of dicarboxylic acids, depending on the production conditions, only one of the dicarboxylic anhydride groups may react with alcohols to form a monocarboxylic acid compound having a dicarboxylic anhydride group, or a part of the tetracarboxylic dianhydride may react with water in the reaction system to form a tetracarboxylic acid compound or a tricarboxylic acid compound. As long as the desired effects are not impaired, a dicarboxylic acid containing at least one selected from the above-mentioned monocarboxylic acid compound, tricarboxylic acid compound, and tetracarboxylic acid compound can be used in the production of a polyimide resin precursor. When the dicarboxylic acid contains at least one selected from the above-mentioned monocarboxylic acid compound, tricarboxylic acid compound, and tetracarboxylic acid compound as an impurity, the content of at least one selected from the above-mentioned monocarboxylic acid compound, tricarboxylic acid compound, and tetracarboxylic acid compound as an impurity in the dicarboxylic acid is preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 1% by mass or less with respect to the mass of the dicarboxylic acid including the mass of the impurity.

[0131] 〔Constituent unit (2)〕 The polyimide resin precursor may contain a constituent unit (2) which is a constituent unit not corresponding to the constituent unit (1). The constituent unit (2) is represented by the following formula (2). In formula (2), two Rs A3 are each independently a hydrogen atom or a monovalent organic group. In formula (2), two Rs A3 may be the same or different.

Chemical formula

[0132] In formula (2), when both of the two Rs A3 are hydrogen atoms, the constituent unit (2) is formed by reacting a diamine compound with a tetracarboxylic dianhydride represented by the following formula (A3b).

Chemical formula

[0133] In formula (2), when both two Rs A3 are monovalent organic groups, a structural unit (2) is formed by reacting a diamine compound with a dicarboxylic acid compound. The dicarboxylic acid compound for forming the structural unit (2) is a reaction product of the tetracarboxylic dianhydride represented by the above formula (A3b) and an alcohol represented by the following formula (a3b). R A3 -OH ··· (a3b)

[0134] When both two Rs A3 are monovalent organic groups, one of the Rs A3 may be an organic group represented by -R A1 -R A2 -(OH) a , and the other R A3 may be an organic group that does not correspond to the group represented by -R A1 -R A2 -(OH) a . R A1 , R A2 , and a are the same as R A1 , R A2 , and a in formula (1). The structural unit (2) is a structural unit that does not correspond to the structural unit (1). Therefore, both two Rs in formula (2) A3 are not groups represented by -R A1 -R A2 -(OH) a .

[0135] Also, by reacting a product obtained by reacting an alcohol with only one of the dicarboxylic anhydride groups in the tetracarboxylic dianhydride represented by the above formula (A3b) with a diamine, a structural unit (2) in which one of the Rs A3 is a hydrogen atom and the other R A3 is a monovalent organic group is formed. The product obtained by reacting an alcohol represented by the formula (a3b) with only one of the dicarboxylic anhydride groups in the tetracarboxylic dianhydride represented by the above formula (A3b) is represented by the following formula (A3c). In the formula (A3c), X A2 , and R A3 are the same as X A2 , and R A3 in the formula (2). [Chemical formula]

[0136] The structural unit (2) is represented by the formula (2) and is preferably a structural unit in which two R A3 are hydrogen atoms or a structural unit represented by the formula (2) in which two R A3 are monovalent organic groups. Since it is easy to form a polyimide resin excellent in dielectric properties in the high-frequency band, the structural unit (2) is more preferably a structural unit represented by the formula (2) in which two R A3 are monovalent organic groups.

[0137] Hereinafter, the diamine compound and the dicarboxylic acid that give the structural unit (1) will be described.

[0138] (Diamine compound) The diamine compound that gives the structural unit (2) represented by the formula (2) is represented by the following formula (A2b). H2N-Y A2 -NH2 ··· (A2b) (In the formula (Ab), Y A2 represents a divalent organic group having 4 to 40 carbon atoms.)

[0139] Y A2 in the formula (A2b) is the same as Y A1 in the formula (A2a). That is, the diamine compound represented by the formula (A2b) is the same as the diamine compound represented by the formula (A2a).

[0140] (Dicarboxylic acid) The dicarboxylic acid is a reaction product of a tetracarboxylic dianhydride and alcohols. The dicarboxylic acid that provides the structural unit (2) is a reaction product of the tetracarboxylic dianhydride represented by the above formula (A3b) and the alcohol represented by the above formula (a3b). In formula (A3b) and formula (a3b), R A3 , and X A2 are the same as R A3 , and X A2 in formula (2).

[0141] Hereinafter, the tetracarboxylic dianhydride represented by formula (A3b) and the polyol represented by formula (a3b) will be described.

[0142] The tetracarboxylic dianhydride is represented by the above formula (a3b). X A2 in formula (A3b) is the same as X A1 in formula (A3a). That is, the tetracarboxylic dianhydride represented by formula (A3b) is the same as the tetracarboxylic dianhydride represented by formula (A3a).

[0143] As described above, as long as the structural unit (2) does not correspond to the structural unit (1), the alcohol represented by the above formula (a3b) may be the polyol represented by the above formula (a3a). Examples of suitable alcohols represented by formula (a3b) that do not correspond to the polyol represented by formula (a3a) include alkanemonoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol; phenols or naphthols such as phenol, p-cresol, m-cresol, o-cresol, α-naphthol, and β-naphthol; and monoethers of glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, 1,3-propanediol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.

[0144] (Production of dicarboxylic acid) The method for producing the dicarboxylic acid that provides structural unit (2) is the same as that described for structural unit (1).

[0145] [Method for producing polyimide resin precursor] The method for producing the polyimide resin precursor is not particularly limited as long as it is a method capable of polycondensing the aforementioned diamine compound and dicarboxylic acid until the weight average molecular weight of the polyimide resin precursor increases to a desired level. Note that, within a range where the desired effect is not impaired, a compound capable of polymerizing with the diamine compound such as tetracarboxylic dianhydride may be used together with the dicarboxylic acid.

[0146] A preferred method includes a method of condensing the aforementioned diamine compound and dicarboxylic acid in the presence of a condensing agent. It is also preferable to use a condensation aid together with the condensing agent as necessary. The condensing agent and condensation aid are not particularly limited as long as they are compounds conventionally used for the condensation of dicarboxylic acid and diamine compound.

[0147] Preferred condensing agents include at least one selected from the group consisting of dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, diisopropylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1-cyclohexyl-3-(2-morpholinoethyl)-carbodiimide metho-p-toluenesulfonate, 1,3-bis(2,2-dimethyl-1,3-dioxolan-4-ylmethyl)carbodiimide, polymer-supported 1-benzyl-3-cyclohexylcarbodiimide, and polymer-supported 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide.

[0148] The amount of the condensing agent used is not particularly limited as long as a polyimide resin precursor having a desired molecular weight can be obtained. The amount of the condensing agent used is typically preferably 1 mol or more and 5 mol or less, more preferably 2 mol or more and 4 mol or less, and even more preferably 2 mol or more and 3 mol or less per 1 mol of the dicarboxylic acid. In addition, the ratio of the amount of the dicarboxylic acid to the amount of the diamine compound in producing the polyimide resin precursor is not particularly limited as long as a polyimide resin precursor having a desired molecular weight can be produced. When the polyimide resin precursor has an amino group terminal, the raw material ratio represented by (the number of moles of carboxy groups of the dicarboxylic acid) / (the number of moles of amino groups of the diamine compound) is preferably adjusted within the range of 0.5 / 1 to 0.95 / 1, more preferably 0.55 / 1 to 0.80 / 1. The smaller the value of (the number of moles of carboxy groups of the dicarboxylic acid) / (the number of moles of amino groups of the diamine compound), the less likely the molecular chain of the polyimide resin precursor is to elongate, and the easier it is to obtain a low-molecular-weight polyimide resin precursor. When the polyimide resin precursor has a carboxyl group at its terminal, the raw material ratio represented by (the number of moles of amino groups in the diamine compound) / (the number of moles of carboxyl groups in the dicarboxylic acid) is preferably adjusted within the range of 0.5 / 1 to 0.95 / 1, more preferably within the range of 0.55 / 1 to 0.80 / 1. The smaller the value of (the number of moles of amino groups in the diamine compound) / (the number of moles of carboxyl groups in the dicarboxylic acid), the more difficult it is for the molecular chain of the polyimide resin precursor to elongate, and the easier it is to obtain a low molecular weight polyimide resin precursor.

[0149] Specifically, a dicarboxylic acid and a diamine compound are reacted in an organic solvent in the presence of the above-mentioned condensing agent, for example, at -20°C or higher and 150°C or lower, preferably at 0°C or higher and 50°C or lower, for 30 minutes or longer and 24 hours or shorter, preferably for 1 hour or longer and 4 hours or shorter.

[0150] As the solvent used for polycondensation, the above-mentioned solvents that can be used in the reaction between a tetracarboxylic dianhydride and alcohols can be used. The amount of the solvent used is preferably 50 parts by mass or more and 10,000 parts by mass or less, more preferably 100 parts by mass or more and 2,000 parts by mass or less, and even more preferably 150 parts by mass or more and 1,000 parts by mass or less, based on 100 parts by mass in total of the mass of the dicarboxylic acid and the mass of the diamine compound.

[0151] The amounts of the dicarboxylic acid and the diamine compound used in producing the polyimide resin precursor are not particularly limited, but it is preferable to use 0.8 mol or more and 1.2 mol or less, more preferably 0.9 mol or more and 1.1 mol or less, and particularly preferably 0.95 mol or more and 1.05 mol or less of the diamine compound per 1 mol of the dicarboxylic acid.

[0152] From the viewpoint of easily obtaining a polyimide resin precursor that gives a polyimide resin having excellent dielectric properties in a high frequency band, the polyimide resin precursor preferably contains a divalent aliphatic hydrocarbon group having 2 or more and 50 or less carbon atoms, more preferably 3 or more and 40 or less carbon atoms. The position of such a divalent aliphatic hydrocarbon group in the molecular chain of the polyimide resin precursor is not particularly limited. Examples of the monomer that provides a divalent aliphatic hydrocarbon group having 2 to 50 carbon atoms in the molecular chain include the aforementioned dimer diamine compound (A-4) and the aforementioned α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride.

[0153] From the viewpoint of easily obtaining a polyimide resin precursor that gives a polyimide resin having excellent dielectric properties in a high-frequency band, it is preferable that the photosensitive composition contains a structural unit derived from a carboxylic acid derived from a tetracarboxylic dianhydride represented by the following formula (a1) and / or a structural unit derived from a diamine compound represented by the following formula (a2). The tetracarboxylic dianhydride represented by the formula (a1) and the diamine compound represented by the formula (a2) are as described above. [Chemical formula] (In the formulas (a1) and (a2), n is an integer of 1 or more.)

