Polyimide resin precursor and photosensitive composition

Abstract

To provide a polyimide resin precursor that yields a polyimide resin film having superior chemical resistance and also produces a photosensitive composition having superior 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 photosensitive composition comprises a polyimide resin precursor comprising a structural unit with a specific structure having a side chain terminated by a specific aromatic group, together with a photoacid generator and a methylol-type crosslinker.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 thus are 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 parts that insulate metal wiring in 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, 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] In response to the above requirements, a photosensitive resin composition containing a resin and a photosensitizer has been proposed as a photosensitive resin composition capable of forming a patterned resin film with a low dielectric tangent by applying the photolithography method. 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. A photosensitive resin composition (Patent Document 1) selected from the group consisting of at least one kind 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, for the photosensitive resin composition described in Patent Document 1, further improvement is required in terms of chemical resistance and resolution.

[0008] The present invention has been made in view of the above problems, and aims to provide 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 of a specific structure having a side chain whose terminal is composed of a specific aromatic group to a photosensitive composition together with a photoacid generator and a methylol type crosslinking agent, and have thus 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 either 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

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 , and the two Rs A2 may be the same or different from each other.

[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 and a dicarboxylic acid which is a reaction product of a tetracarboxylic dianhydride and alcohols. However, the diamine compound, dicarboxylic acid, tetracarboxylic dianhydride, and alcohols are selected such that the polyimide resin precursor satisfies the above-described predetermined requirements.

[0018] 〔Constituent unit (1)〕 As described above, the constituent unit (1) is the constituent unit represented by the above formula (1). Hereinafter, the diamine compound that provides the constituent unit (1) and the dicarboxylic acid will be described.

[0019] (Diamine compound) The diamine compound that provides the constituent 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, and the upper limit is 40, 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 A1 When Y is an organic group containing one or more aromatic rings, the organic group may be an aromatic group itself, or a group in which two 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 Y include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -S-S-. Among them, -COO-, -O-, -CO-, and -S- are preferred.

[0023] Y A1 The aromatic ring bonded to the amino group in Y is preferably a benzene ring. Y A1 When the ring bonded to the amino group in Y is a condensed ring containing two or more rings, the ring bonded to the amino group in the condensed ring is preferably a benzene ring. Also, Y A1 The aromatic ring contained in Y 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- in Q is a phenylene group, an m-phenylene group and a p-phenylene group are preferred, and a p-phenylene group is more preferred. Also, -C 10 H6- is a naphthalenediyl group, 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 are preferred, and a naphthalene-1,4-diyl group and a naphthalene-2,6-diyl group are more preferred. Q 1 In the exemplification of n in Q is an integer of 1 or more, an integer of 1 or more and 20 or less is preferred, an integer of 1 or more and 12 or less is more preferred, and an integer of 1 or more and 6 or less is even more preferred.

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

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, -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- are both p-phenylene groups 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, as the aromatic diamine compound, 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, etc. 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 Corporation).

[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)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, and the like.

[0034] Since the diamine compound is excellent in solubility in an organic solvent of the polyimide resin precursor and dielectric properties in a high-frequency band of the polyimide resin formed using the polyimide resin precursor, the diamine compound is represented by the formula (A2a) and Y A1 is a diamine compound (A-1) which is a group represented by the following formula (A1-1), is 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), has 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), and a diamine compound (A-3), and preferably contains one or more selected from the group consisting of a dimer diamine compound (A-4). Among these, the diamine compound (A-1) and the diamine compound (A-2) are preferable.

[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 which may be substituted with R a2 or a naphthyl group which may be 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 number of carbon atoms of the aliphatic group as R

[0038] is preferably 1 to 12, more preferably 1 to 6.) a2Examples of the aliphatic group 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; and 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;

[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, 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, 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-, with -O-, -CO-, and -S- being 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 exemplified by the 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), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2. In formula (12), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2. In formula (13), ma2 is preferably 0, ma4 and ma5 are each preferably 0, ma6 and ma7 are each preferably 0, 1, or 2, the sum of ma6 and ma7 is 1 or more, and preferably 4 or less. In formula (14), ma2 is preferably 0, ma8, ma9, and ma10 are each preferably 0, ma11, ma12, and ma13 are each preferably 0, 1, or 2, the sum of ma11, ma12, and ma13 is 1 or more, and preferably 6 or less. In formula (15), ma2 is preferably 0, ma14 and ma15 are each preferably 0, ma16 and ma17 are each preferably 0, 1, or 2, 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. However, the divalent linking group is not a group containing an aromatic group. Examples of the divalent linking group include an aliphatic hydrocarbon group having 1 to 20 carbon atoms, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -S-S-, and a group 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 a methylene group, an ethane-1,2-diyl group (ethylene group), an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a propane-1,1-diyl group, a propane-2,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, a heptadecane-1,17-diyl group, an octadecane-1,18-diyl group, a nonadecane-1,19-diyl group, an icosane-1,20-diyl group, an ethene-1,2-diyl group (vinylene group), a propene-1,3-diyl group, an ethyne-1,2-diyl group, and a 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- and the like.

[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 a hetero atom such as O, N, S, P, B, Si, and a halogen atom. 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), it is preferable that ma1 is 0, it is preferable that ma2 is 0, and it is preferable that ma3 is 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 preferable, and a methyl group is more preferable. 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 preferable, and a methoxy group is more preferable. 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 preferable.

[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

[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 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.)

[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. Among them, p-phenylene group and biphenyl-4,4'-diyl group are more preferred, and p-phenylene group is 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

[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. Since the diamine compound (A-3) is easily available, etc., 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 the following compounds. Preferred examples of the group represented by X include a p-phenylene group, an m-phenylene group, a naphthalene-1,4-diyl group, and a biphenyl-4,4'-diyl group. More preferred examples include a p-phenylene group and a biphenyl-4,4'-diyl group. Even more preferred is a p-phenylene group.

[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 preferred 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, monomeric acids having 18 carbon atoms, trimeric 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 an alcohol represented by the following formula (a3a). In formula (A3a) and formula (a3a), RA1 , R A2 , and X A1 in formula (1), R A1 , R A2 , and X A1 is the same as

Chemical formula

[0086] Hereinafter, the tetracarboxylic dianhydride represented by formula (A3a) and the