[0154] The weight average molecular weight of the polyimide resin precursor may be appropriately set according to its use. The weight average molecular weight of the polyimide resin precursor can be measured as the weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography). The weight average molecular weight of the polyimide resin precursor is, for example, 5000 or more, preferably 15000 or more, and more preferably 250000000 or more in terms of polystyrene from the viewpoint of obtaining a resin film with good mechanical properties. On the other hand, the weight average molecular weight of the obtained polyimide resin precursor is, for example, 100000 or less, preferably 80000 or less, and more preferably 50000 or less in terms of polystyrene from the viewpoint of solubility in an organic solvent and the like. This weight average molecular weight can be adjusted to the above values by adjusting the blending amounts of the aforementioned dicarboxylic acid and diamine compound, and reaction conditions such as the solvent and reaction temperature.

[0155] For the purpose of improving the storage stability of a chemically amplified negative photosensitive composition containing a polyimide resin precursor, further improving the mechanical properties of a polyimide resin film, and improving the reproducibility of polymerization when producing a polyimide resin precursor, etc., the main chain terminals of the polyimide resin precursor may be capped with a terminal capping agent. Examples of the terminal capping agent include monoamines, acid anhydrides, monocarboxylic acids, monoacid halides, monoactive ester compounds, etc. As the monoamine used for terminal capping, known compounds can be used. Examples of the monoamine include aromatic monoamines such as aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 3-hydroxyaniline, 4-hydroxyaniline, 3-aminothiophenol, and 4-aminothiophenol; aliphatic monoamines having a branched structure with 3 or more and 20 or less carbon atoms such as hexylamine and octylamine; monoamines having an alicyclic structure such as cyclohexylamine; and aminosilanes such as trimethoxyaminopropylsilane and triethoxyaminopropylsilane. Among the acid anhydrides, monoacid halides, and monoactive ester compounds used as the terminal capping agent, acid anhydrides are preferred. As the acid anhydride, known acid anhydrides and their derivatives can be used. For example, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, xo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and their derivatives can be mentioned. From the viewpoint of excellent mechanical properties of the formed polyimide resin film, the introduction rate of the terminal capping agent in the polyimide resin precursor is preferably 40 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less, based on the total number of moles of all monomers.

[0156] The polyimide resin precursor produced as described above is used in the production of a photosensitive composition after being in a solution or suspension state, or separated and recovered from the reaction solution by a well-known method.

[0157] ≪Photosensitive Composition≫ The polyimide resin precursor described above can be preferably used as a component of a photosensitive composition. The photosensitive composition includes a photosensitizer (B) that imparts photosensitivity to the photosensitive composition, together with the polyimide resin precursor (A) which is the aforementioned polyimide resin precursor.

[0158] Preferable examples of such a photosensitive composition include those containing a polyimide resin precursor (A), a photosensitizer (B), and a crosslinking agent (C), wherein the photosensitizer (B) is a photoacid generator (B1), and the crosslinking agent (C) is a compound capable of forming a crosslink by reaction with a phenolic hydroxyl group or an aromatic group having a phenolic hydroxyl group. Such a composition is a chemically amplified negative photosensitive composition that cures upon exposure.

[0159] Also, compositions containing a polyimide resin precursor (A), a photosensitizer (B), and a crosslinking agent (C) are preferred, wherein the photosensitizer (B) is a quinonediazide group-containing compound (B2), and the crosslinking agent (C) is a compound capable of forming a crosslink by reaction with a phenolic hydroxyl group or an aromatic group having a phenolic hydroxyl group. Such a composition is a positive photosensitive composition that solubilizes in an alkaline developer upon exposure.

[0160] Hereinafter, the chemically amplified negative photosensitive composition and the positive photosensitive composition will be described.

[0161] <Chemically Amplified Negative Photosensitive Composition> The chemically amplified negative photosensitive composition includes a polyimide resin precursor (A), a photosensitizer (B), and a crosslinking agent (C). The photosensitizer (B) is a photoacid generator (B1). The crosslinking agent (C) is a compound capable of forming a crosslink by reaction with a phenolic hydroxyl group or an aromatic group having a phenolic hydroxyl group. Hereinafter, the essential, or optional components that the chemically amplified negative photosensitive composition may contain will be described.

[0162] [Polyimide resin precursor (A)] The polyimide resin precursor (A) is the aforementioned polyimide resin precursor.

[0163] [Photosensitizer (B)] The photosensitizer (B) is a photoacid generator (B1). The photoacid generator (B1) is not particularly limited, and the photoacid generators that have been blended in photosensitive compositions can be used without particular limitation. Examples of the photoacid generator (B1) include onium salt type photoacid generators such as iodonium salts and sulfonium salts; sulfonate type photoacid generators such as oxime sulfonate type photoacid generators and imide sulfonate type photoacid generators; diazomethane type photoacid generators; and disulfone type photoacid generators. Among these, sulfonate type photoacid generators and onium salt type photoacid generators are preferred because it is easy to obtain a chemically amplified negative type photosensitive composition having excellent photolithography characteristics. That is, it is preferable that the photoacid generator (B1) contains a sulfonate type photoacid generator (B1-1) and / or an onium salt type photoacid generator (B1-2). Hereinafter, the sulfonate type photoacid generator (B1-1) and the onium salt type photoacid generator (B1-2) will be described.

[0164] [Sulfonate type photoacid generator (B1-1)] The sulfonate type photoacid generator (B1-1) is not particularly limited as long as it is a compound having a sulfonate structure represented by -O-SO2-. As the sulfonate type photoacid generator (B1-1), for example, a compound represented by the following formula (b0-1) is preferable.

[0165] [Chemical formula]

[0166] In formula (b0-1), Rb 1 is an organic group. Rb 2 is a group represented by the following formula (b0-r-1) or the following formula (b0-r-2).

[0167]

Chem.

[0168] In formula (b0-r-1), Rb 201 , and Rb 202 are each independently an organic group. * represents a bond. In formula (b0-r-2), Xb is a group that forms a cyclic group having a cyclic imide structure together with -(O=)C-N-C(=O)-. * represents a bond.]

[0169] Preferable examples of the compound represented by formula (b0-1) include compounds represented by any of the following formulas (b0-1-1) to (b0-1-6). As the sulfonate-type photoacid generator (B1-1), an oxime sulfonate-type photoacid generator (B1-1a) and an imide sulfonate-type photoacid generator (B1-1b) are preferable. The compound represented by any of the following formulas (b0-1-1) to (b0-1-6) is an oxime sulfonate compound having a structure represented by >C=N-O-SO2- or an imide sulfonate compound having a structure represented by >N-O-SO2-. The nitrogen atom in the structure represented by >N-O-SO2- constitutes a dicarboxylic acid imide ring.

[0170]

Chem.

[0171] In formula (b0-1-1), Rb 11 , and Rb 21 are each independently an aliphatic group.

[0172]

Chem.

[0173] In formula (b0-1-2), Rb 12is an alkyl group or a halogenated alkyl group. Rb 22 is an aromatic group.

[0174]

Chemical formula

[0175] In formula (b0-1-3), Rb 13 is an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group. nb3 is 2 or 3. Ab is a divalent or trivalent organic group.

[0176]

Chemical formula

[0177] In formula (b0-1-4), Rb 14 is an optionally substituted polycyclic aromatic hydrocarbon group or an optionally substituted polycyclic aliphatic hydrocarbon group which may have an unsaturated bond. Rb 24 is an inert organic group.

[0178]

Chemical formula

[0179] In formula (b0-1-5), Rb 15 is a monovalent aliphatic hydrocarbon group which may have a substituent and may have an unsaturated bond, or an optionally substituted aromatic group. Xb 5 is a group which forms a cyclic group having a cyclic imide structure together with -(O=)C-N-C(=O)-.

[0180]

Chemical formula

[0181] In formula (b0-1-6), Rb 16is an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. Rb 261 ~Rb 263 are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. nb6 is an integer of 0 or more and 5 or less.

[0182] In formula (b0-1-1), Rb 11 , and Rb 21 Examples of the aliphatic group as Rb

[0183] Rb 11 , and Rb 21 Examples of the alkyl group as Rb

[0184] Rb 11 , and Rb 21 The number of halogen atoms in the halogenated alkyl group as Rb is not particularly limited. The number of halogen atoms may be 1 or may be 2 or more. Examples of the halogen atom include any of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0185] Rb 11 , and Rb 21As the alkenyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms is preferable. Examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, a 1-propenyl group, an isopropenyl group, and a 2-butenyl group.

[0186] Rb 11 , and Rb 21 As the cycloalkyl group, a cycloalkyl group having 5 to 12 carbon atoms is preferable. Examples of the cycloalkyl group having 5 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a cyclododecyl group.

[0187] Rb 11 , and Rb 21 As the cycloalkenyl group, a cycloalkenyl group having 4 to 8 carbon atoms is preferable. Examples of the cycloalkenyl group having 4 to 8 carbon atoms include a 1-cyclobutenyl group, a 1-cyclopentenyl group, a 1-cyclohexenyl group, a 1-cycloheptenyl group, and a 1-cyclooctenyl group.

[0188] Rb 11 , and Rb 21 As the alkoxy group, an alkoxy group having 1 to 8 carbon atoms is preferable. Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an n-butyloxy group, and an n-pentyloxy group.

[0189] Rb 11 and Rb 21 As the cycloalkoxy group, a cycloalkoxy group having 5 to 8 carbon atoms is preferable. Examples of the cycloalkoxy group having 5 to 8 carbon atoms include a cyclopentyloxy group and a cyclohexyloxy group.

[0190] Rb in formula (b0-1-1) 11 is preferably an alkyl group, a halogenated alkyl group, or a cycloalkyl group, and more preferably an alkyl group. Rb21 Examples thereof preferably include an alkyl group, a cycloalkyl group, and a cycloalkenyl group, with a cycloalkenyl group being more preferred. In formula (b0-1-1), Rb 11 is an alkyl group having 1 to 4 carbon atoms, and Rb 21 is particularly preferably a cyclopentenyl group.

[0191] Specific examples of the compound represented by formula (b0-1-1) include α-(methylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(methylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-1-cycloheptenylacetonitrile, α-(methylsulfonyloxyimino)-1-cyclooctenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-cyclohexylacetonitrile, α-(ethylsulfonyloxyimino)-ethylacetonitrile, α-(propylsulfonyloxyimino)-propylacetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclopentylacetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclohexylacetonitrile, α-(cyclohexylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(n-butylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclohexenylacetonitrile, and α-(n-butylsulfonyloxyimino)-1-cyclohexenylacetonitrile.

[0192] Rb in formula (b0-1-2) 12Examples of the alkyl group as such include linear or branched alkyl groups having 1 to 4 carbon atoms. Specific examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.

[0193] Rb 12 Examples of the alkyl halide group as such include alkyl halide groups having 1 to 4 carbon atoms. Specific examples of the alkyl halide group having 1 to 4 carbon atoms include chloromethyl group, trichloromethyl group, trifluoromethyl group, and 2-bromopropyl group.

[0194] In formula (b0-1-2), Rb 22 The aromatic group as such is a group that exhibits physical and chemical properties peculiar to aromatic compounds. Specific examples of the aromatic group include phenyl group, naphthyl group, furyl group, and thienyl group. Rb 22 The aromatic group as such may have one or more substituents. Examples of the substituent include halogen atom, alkyl group, alkoxy group, and nitro group.

[0195] Specific examples of the compound represented by formula (b0-1-2) include α-(methylsulfonyloxyimino)-phenylacetonitrile, α-(methylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(methylsulfonyloxyimino)-4-methylphenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(propylsulfonyloxyimino)-4-methylphenylacetonitrile, and α-(methylsulfonyloxyimino)-4-bromophenylacetonitrile.

[0196] In formula (b0-1-3), Rb 13Examples of the hydrocarbon group which may have a substituent include an aromatic hydrocarbon group which may have a substituent and an aliphatic hydrocarbon group which may have a substituent. As the aromatic group, a hydrocarbon group having 6 to 14 carbon atoms is preferable. Specific examples of the aromatic hydrocarbon group which may have a substituent include a phenyl group, a tolyl group, a methoxyphenyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, and the like.

[0197] Rb 13 The aliphatic hydrocarbon group as may be a chain aliphatic hydrocarbon group or an alicyclic hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, and a cycloalkenyl group. The alkyl group and the alkenyl group may be linear or branched. The number of carbon atoms of the alkyl group and the alkenyl group is preferably 1 or more and 12 or less. The number of carbon atoms of the cycloalkyl group and the cycloalkenyl group is preferably 4 or more and 12 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-octyl group, and an n-dodecyl group. Specific examples of the alkenyl group include an ethenyl group, a propenyl group, a butenyl group, and a hexenyl group. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, and examples of the cycloalkenyl group include a 1-cyclobutenyl group, a 1-cyclopentenyl group, a 1-cyclohexenyl group, a 1-cycloheptenyl group, a 1-cyclooctenyl group, and the like.

[0198] Rb 13 The heterocyclic group may be an aromatic heterocyclic group or an aliphatic heterocyclic group. As the heterocyclic group, an aromatic heterocyclic group is preferable. Specific examples of the aromatic heterocyclic group include a furanyl group, a pyridyl group, and a quinolyl group.

[0199] Rb in formula (b0-1-3) 13 The hydrocarbon group and the heterocyclic group as such may have substituents. Examples of the substituents include a halogen atom, a hydroxyl group, an alkoxy group, and an acyl group etc.

[0200] Examples of the divalent or trivalent organic group as Ab in formula (b0-1-3) include a divalent or trivalent aliphatic hydrocarbon group and a divalent or trivalent aromatic hydrocarbon group.

[0201] Specific examples of the compound represented by formula (b0-1-3) are shown below.

[0202]

Chemical formula

[0203]

Chemical formula

[0204] Rb in formula (b0-1-4) 14 Examples of the polycyclic aromatic hydrocarbon group as such include fused polycyclic aromatic hydrocarbon groups such as 2-indenyl group, 1-naphthyl group, 2-naphthyl group, and 2-anthryl group; non-fused polycyclic aromatic hydrocarbon groups such as biphenyl group and terphenyl group. The polycyclic aromatic hydrocarbon group may have substituents such as halogen atoms such as chlorine atom, bromine atom, and iodine atom, nitro group, amino group, hydroxyl group, alkyl group, and alkoxyl group etc. Specific examples of the polycyclic aromatic hydrocarbon group having substituents include 5-hydroxynaphthalen-1-yl group and 4-aminonaphthalen-1-yl group etc.

[0205] Rb in formula (b0-1-4) 14Examples of the polycyclic aliphatic hydrocarbon group which may have an unsaturated bond include polycyclic terpene residues, adamantyl, etc. As the polycyclic aliphatic hydrocarbon group, a polycyclic terpene residue is preferred. The polycyclic aliphatic hydrocarbon group may have substituents such as halogen atoms such as chlorine atom, bromine atom and iodine atom, nitro group, amino group, hydroxyl group, alkyl group, alkoxyl group and the like.

[0206] Rb 14 In the polycyclic aliphatic hydrocarbon group, one or more methylene groups constituting the polycyclic aliphatic hydrocarbon group may be substituted with a carbonyl group (>C=O). However, in the polycyclic aliphatic hydrocarbon group, not all methylene groups are substituted with a carbonyl group.

[0207] Rb 14 Preferable examples of the polycyclic aliphatic hydrocarbon group include camphor-3-yl group, camphor-8-yl group, camphor-10-yl group, 3-bromocamphor-10-yl group and the like.

[0208] Among the groups described above, Rb 14 As, a naphthyl group and a camphor-10-yl group are preferred, and a 1-naphthyl group is particularly preferred in terms of excellent resolution of the chemically amplified negative photosensitive composition.

[0209] In formula (b0-1-4), Rb 24 The inert organic group as is not particularly limited as long as it is an organic group inert to the coexisting components under the use conditions. As the inert organic group, an aromatic group is preferred from the viewpoint of sensitivity to excimer laser, electron beam, and X-ray. Examples of the aromatic group include phenyl group, naphthyl group, furyl group, thienyl group and the like. The aromatic group may have inert substituents such as halogen atoms such as chlorine atom, bromine atom and iodine atom, alkyl group, alkoxyl group, nitro group and the like.

[0210] Specific examples of the compound represented by the formula (b0-1-4) include α-(1-naphthylsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(2-naphthylsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(1-naphthylsulfonyloxyimino)benzyl cyanide, α-(2-naphthylsulfonyloxyimino)benzyl cyanide, α-(10-camphorsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(10-camphorsulfonyloxyimino)benzyl cyanide, α-(3-camphorsulfonyloxyimino)-4-methoxybenzyl cyanide, and α-(3-bromo-10-camphorsulfonyloxyimino)-4-methoxybenzyl cyanide, etc.

[0211] Rb in the formula (b0-1-5) 15 The number of carbon atoms of the monovalent aliphatic hydrocarbon group which may have a substituent and may have an unsaturated bond as is preferably 1 or more and 8 or less. Note that the number of carbon atoms does not include the carbon atoms of the substituent. The structure of the aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures. Examples of the substituent include a halogen atom, nitro group, acetylamino group, alkoxy group, and phenyl group, etc. Among these substituents, a halogen atom and an alkoxy group are preferable. Rb 15 Examples of the aromatic group which may have a substituent as Rb include a monocyclic aromatic group and a bicyclic aromatic group. As the aromatic group, a phenyl group substituted with one or more groups selected from a vinyl group, alkyl group, alkoxy group, and halogen atom, etc. is preferable.

[0212] In the formula (b0-1-5), Xb 5 Examples of the ring having a cyclic imide structure formed by Xb and -(O=)C-N-C(=O)- include a succinimide ring, maleimide ring, glutarimide ring, phthalimide ring, and naphthalimide ring, etc. Xb 5The ring having a cyclic imide structure formed by -(O=)C-N-C(=O)- may have a substituent. Examples of the substituent include a halogen atom, a nitro group, an acetylamino group, an alkoxy group, and a phenyl group.

[0213] Specific examples of the compound represented by the formula (b0-1-5) include N-methylsulfonyloxysuccinimide, N-isopropylsulfonyloxysuccinimide, N-chloroethylsulfonyloxysuccinimide, N-(p-methoxyphenyl)sulfonyloxysuccinimide, N-(p-vinylphenyl)sulfonyloxysuccinimide, N-naphthylsulfonyloxysuccinimide, N-phenylsulfonyloxysuccinimide, N-(2,4,6-trimethylphenyl)sulfonyloxysuccinimide, N-methylsulfonyloxymaleimide, N-isopropylsulfonyloxymaleimide, N-chloroethylsulfonyloxymaleimide, N-(p-methoxyphenyl)sulfonyloxymaleimide, N-(p-vinylphenyl)sulfonyloxymaleimide, N-naphthylsulfonyloxymaleimide, N-phenylsulfonyloxymaleimide, N-(2,4,6-trimethylphenyl)sulfonyloxymaleimide, N-methylsulfonyloxyphthalimide, N-isopropylsulfonyloxyphthalimide, N-chloroethylsulfonyloxyphthalimide, N-(p-methoxyphenyl)sulfonyloxyphthalimide, N-(p-vinylphenyl)sulfonyloxyphthalimide, N-naphthylsulfonyloxyphthalimide, N-phenylsulfonyloxyphthalimide, and N-(2,4,6-trimethylphenyl)sulfonyloxyphthalimide, and the compounds described in paragraphs

[0089] to

[0091] of JP-A-10-097075, etc.

[0214] In the formula (b0-1-6), Rb 16As the alkyl group, a linear or branched alkyl group having 1 to 18 carbon atoms is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms is even more preferable. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, and n-octadecyl group.

[0215] In formula (b0-1-6), Rb 16 As the cycloalkyl group, a cycloalkyl group having 3 to 18 carbon atoms is preferable. Rb 16 Examples of the cycloalkyl group include cyclopentyl group, cyclohexyl group, cyclooctyl group, and cyclododecyl group.

[0216] Rb 16 The alkyl group and cycloalkyl group as Rb may have substituents. Examples of the substituents include halogen atom, halogenated alkyl group, cyano group, nitro group, phenyl group, alkoxy group, carboxy group, sulfonyl group, and amino group.

[0217] Rb 16 In the alkyl group or cycloalkyl group as Rb, one or more methylene groups constituting the alkyl group or cycloalkyl group may be substituted with a carbonyl group (>C=O). However, in the alkyl group or cycloalkyl group, not all methylene groups are substituted with a carbonyl group.

[0218] In formula (b0-1-6), Rb 16Examples of the aromatic group as such include a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, and a heteroaryl group, etc. Rb 16 The aromatic group as such may have a substituent. Examples of the substituent include a halogen atom, a halogenated alkyl group, a cyano group, a nitro group, a phenyl group, an alkoxy group, a carboxy group, a sulfonyl group, and an amino group, etc.

[0219] Specific examples of the compound represented by the formula (b0-1-6) include the compound represented by the following formula (b0-1-61), the compounds of Examples 25 to 40 and 53 of JP-T-2002-508774, etc.

[0220]

Chemical formula

[0221] Other specific examples of the sulfonate type photoacid generator (B1-1) other than the sulfonate type photoacid generator (B1-1) described above include the compounds described in paragraphs

[0056] ,

[0058] ,

[0060] , and

[0063] of Japanese Patent No. 4110392, and the compounds described in paragraphs

[0053] ,

[0054] ,

[0056] ,

[0058] , and

[0060] -

[0062] of Japanese Patent No. 4000469, etc.

[0222] Among the sulfonate type photoacid generators (B1-1) described above, at least one selected from the group consisting of the compound represented by the formula (b0-1-2), the compound represented by the formula (b0-1-3), the compound represented by the formula (b0-1-5), and the compound represented by the formula (b0-1-6) is preferable, and at least one selected from the group consisting of the compound represented by the formula (b0-1-2), the compound represented by the formula (b0-1-3), and the compound represented by the formula (b0-1-6) is more preferable.

[0223] As the sulfonate type photoacid generator (B1-1), the compounds represented by the following formulas (B0-1) to (B0-3) are particularly preferable.

[0224]

Chem.

[0225] 〔onium salt type photoacid generator (B1-2)〕 As the onium salt type photoacid generator (B1-2), conventionally known onium salt type photoacid generators such as iodonium salts and sulfonium salts can be used without particular limitation.

[0226] Examples of the onium salt type photoacid generator (B1-2) include onium salts having a naphthalene ring in the cation moiety. The phrase "having a naphthalene ring" means having a structure derived from naphthalene, which means having at least two ring structures and maintaining their aromaticity. This naphthalene ring may have substituents such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, and a linear or branched alkoxy group having 1 to 6 carbon atoms. The structure derived from the naphthalene ring may be a monovalent group (with one free valence) or a divalent group (with two or more free valences) or more, but a monovalent group is desirable (however, when this is the case, the free valence is counted excluding the part that binds to the above substituents). The number of naphthalene rings is preferably 1 to 3.

[0227] As the cation moiety of such an onium salt having a naphthalene ring in the cation moiety, the structure represented by the following formula (b1) is preferable.

[0228]

Chem.

[0229] In the above formula (b1), R 1b , R 2b , R 3bAt least one of them represents a group represented by the following formula (b2), and the rest represent a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group which may have a substituent, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, R 1b R 2b R 3b One of them is a group represented by the following formula (b2), and the remaining two are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and the ends of these may be bonded to form a ring. R 1b R 2b R 3b Specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms as R R 1b R 2b R 3b Specific examples of the linear or branched alkoxy group having 1 to 6 carbon atoms as R R 1b R 2b R 3b When R

[0230]

Chemical formula

[0231] In the above formula (b2), R 4b R 5beach independently represents a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms, and R 6b represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms which may have a substituent. l and m each independently represent an integer of 0 or more and 2 or less, and l + m is 3 or less. However, when R 4b is present in a plurality, they may be the same as or different from each other. Also, when R 5b is present in a plurality, they may be the same as or different from each other. R 4b , and R 5b Specific examples of the linear or branched alkoxy group having 1 to 6 carbon atoms as R and R 4b include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, and an n-hexyloxy group. 5b Specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms as R and R 6b include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.

[0232] The above R 1b , R 2b , R 3bAmong them, the number of the groups represented by the above formula (b2) is preferably one from the viewpoint of the stability of the compound, and the rest are linear or branched alkylene groups having 1 to 6 carbon atoms, and the ends thereof may be bonded to form a ring. In this case, the above two alkylene groups form a 3- to 9-membered ring including a sulfur atom. The number of atoms (including the sulfur atom) constituting the ring is preferably 5 or more and 6 or less.

[0233] Examples of the substituent that the alkylene group may have include an oxygen atom (in this case, forming a carbonyl group together with the carbon atom constituting the alkylene group), a hydroxyl group, and the like.

[0234] Examples of the substituent that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms, and the like.

[0235] Preferred examples of these cation moieties include those represented by the following formulas (b3), (b4-1), and (b4-2), and particularly, the structures represented by the following formulas (b4-1) and (b4-2) are preferred.

[0236]

Chemical formula

[0237] Such a cation moiety may be an iodonium salt or a sulfonium salt, but a sulfonium salt is desirable from the viewpoint of acid generation efficiency and the like.

[0238] Therefore, as a suitable anion moiety of an onium salt having a naphthalene ring in the cation moiety, an anion capable of forming a sulfonium salt is desirable.

[0239] Such an anion moiety of the acid generator is a fluoroalkylsulfonate ion or an arylsulfonate ion in which some or all of the hydrogen atoms are fluorinated.

[0240] In the fluoroalkylsulfonate ion, the alkyl group may be linear, branched, or cyclic and have 1 to 20 carbon atoms. Considering the bulkiness of the generated acid and its diffusion distance, it preferably has 1 to 10 carbon atoms. In particular, branched or cyclic ones are preferred because of their short diffusion distance. Also, due to their synthesizability at low cost, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, etc. can be mentioned as preferred ones.

[0241] In the arylsulfonate ion, the aryl group is an aryl group having 6 to 20 carbon atoms, and examples include a phenyl group and a naphthyl group which may or may not be substituted with an alkyl group or a halogen atom. In particular, due to their synthesizability at low cost, an aryl group having 6 to 10 carbon atoms is preferred. Specific examples of preferred ones include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, a methylnaphthyl group, etc.

[0242] In the above fluoroalkylsulfonate ion or arylsulfonate ion, when part or all of the hydrogen atoms are fluorinated, the fluorination rate is preferably 10% or more and 100% or less, more preferably 50% or more and 100% or less. In particular, those in which all hydrogen atoms are replaced with fluorine atoms are preferred because the acid strength becomes stronger. Specific examples of such include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, perfluorobenzenesulfonate, etc.

[0243] Among these, as a preferred anion part, those represented by the following formula (b5) can be mentioned.

[0244]

Chemical formula

[0245] In the above formula (b5), R 7b is a group represented by the following formulas (a10), (a11), and (a12).

[0246] [Chemical formula]

[0247] In the above formula (b6), x represents an integer of 1 or more and 4 or less. Further, in the above formula (b7), R 8b represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms, and y represents an integer of 1 or more and 3 or less. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferable from the viewpoint of safety.

[0248] Further, as the anion part, those containing nitrogen represented by the following formulas (b9) and (b10) can also be used.

[0249] [Chemical formula]

[0250] In the above formulas (b9) and (b10), X b represents a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and most preferably 3 carbon atoms. Further, Y b , Z b each independently represents a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, the alkyl group has 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and more preferably 1 to 3 carbon atoms.

[0251] X b The smaller the number of carbon atoms in the alkylene group of, or Y a , Z a the alkyl group of, the better the solubility in the organic solvent, which is preferable.

[0252] Further, X bThe alkylene group or Y b and Z b In the alkyl group, the larger the number of hydrogen atoms substituted by fluorine atoms, the stronger the acid strength, which is preferable. The ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate, is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and most preferably, a perfluoroalkylene group or perfluoroalkyl group in which all hydrogen atoms are substituted by fluorine atoms.

[0253] Preferred examples of such an onium salt having a naphthalene ring in the cation moiety include compounds represented by the following formulas (b11-1), (b11-2), and (b12).

[0254] [Chemical formula]

[0255] In the chemically amplified negative photosensitive composition, the photoacid generator (B1) may be used alone or in combination of two or more. The content of the photoacid generator (B1) in the chemically amplified negative photosensitive composition is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 0.2 part by mass or more and 20 parts by mass or less, and still more preferably 0.5 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polyimide resin precursor (A). When the content of the photoacid generator (B1) is within the above range, it is easy to obtain a chemically amplified negative photosensitive composition having particularly good photolithography characteristics.

[0256] [Crosslinking agent (C)] The crosslinking agent (C) is a compound capable of forming a crosslink by reacting with a phenolic hydroxyl group or an aromatic group having a phenolic hydroxyl group. As described above, the polyimide resin precursor (A) has a phenolic hydroxyl group in the side chain in the structural unit (1). Further, the chemically amplified negative photosensitive composition contains a photoacid generator (B1). Therefore, when the chemically amplified negative photosensitive composition is exposed, the chemically amplified negative photosensitive composition is cured by the crosslinking of the polyimide resin precursor (A) and the crosslinking agent (C) by the action of the acid generated by the photoacid generator (B1).

[0257] Examples of the crosslinking agent (C) include melamine-based crosslinking agents, urea-based crosslinking agents, alkylene urea-based crosslinking agents, glycoluril-based crosslinking agents, phenol-based crosslinking agents, epoxy-based crosslinking agents, oxetane-based crosslinking agents, and the like. In the following, "lower" means having 1 to 5 carbon atoms.

[0258] Examples of the melamine-based crosslinking agent include compounds obtained by reacting melamine with formaldehyde to substitute the hydrogen atom of the amino group with a hydroxymethyl group, and compounds obtained by reacting melamine with formaldehyde and a lower alcohol to substitute the hydrogen atom of the amino group with a lower alkoxymethyl group. Specifically, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, and the like can be mentioned. Among them, hexamethoxymethylmelamine is preferable.

[0259] Examples of the urea-based crosslinking agent include compounds obtained by reacting urea with formaldehyde to substitute the hydrogen atom of the amino group with a hydroxymethyl group, and compounds obtained by reacting urea with formaldehyde and a lower alcohol to substitute the hydrogen atom of the amino group with a lower alkoxymethyl group. Specifically, bis(methoxymethyl)urea, bis(ethoxymethyl)urea, bis(propoxymethyl)urea, bis(butoxymethyl)urea, and the like can be mentioned. Among them, bis(methoxymethyl)urea is preferable.

[0260] Examples of the alkylene urea-based crosslinking agent include compounds represented by the following formula (CA-1).

[0261] [Chemical formula] (In formula (CA-1), Rc 1 and Rc 2 are each independently a hydroxyl group or a lower alkoxy group. Rc 3 and Rc 4 are each independently a hydrogen atom, a hydroxyl group or a lower alkoxy group. vc is an integer of 0 or more and 2 or less.)

[0262] Rc 1 and Rc 2 When they are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms, and may be linear or branched. Rc 1 and Rc 2 may be the same or different from each other, and it is more preferable that they are the same. Rc 3 and Rc 4 When they are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms, and may be linear or branched. Rc 3 and Rc 4 may be the same or different from each other, and it is more preferable that they are the same. vc is preferably 0 or 1. As the alkylene urea-based crosslinking agent, in particular, a compound in which vc is 0 (ethylene urea-based crosslinking agent) and / or a compound in which vc is 1 (propylene urea-based crosslinking agent) is preferable.

[0263] The compound represented by the above formula (CA-1) can be obtained by subjecting alkylene urea and formalin to a condensation reaction, and further reacting this product with a lower alcohol.

[0264] Specific examples of the alkylene urea-based crosslinking agent include, for example, ethylene urea-based crosslinking agents such as mono- and / or dihydroxymethylated ethylene urea, mono- and / or dimethoxymethylated ethylene urea, mono- and / or diethoxymethylated ethylene urea, mono- and / or dipropoxymethylated ethylene urea, mono- and / or dibutoxymethylated ethylene urea; propylene urea-based crosslinking agents such as mono- and / or dihydroxymethylated propylene urea, mono- and / or dimethoxymethylated propylene urea, mono- and / or diethoxymethylated propylene urea, mono- and / or dipropoxymethylated propylene urea, mono- and / or dibutoxymethylated propylene urea; 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[0265] Examples of the glycoluril-based crosslinking agent include glycoluril derivatives in which the N-position is substituted with one or both of a hydroxyalkyl group and an alkoxyalkyl group having 1 to 4 carbon atoms. The glycoluril derivative can be obtained by subjecting glycoluril and formalin to a condensation reaction and then reacting the product with a lower alcohol. Specific examples of the glycoluril-based crosslinking agent include, for example, mono-, di-, tri- and / or tetrahydroxymethylated glycoluril; mono-, di-, tri- and / or tetramethoxymethylated glycoluril; mono-, di-, tri- and / or tetraethoxymethylated glycoluril; mono-, di-, tri- and / or tetrapropoxymethylated glycoluril; mono-, di-, tri- and / or tetrabutoxymethylated glycoluril, and the like.

[0266] The phenol-based crosslinking agent is not particularly limited as long as it is a compound having a plurality of phenol nuclear structures in the same molecule, and can be arbitrarily selected and used. Having a plurality of phenol nuclear structures improves the crosslinking reactivity. The number of phenol nuclear structures is preferably 2 or more and 5 or less, more preferably 2 or more and 4 or less, and still more preferably 2 or 3.

[0267] Specific examples suitable as glycoluril - based cross - linking agents or phenolic - based cross - linking agents are shown below.

[0268]

Chem.

[0269] As the epoxy - based cross - linking agent, there is no particular limitation as long as it is a cross - linking agent having an epoxy group, and it can be arbitrarily selected and used. Among them, a cross - linking agent having two or more epoxy groups is preferred. By having two or more epoxy groups, the cross - linking reactivity is improved. The number of epoxy groups is preferably two or more, more preferably two or more and four or less, and most preferably two. Specific examples suitable as the epoxy - based cross - linking agent are shown below.

[0270]

Chem.

[0271] Among the cross - linking agents (C) described above, the methylol - type cross - linking agent (C1) is preferred. The methylol - type cross - linking agent (C1) is a cross - linking agent having two or more cross - linkable groups selected from methylol groups and alkoxymethyl groups.

[0272] In the chemically amplified negative - type photosensitive composition, the cross - linking agent (C) may be used alone or in combination of two or more. The content of the cross - linking agent (C) in the chemically amplified negative - type photosensitive composition is preferably 1 part by mass or more and 70 parts by mass or less, more preferably 3 parts by mass or more and 50 parts by mass or less, and even more preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyimide resin precursor (A). When the content of the cross - linking agent (C) is within the above range, it is easy to obtain a chemically amplified negative - type photosensitive composition that gives a polyimide resin excellent in chemical resistance.

[0273] 〔Solvent (S)〕 The chemically amplified negative photosensitive composition preferably contains a solvent (S) for the purpose of adjusting coatability and the like. The type of the solvent (S) is not particularly limited as long as the polyimide resin precursor (A) and other components are well dissolved. Usually, an organic solvent is used as the solvent (S).

[0274] From the viewpoint of the good solubility of the polyimide resin precursor (A), specific examples of the solvent (S) include nitrogen-containing polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylpropionamide, N,N-dimethylisobutylamide, N,N-dimethylethyleneurea, N,N-dimethylpropyleneurea, N,N,N',N'-tetramethylurea, N,N,N',N'-tetraethylurea, and N,N,N',N'-tetrabutylurea; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, diisobutyl ketone, cyclopentanone, cyclohexanone, and isophorone;γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, isopentyl acetate, n-pentyl formate, n-butyl propionate, isopropyl butyrate, ethyl butyrate, n-butyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, methyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and other esters; diacetone alcohol, and alcohols such as 3-methyl-3-methoxybutanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, and other glycol ethers; aromatic ethers such as anisole; cyclic ethers such as dioxane and tetrahydrofuran; cyclic esters such as ethylene carbonate and propylene carbonate; aromatic solvents such as anisole, toluene, and xylene; aliphatic hydrocarbons such as limonene; and sulfoxides such as dimethyl sulfoxide.

[0275] The amount of the solvent (S) used is not particularly limited as long as a uniform liquid chemically amplified negative photosensitive composition can be prepared. The chemically amplified negative photosensitive composition may be a suspension or a solution, and a solution is preferred. Typically, the solvent (S) is used such that the solid content concentration of the chemically amplified negative photosensitive composition is preferably 15% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 45% by mass or less.

[0276] 〔Other Components〕 The chemically amplified negative photosensitive composition may contain various additives other than the components described above, if necessary. Examples of the additives include coloring agents, dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, defoaming agents, surfactants, imidization promoters, nitrogen-containing heterocyclic compounds as adhesion improvers, and silane coupling agents. Further, the chemically amplified negative photosensitive composition may contain various fillers or reinforcing materials, if necessary.

[0277] The nitrogen-containing heterocyclic compound improves the adhesion of the resin film formed using the chemically amplified negative photosensitive composition to the metal surface by coordinating and stabilizing on the metal surface. Known compounds can be used as the nitrogen-containing heterocyclic compound. Examples of the nitrogen-containing heterocyclic compound include imidazole, pyrazole, indazole, carbazole, triazole, pyrazoline, pyrazolidine, tetrazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid, and derivatives thereof. Specific examples of the nitrogen-containing heterocyclic compound preferred from the viewpoint of coordination with metals include triazoles such as 1H-benzotriazole, 4-methyl-1H-methylbenzotriazole, 5-methyl-1H-methylbenzotriazole, 4-carboxy-1H-methylbenzotriazole, and 5-carboxy-1H-methylbenzotriazole, and tetrazoles such as 1H-tetrazole, 5-methyl-1H-tetrazole, and 5-phenyl-1H-tetrazole.

[0278] From the perspective of achieving both excellent developability of the chemically amplified negative photosensitive composition and improved adhesion of the polyimide resin film formed using the chemically amplified negative photosensitive composition to substrates and the like, the amount of the nitrogen-containing heterocyclic compound used is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 3% by mass or less, based on the mass of the polyimide resin precursor (A).

[0279] By incorporating a silane coupling agent into the chemically amplified negative photosensitive composition, the adhesion of the resin film formed using the chemically amplified negative photosensitive composition to substrates and the like can be improved. Known compounds can be used as the silane coupling agent. Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(epoxycyclohexyl)ethyltrimethoxysilane, 2-(epoxycyclohexyl)triethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, tris(3-triethoxysilylpropyl)isocyanurate, the reaction product of 3-aminopropyltrimethoxysilane and an acid anhydride, the reaction product of 3-aminopropyltriethoxysilane and an acid anhydride, and the like. Examples of the acid anhydride to be reacted with 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane include succinic anhydride, maleic anhydride, nadic anhydride, 3-hydroxyphthalic anhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, and 4,4'-oxydiphthalic dianhydride.

[0280] The amount of the silane coupling agent used is preferably 0.01% by mass or more and 10% by mass or less, based on the mass of the polyimide resin precursor (A).

[0281] By incorporating a surfactant into the chemically amplified negative photosensitive composition, the coatability of the chemically amplified negative photosensitive composition is improved, and the wettability of the chemically amplified negative photosensitive composition with the substrate is also improved. As the surfactant, known compounds can be used. Examples of the surfactant include fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.

[0282] The amount of the surfactant used is preferably 0.001% by mass or more and 1% by mass or less based on the mass of the polyimide resin precursor (A).

[0283] The polyimide resin precursor (A) can be converted into a polyimide resin by heating. Therefore, the chemically amplified negative photosensitive composition may contain a cyclization accelerator. The cyclization accelerator promotes the formation of a polyimide resin by cyclization of a polyamide resin containing a structural unit derived from a polyamic acid or a dicarboxylic acid compound that can be synthesized by the reaction of a tetracarboxylic dianhydride and alcohols. When the chemically amplified negative photosensitive composition contains a cyclization accelerator, the mechanical properties and weather reliability of the resin film formed while generating a polyimide resin by cyclization using the chemically amplified negative photosensitive composition are improved. As the cyclization accelerator, known thermal base generators and thermal acid generators are used.

[0284] The amount of use of various additives is not particularly limited as long as it does not inhibit the object of the present invention. The amount of use of additives for which the amount of use is not described above may be appropriately adjusted within a range of, for example, 0.001% by mass or more and 60% by mass or less based on the mass of the solid content of the chemically amplified negative photosensitive composition, and preferably 0.01% by mass or more and 5% by mass or less.

[0285] 〔Method for preparing chemically amplified negative photosensitive composition〕 The chemically amplified negative photosensitive composition can be prepared by uniformly mixing the essential components and optional components described above in desired amounts respectively. The mixing method is not particularly limited. For the purpose of removing foreign matters in the chemically amplified negative photosensitive composition, it is preferable to filter the chemically amplified negative photosensitive composition through a filter.

[0286] <Positive photosensitive composition> The positive photosensitive composition contains a polyimide resin precursor (A), a photosensitizer (B), and a crosslinking agent (C). The photosensitizer (B) is a quinonediazide group-containing compound (B2). The crosslinking agent (C) is a compound capable of forming a crosslink by reaction with a phenolic hydroxyl group or an aromatic group having a phenolic hydroxyl group. Note that the positive photosensitive composition is solubilized in an alkaline developer upon exposure. Hereinafter, for the photosensitive composition containing the polyimide resin precursor (A), the quinonediazide group-containing compound (B2), and the crosslinking agent (C), it is conveniently referred to as a "positive photosensitive composition". Hereinafter, the essential or optional components that the positive photosensitive composition may contain will be described.

[0287] 〔Polyimide resin precursor (A)〕 The polyimide resin precursor (A) is the aforementioned polyimide resin precursor.

[0288] 〔Photosensitizer (B)〕 The photosensitizer (B) is a quinonediazide group-containing compound (B2). As the quinonediazide group-containing compound (B2), it can be appropriately selected from compounds having a quinonediazide group that have been conventionally incorporated into various positive photosensitive compositions.

[0289] Preferable specific examples of the quinonediazide group-containing compound (B2) include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,2',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, 2,3,3', and 4,4',5'-hexahydroxybenzophenone; bis[(poly)hydroxyphenyl]alkanes such as bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 4,4'-{1-[4-[2-(4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol, and 3,3'-dimethyl-{1-[4-[2-(3-methyl-4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol, 1-[(1-(4-hydroxyphenyl)-1-methyl)ethyl]-4-[(1,1-di(4-hydroxyphenyl)ethyl]benzene;Tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, and bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, etc., tris(hydroxyphenyl)methanes or their methyl-substituted derivatives; bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, and bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane, etc., bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methanes or their methyl-substituted derivatives;Compounds having a hydroxyl group or an amino group such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, and 4,4'-diaminobenzophenone; and complete ester compounds, partial ester compounds, amidated compounds, or partial amidated compounds, etc. of pyrogallol-acetone resin, etc. with a quinonediazide group-containing sulfonic acid. These quinonediazide group-containing compounds (B2) may be used alone or in combination of two or more.

[0290] The quinonediazide group-containing sulfonic acid used as the quinonediazide group-containing compound (B2) is not particularly limited. For example, naphthoquinonediazide sulfonic acids such as naphthoquinone-1,2-diazide-5-sulfonic acid and naphthoquinone-1,2-diazide-4-sulfonic acid; orthoanthraquinonediazide sulfonic acid, etc. may be mentioned, and naphthoquinonediazide sulfonic acid is preferred. The above ester compounds of the quinonediazide group-containing sulfonic acid, preferably naphthoquinonediazide sulfonic acid, are well dissolved in solvents usually used when the positive photosensitive composition is used as a solution. When these compounds are blended into the positive photosensitive composition as the quinonediazide group-containing compound (B2), a high-sensitivity positive photosensitive composition is easily obtained.

[0291] The production method of the above ester compound as the quinonediazide group-containing compound (B2) is not particularly limited. For example, a quinonediazide group-containing sulfonic acid is added as a sulfonyl chloride such as naphthoquinone-1,2-diazide-sulfonyl chloride, and condensed in a solvent such as dioxane in the presence of an alkali such as triethanolamine, alkali carbonate, or alkali hydrogencarbonate to perform complete esterification or partial esterification.

[0292] In addition, it is also preferable that the positive photosensitive composition contains, as a quinonediazide group-containing compound, a combination of a compound represented by the following formula (B2-1), a compound represented by the following formula (B2-2), and a compound represented by the following formula (B2-3) in terms of the good sensitivity and resolution of the positive photosensitive composition and the ease of forming a well-shaped patterned resist film using the positive photosensitive composition.

[0293] [Chemical formula] (In formula (B2-1), R b01 are each independently an alkyl group having 1 to 5 carbon atoms, D is each independently a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of the 2 + m Ds is a 1,2-naphthoquinonediazide-5-sulfonyl group, and l and m are each independently 1 or 2.)

[0294] [Chemical formula] (In formula (B2-2), D is each independently a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of the 3 Ds is a 1,2-naphthoquinonediazide-5-sulfonyl group.) and a compound represented by the following formula (B3):

[0295] [Chemical formula] (In formula (B2-3), R b02 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R b03 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, D is each independently a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of the 4 Ds is a 1,2-naphthoquinonediazide-5-sulfonyl group.)

[0296] In formula (B2-1), R b01 is, independently of each other, an alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms may be linear or branched. Preferable specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group. R b01 is preferably a methyl group and an ethyl group, more preferably a methyl group.

[0297] From the viewpoint that it is easy to keep the solubility of the positive photosensitive composition in the developer and the sensitivity within an appropriate range, the average ratio (average esterification rate) of D being a 1,2-naphthoquinonediazide-5-sulfonyl group in the quinonediazide ester compound represented by formula (B2-1) is preferably 40% or more and 60% or less, more preferably 50% or more and 55% or less.

[0298] From the viewpoint that it is easy to keep the solubility of the positive photosensitive composition in the developer and the sensitivity within an appropriate range, the average ratio (average esterification rate) of D being a 1,2-naphthoquinonediazide-5-sulfonyl group in the quinonediazide ester compound represented by formula (B2-2) is preferably 65% or more and 85% or less, more preferably 70% or more and 75% or less.

[0299] In formula (B2-3), R b02 is, independently of each other, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be linear or branched. Preferable specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group. R b3As for this, a hydrogen atom or a methyl group is preferable, and a hydrogen atom group is more preferable.

[0300] In formula (B2-3), R b03 is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms is the same as the alkyl group as R b02 is. Specific examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, an isopentyloxy group, a neopentyloxy group, and an n-hexyloxy group and the like. Specific examples of the cycloalkyl group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Among these, a cyclohexyl group is preferable.

[0301] When the compound represented by formula (B2-1), the compound represented by formula (B2-2), and the compound represented by formula (B2-3) are used in combination, the mass M1 of the compound represented by formula (B2-1), the mass M2 of the compound represented by formula (B2-2), and the total (M2 + M3) of the mass M3 of the compound represented by formula (B2-3), the ratio M1 / (M2 + M3) is preferably 30 / 70 or more and 70 / 30 or less, and more preferably 40 / 60 or more and 60 / 40 or less. The ratio M2 / M3 of the mass M2 of the compound represented by formula (B2-2) and the mass M3 of the compound represented by formula (B2-3) is preferably 30 / 70 or more and 70 / 30 or less, and more preferably 40 / 60 or more and 60 / 40 or less.

[0302] The content of the quinonediazide group-containing compound (B2) is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the polyimide resin precursor (A) from the viewpoint of the sensitivity of the positive photosensitive composition.

[0303] [Sensitizer (C)] The positive photosensitive composition may contain a sensitizer (C). The sensitizer (C) is a compound having a phenolic hydroxyl group with a molecular weight of 1000 or less. When the positive photosensitive composition contains a combination of the polyimide resin precursor (A), the quinonediazide group-containing compound (B2), and the sensitizer (C), it is easy to achieve both a good cross-sectional shape of the patterned resin film and high sensitivity.

[0304] Preferable examples of the compound that can be used as the sensitizer (C) include various phenolic hydroxyl group-containing compounds described for the quinonediazide group-containing compound (B2). That is, preferred specific examples of the sensitizer (C) include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,2',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, 2,3,3', and 4,4',5'-hexahydroxybenzophenone; bis[(poly)hydroxyphenyl]alkanes such as bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 4,4'-{1-[4-[2-(4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol, and 3,3'-dimethyl-{1-[4-[2-(3-methyl-4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol; tris(hydroxyphenyl)methanes or their methyl-substituted products such as tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, and bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane;Bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, and bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane, etc., bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methanes or their methyl-substituted derivatives; compounds having a hydroxyl group such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, and gallic acid are exemplified.;

[0305] The content of the sensitizer (C) is not particularly limited as long as it does not inhibit the object of the present invention. Since it is easy to obtain the desired effects regarding the cross-sectional shape and sensitivity of the resin film formed using the positive photosensitive composition, the content of the sensitizer (C) is preferably 10 parts by mass or more and 30 parts by mass or less, more preferably 13 parts by mass or more and 27 parts by mass or less, and still more preferably 15 parts by mass or more and 20 parts by mass or more with respect to 100 parts by mass of the polyimide resin precursor (A).

[0306] 〔Crosslinking agent (C)〕 The crosslinking agent (C) is a compound capable of forming a crosslink by reaction with a phenolic hydroxyl group or an aromatic group having a phenolic hydroxyl group. The crosslinking agent (C) contained in the positive photosensitive composition is the same as the crosslinking agent (C) contained in the chemically amplified negative photosensitive composition. The content of the crosslinking agent (C) in the positive photosensitive composition is also the same as the content of the crosslinking agent (C) in the chemically amplified negative photosensitive composition.

[0307] 〔Solvent (S)〕 The positive photosensitive composition preferably contains a solvent (S) for the purpose of adjusting coatability, etc. The type of the solvent (S) is not particularly limited as long as the polyimide resin precursor (A) and other components are well dissolved. The solvent (S) that the positive photosensitive composition may contain is the same as the solvent (S) that the chemically amplified negative photosensitive composition may contain. The content of the solvent (S) in the positive photosensitive composition is also the same as the content of the solvent (S) in the chemically amplified negative photosensitive composition.

[0308] 〔Other components〕 The positive photosensitive composition may contain various additives other than the components described above as necessary. Examples of the additives include colorants, dispersants, adhesion promoters, polymerization inhibitors, antioxidants, ultraviolet absorbers, anti-aggregation agents, defoaming agents, surfactants, imidization accelerators, nitrogen-containing heterocyclic compounds as adhesion improvers, and silane coupling agents. Further, the positive photosensitive composition may contain various fillers or reinforcing materials as necessary.

[0309] The nitrogen-containing heterocyclic compound coordinates to the metal surface and stabilizes it, thereby improving the adhesion of the resin film formed using the positive photosensitive composition to the metal surface. As the nitrogen-containing heterocyclic compound, known compounds can be used. Examples of the nitrogen-containing heterocyclic compound include imidazole, pyrazole, indazole, carbazole, triazole, pyrazoline, pyrazolidine, tetrazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid, and their derivatives. Specific examples of the nitrogen-containing heterocyclic compound preferable from the viewpoint of coordination with the metal include triazoles such as 1H-benzotriazole, 4-methyl-1H-methylbenzotriazole, 5-methyl-1H-methylbenzotriazole, 4-carboxy-1H-methylbenzotriazole, and 5-carboxy-1H-methylbenzotriazole, and tetrazoles such as 1H-tetrazole, 5-methyl-1H-tetrazole, and 5-phenyl-1H-tetrazole.

[0310] From the viewpoint of achieving both excellent developability of the positive photosensitive composition and improved adhesion of the polyimide resin film formed using the positive photosensitive composition to a substrate or the like, the amount of the nitrogen-containing heterocyclic compound used is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 3% by mass or less, based on the mass of the polyimide resin precursor (A).

[0311] By incorporating a silane coupling agent into a positive photosensitive composition, the adhesion of a resin film formed using the positive photosensitive composition to a substrate or the like can be improved. As the silane coupling agent, known compounds can be used. Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(epoxycyclohexyl)ethyltrimethoxysilane, 2-(epoxycyclohexyl)triethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, tris(3-triethoxysilylpropyl)isocyanurate, a reaction product of 3-aminopropyltrimethoxysilane and an acid anhydride, a reaction product of 3-aminopropyltriethoxysilane and an acid anhydride, and the like. Examples of the acid anhydride to be reacted with 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane include succinic anhydride, maleic anhydride, nadic anhydride, 3-hydroxyphthalic anhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, and 4,4'-oxydiphthalic dianhydride.

[0312] The amount of the silane coupling agent used is preferably 0.01% by mass or more and 10% by mass or less based on the mass of the polyimide resin precursor (A).

[0313] By incorporating a surfactant into a positive photosensitive composition, the coatability of the positive photosensitive composition is improved, and the wettability of the positive photosensitive composition with a substrate is also improved. As the surfactant, known compounds can be used. Examples of the surfactant include fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.

[0314] The amount of the surfactant used is preferably 0.001% by mass or more and 1% by mass or less based on the mass of the polyimide resin precursor (A).

[0315] The polyimide resin precursor (A) can be converted into a polyimide resin by heating. Therefore, the positive photosensitive composition may contain a cyclization accelerator. When the positive photosensitive composition contains a cyclization accelerator, the mechanical properties and weather reliability of the resin film formed while producing a polyimide resin by cyclization are improved by using the positive photosensitive composition. As the cyclization accelerator, known thermal base generators and thermal acid generators are used.

[0316] The amount of use of various additives is not particularly limited as long as it does not inhibit the object of the present invention. The amount of use of additives for which the amount of use is not described above may be appropriately adjusted within the range of, for example, 0.001% by mass or more and 60% by mass or less based on the mass of the solid content of the positive photosensitive composition, and is preferably 0.01% by mass or more and 5% by mass or less.

[0317] <Method for preparing a positive photosensitive composition> The positive photosensitive composition can be prepared by uniformly mixing the essential components and the optional components as required in the desired amounts. The mixing method is not particularly limited. For the purpose of removing foreign matters in the positive photosensitive composition, it is preferable to filter the positive photosensitive composition through a filter.

[0318] ≪Photosensitive dry film≫ The photosensitive dry film has a base film and a photosensitive layer formed on the surface of the base film, and the photosensitive layer is composed of the aforementioned photosensitive composition.

[0319] As the base film, those having light transmittance are preferable. Specifically, polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, etc. can be mentioned, but polyethylene terephthalate (PET) film is preferable in terms of excellent balance between light transmittance and breaking strength.

[0320] A photosensitive dry film is manufactured by applying the aforementioned photosensitive composition onto a base film to form a photosensitive layer. When forming a photosensitive layer on a base film, an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, etc. are used to apply the photosensitive composition onto the base film so that the film thickness after drying is preferably 0.5 μm or more and 300 μm or less, more preferably 1 μm or more and 300 μm or less, and particularly preferably 3 μm or more and 100 μm or less, followed by drying.

[0321] The photosensitive dry film may further have a protective film on the photosensitive layer. Examples of this protective film include a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, etc.

[0322] ≪Method for manufacturing a polyimide resin film≫ Applying the aforementioned photosensitive composition onto a substrate to form a coating film, heating the coating film to imidize the polyimide resin precursor (A) contained in the coating film. A polyimide resin film can be manufactured by a method including these steps.

[0323] In the above method, a patterned polyimide resin film can be manufactured by selectively exposing the coating film, developing the exposed coating film with a developer, and heating the developed coating film to imidize the polyimide resin precursor (A) contained in the coating film.

[0324] The substrate is not particularly limited, and conventionally known substrates can be used. For example, substrates for electronic components, those with a predetermined wiring pattern formed thereon, etc. can be exemplified. As the substrate, a silicon substrate, a glass substrate, etc. can also be used.

[0325] The thickness of the coating film is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, particularly preferably 1 μm or more and 150 μm or less, and most preferably 3 μm or more and 100 μm or less.

[0326] As a method for applying the photosensitive composition onto the substrate, methods such as spin coating method, slit coating method, roll coating method, screen printing method, applicator method, etc. can be adopted.

[0327] The photosensitive composition applied onto the substrate is usually made into a coating film by drying. The method for drying the photosensitive composition applied onto the substrate is not particularly limited. Preferably, drying is carried out by heating. The heating conditions during drying vary depending on the types of each component in the photosensitive composition, the blending ratio, the coating film thickness, etc., but usually it is at 70 °C or more and 200 °C or less, preferably 80 °C or more and 150 °C or less, and about 2 minutes or more and 120 minutes or less.

[0328] By heating the coating film formed as described above to imidize the polyimide resin precursor (A) contained in the coating film, a polyimide resin film is formed. The heating conditions for imidization are not particularly limited as long as the polyimide resin precursor does not decompose and imidization proceeds well. Typically, as the heating temperature, 180 °C or more and 400 °C or less is preferable, and 200 °C or more and 350 °C or less is more preferable. The heating time depends on the heating temperature, but typically, 1 hour or more and 24 hours or less is preferable, and 2 hours or more and 12 hours or less is more preferable. Heating is preferably carried out in an inert gas atmosphere such as nitrogen or argon from the viewpoint of preventing oxidation of the resin film and obtaining a resin film with good mechanical properties.

[0329] Also, the coating film formed as described above is selectively exposed to actinic rays or radiation, and then the exposed coating film is developed with a developer to form a patterned resin film. The patterned resin film is imidized by heating according to the above method to form a patterned polyimide resin film.

[0330] The selective exposure is usually performed by selectively irradiating actinic rays or radiation, such as ultraviolet rays or visible light having a wavelength of 300 nm or more and 500 nm or less, through a mask having a predetermined pattern.

[0331] As the radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. can be used. Also, radiation includes microwaves, infrared rays, visible light, ultraviolet rays, X-rays, γ-rays, electron beams, proton beams, neutron beams, ion beams, etc. The radiation dose varies depending on the composition of the resin film-forming photosensitive resin, the film thickness of the photosensitive layer, etc. For example, when using an ultra-high-pressure mercury lamp, it is 20 mJ / cm 2 or more and 10000 mJ / cm 2 or less.

[0332] Next, the exposed coating film is developed according to a conventionally known method, and unnecessary portions are dissolved and removed to form a resin film patterned into a predetermined shape. At this time, a developer corresponding to the components contained in the photosensitive composition is used. When the aforementioned polyimide resin precursor is a resin having an alkali-soluble group such as a carboxy group, an alkaline aqueous solution can be used as the developer. Also, as the developer, the aforementioned solvent (S) can be used.

[0333] As the alkaline developer, for example, aqueous solutions of alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (tetramethylammonium hydroxide), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above aqueous solution of alkalis can also be used as the developer.

[0334] The development time varies depending on the composition of the photosensitive composition, the film thickness of the coating film, etc., but is usually between 1 minute and 30 minutes. The development method may be any of a puddle method, a dipping method, a paddle method, a spray development method, etc.

[0335] After development, washing is performed for 30 seconds or more and 90 seconds or less as necessary, and the patterned resin film is dried using an air gun, an oven, etc. In this way, a resin film patterned in a desired shape is formed on the surface of the substrate. The washing solvent is not particularly limited. As an example, water, alcohols, etc. can be used as the washing solvent in the case of alkaline development. When developing with the solvent (S), the solvent (S) can be used as long as solvent shock does not occur.

[0336] The patterned resin film thus formed is imidized by heating according to the above method, whereby a patterned polyimide resin film is formed.

[0337] The patterned polyimide resin film formed as described above is suitably used, for example, as an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, an insulating film or a protective film in a touch panel display, an organic electroluminescence display panel, or the like. Since the photosensitive composition described above has good resolution, the patterned resin film formed as described above can be preferably used particularly as an interlayer insulating film for a rewiring layer in a three-dimensional mounting device. Further, the patterned resin film formed as described above can also be suitably used as a photoresist for electronics, a galvanic (electrolytic) resist, an etching resist, a solder top resist, or the like. Furthermore, the patterned resin film formed as described above can also be used in the manufacture of a printing plate surface such as an offset printing plate surface or a screen printing plate surface, the formation of an etching mask when etching a molded part, a protective lacquer in electronic parts, particularly microelectronic parts, and the manufacture of a dielectric layer.

Examples

[0338] Hereinafter, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to these examples.

[0339] 〔Examples 1 to 10, Comparative Example 1, and Comparative Example 2〕 In the examples and the comparative examples, the following DA1 was used as the diamine compound.

Chemical formula

[0340] In the examples and the comparative examples, the following TC1 and TC2 were used as the tetracarboxylic dianhydride.

Chemical formula

[0341] In the examples and comparative examples, the following A1 to A10 were used as the alcohols to react with the tetracarboxylic dianhydride. A1: 2-(4-Hydroxyphenyl)ethanol A2: 2-(2-Hydroxyphenyl)ethanol A3: 4-(4-Hydroxyphenyl)butan-2-ol (rhododendrol) A4: 2-(3,4-Dihydroxyphenyl)ethanol A5: 4-Hydroxyphenyl β-D-glucopyranoside (arbutin) A6: 3-(4-Hydroxyphenyl)propanol A7: 2-(2-Hydroxyethoxy)phenol A8: 4-(2-Hydroxyethoxy)phenol A9: 4-(6-Hydroxyhexyloxy)phenol A10: 2-Hydroxyethyl methacrylate

[0342] In the examples and comparative examples, the following B1 to B3 were used as the photosensitizer (B). B1 is a photoacid generator. B2 is a quinonediazide group-containing compound, and B3 is a photo radical polymerization initiator.

Chemical formula

[0343] In the examples and comparative examples, the following C1, C2, and C3 were used as the crosslinking agent (C). C3 is a polyfunctional thiol compound (pentaerythritol tetrakis(3-mercaptobutyrate)).

Chemical formula

[0344] 〔Production of polyimide resin precursor (A)〕 0.032 mol of the tetracarboxylic dianhydride of the type described in Table 1 was dissolved in N-methyl-2-pyrrolidone (NMP) so that the concentration was 25% by mass. To the resulting solution, 0.068 mol of the alcohol of the type described in Table 1 and 0.068 mol of pyridine were added. Next, the solution to which the alcohol and pyridine were added was stirred at room temperature for 16 hours. After stirring, the solution was cooled to 0 °C. To the cooled solution, a DCC solution in which 0.068 mol of dicyclohexylcarbodiimide (DCC) was dissolved in NMP at a concentration of 25% by mass and a diamine solution in which 0.0322 mol of the above DA1 was dissolved in NMP at a concentration of 25% by mass were each added dropwise. Next, the solution was stirred at room temperature for 4 hours. After completion of stirring, the solution was poured into isopropyl alcohol (IPA). The precipitate deposited in IPA was collected by filtration. The powder recovered by filtration was washed three times with IPA and then dried under reduced pressure to obtain the polyimide resin precursor (A) used in each example and each comparative example.

[0345] 〔Examples 1 to 9〕 The polyimide resin precursor (A) was dissolved in γ-butyrolactone so that the concentration was 30% by mass. To the resulting solution, 1% by mass of the above B1 with respect to the mass of the polyimide resin precursor (A) was dissolved as the photosensitizer (B). Further, 10% by mass of the above C1 with respect to the mass of the polyimide resin precursor (A) was dissolved as the crosslinking agent (C) in the resulting solution. In this way, the photosensitive compositions of Examples 1 to 9 were obtained. The photosensitive compositions of Examples 1 to 9 are chemically amplified negative-type photosensitive compositions.

[0346] 〔Example 10〕 The polyimide resin precursor (A) was dissolved in γ-butyrolactone so that the concentration was 30% by mass. To the resulting solution, 1% by mass of the above B2 with respect to the mass of the polyimide resin precursor (A) was dissolved as the photosensitizer (B). Further, 10% by mass of the above C2 with respect to the mass of the polyimide resin precursor (A) was dissolved as the crosslinking agent (C) in the resulting solution. In this way, the photosensitive composition of Example 10 was obtained. The photosensitive composition of Example 10 is a positive-type photosensitive composition.

[0347] [Comparative Example 1 and Comparative Example 2] The polyimide resin precursor (A) was dissolved in N,N,N’,N’-tetramethylurea so that the concentration was 30% by mass. To the obtained solution, 0.5% by mass of the above B3 with respect to the mass of the polyimide resin precursor (A) was dissolved as the photosensitizer (B). Further, to the obtained solution, 0.5% by mass of the above C3 with respect to the mass of the polyimide resin precursor (A) was dissolved as the crosslinking agent (C). In this way, the photosensitive compositions of Comparative Example 1 and Comparative Example 2 were obtained. The photosensitive compositions of Comparative Example 1 and Comparative Example 2 are negative photosensitive compositions. The polyimide resin precursor (A) contained in the photosensitive compositions of Comparative Example 1 and Comparative Example 2 contains a (meth)acryloyl group in the side chain. Further, the above C3 is a polyfunctional thiol compound. When the photosensitive compositions of Comparative Example 1 and Comparative Example 2 are exposed, an en-thiol reaction occurs between the (meth)acryloyl group of the polyimide resin precursor (A) and the thiol group of the polyfunctional thiol compound. As a result, the photosensitive composition cures.

[0348] Using the obtained photosensitive compositions of each example and each comparative example, the chemical resistance and the resolution of the cured film were evaluated by the following method. These evaluation results are shown in Table 1.

[0349] [Chemical Resistance] The photosensitive composition was applied onto a silicon wafer by a spin coater. Next, the coated film was baked at 90°C for 240 seconds. The film thickness of the formed coated film was about 10 μm. The baked coated film was exposed using a high-pressure mercury lamp with an integrated light amount of 2000 mJ / cm 2 The exposed coated film was heated in an inert oven at a rate of 5°C / min to 230°C under a nitrogen atmosphere. Next, at the same temperature, the coated film was heated for 1 hour to cause imidization. After the heating was completed, the inert oven was allowed to cool, and when the temperature in the oven reached 100°C, the silicon wafer provided with the polyimide resin film was taken out of the oven. The small pieces obtained by cutting the obtained silicon wafer into 5 cm × 5 cm were used as test pieces for chemical resistance evaluation. The obtained test piece was immersed in an aqueous sulfuric acid solution with a concentration of 30% by mass at 25°C for 60 minutes. The polyimide resin film provided on the test piece after immersion was visually observed. Also, the film thickness T1 of the polyimide resin film before immersion and the film thickness T2 of the polyimide resin film after immersion were measured, and the film thickness change rate was calculated based on the following formula. Film thickness change rate (%) = |T1 / T2 × 100 - 100| Based on the results of the visual observation of the polyimide resin film and the film thickness change rate, the chemical resistance of the polyimide resin film was evaluated according to the following criteria. When the evaluation is A or B, the chemical resistance of the polyimide resin film is good. A: The film thickness change rate is less than 5%, and there is no change in the appearance of the polyimide resin film after immersion. B: The film thickness change rate is less than 5%, and there is a change in the appearance of the polyimide resin film after immersion. C: The film thickness change rate is 5% or more.

[0350] <Photolithography characteristics (resolution) evaluation> The photosensitive composition was applied onto the copper sputter film of a silicon wafer on which a copper sputter film was formed using a spin coater. Next, the coated film was baked at 80°C for 300 seconds. The film thickness of the formed coated film was 10 μm. The formed coated film was exposed using a ghi-ray exposure machine (manufactured by Ultratech Inc.) through a negative mask capable of forming via holes with an opening diameter of 3 to 50 μm. The exposed coated film was immersed in a developer for development. In Examples 1 to 9, Comparative Example 1, and Comparative Example 2, cyclopentanone was used as the developer. In Example 10, an aqueous solution of tetramethylammonium hydroxide with a concentration of 2.38% by mass was used as the developer. As a result of the development, the minimum via hole diameter at which a pattern could be formed at an exposure dose of 2000 mJ / cm 2 The minimum via hole diameter at which a pattern could be formed is shown in Table 1 below. The smaller the via hole diameter, the better the resolution.

[0351]

Table 1

[0352] According to Table 1, it can be seen that the photosensitive composition containing the polyimide resin precursor (A) having a structural unit corresponding to the structure of formula (1) having a phenolic hydroxyl group in the side chain and the photosensitizer (B) gives a polyimide resin film excellent in chemical resistance and excellent in resolution. On the other hand, the photosensitive material of the comparative example containing the polyimide resin precursor (A) having a structural unit having a methacryloyl group in the side chain and the photosensitizer (B) gave a polyimide resin film inferior in chemical resistance and also inferior in resolution.

Claims

1. It contains a structural unit (1) represented by the following formula (1), and may or may not contain a structural unit (2) represented by the following formula (2), A polyimide resin precursor, wherein the structural unit (2) is a structural unit that does not correspond to the structural unit (1). 【Chemical 1】 (In formula (1), X Ａ１ is a tetravalent organic group having 4 to 40 carbon atoms, and Y Ａ１ is a divalent organic group having 4 to 40 carbon atoms, R Ａ１ is each independently a divalent aliphatic group having 2 or more carbon atoms which may be substituted with a hydroxyl group, and R Ａ２ is each independently an (a + 1)-valent aromatic group, and a is each independently an integer of 1 or more and 4 or less, Said R Ａ１ The aliphatic group as such is bonded to the non-carbonyl oxygen atom in the formula (1) via a C—O bond.) 【Chemical 2】 (In formula (2), X Ａ２ is a tetravalent organic group having 4 to 40 carbon atoms, and Y Ａ２ is a divalent organic group having 4 to 40 carbon atoms, R Ａ３ is, independently of one another, a hydroxyl group or a monovalent organic group, Said R Ａ３ The organic group as said is bonded to the non-carbonyl oxygen atom in the formula (2) via a C—O bond.)

2. The polyimide resin precursor according to claim 1, wherein the ratio of the structural unit (1) to the total number of moles of all structural units constituting the polyimide resin precursor is 70 mol% or more.

3. In the formula (1), R Ａ１ The polyimide resin precursor according to claim 1, wherein the divalent aliphatic group as is an alkylene group.

4. In the formula (1), R Ａ２ The polyimide resin precursor according to claim 1, wherein the aromatic group as is a group obtained by removing a hydrogen atoms from a monovalent aromatic hydrocarbon group.

5. In the formula (1), R Ａ２ -(OH) ａ The polyimide resin precursor according to claim 4, wherein the group represented by is a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxynaphthyl group, or a dihydroxynaphthyl group.

6. In the formula (1), X Ａ１ wherein the tetravalent organic group as is a residue obtained by removing two acid anhydride groups from an aromatic tetracarboxylic dianhydride, Y Ａ１ The polyimide resin precursor according to claim 1, wherein the divalent organic group as Y is a residue obtained by removing two amino groups from an aromatic diamine.

7. A photosensitive composition comprising a polyimide resin precursor (A) and a photosensitizer (B), The photosensitive composition, wherein the polyimide resin precursor (A) is the polyimide resin precursor according to claim 1.

8. The photosensitive composition contains the polyimide resin precursor (A), the photosensitizer (B), and a crosslinking agent (C), The photosensitizer (B) is a photoacid generator (B1), The photosensitive composition according to claim 7, wherein the crosslinking agent (C) is a compound capable of forming a crosslink by reaction with a phenolic hydroxyl group or an aromatic group having a phenolic hydroxyl group.

9. The crosslinking agent (C) is a methylol type crosslinking agent (C1), The photosensitive composition according to claim 8, wherein the methylol type crosslinking agent (C1) has two or more crosslinkable groups selected from a methylol group and an alkoxymethyl group.

10. The photosensitive composition contains the polyimide resin precursor (A), the photosensitizer (B), and a crosslinking agent (C), The photosensitizer (B) is a quinonediazide group-containing compound (B2), The photosensitive composition according to claim 7, wherein the crosslinking agent (C) is a compound capable of forming a crosslink by reaction with a phenolic hydroxyl group or an aromatic group having a phenolic hydroxyl group.

11. The crosslinking agent (C) is a methylol type crosslinking agent (C1), The photosensitive composition according to claim 10, wherein the methylol type crosslinking agent (C1) has two or more crosslinkable groups selected from a methylol group and an alkoxymethyl group.

12. A method for producing a polyimide resin film, comprising coating the photosensitive composition according to any one of claims 7 to 11 on a substrate to form a coating film, and heating the coating film to imidize the polyimide resin precursor (A) contained in the coating film.

13.

13. A method for producing a polyimide resin film, comprising coating the photosensitive composition according to any one of claims 7 to 11 on a substrate to form a coating film, and selectively exposing the coating film.

13. Developing the exposed coating film with a developer; A method for manufacturing a patterned polyimide resin film, comprising heating the developed coating film to imidize the polyimide resin precursor (A) contained in the coating film.

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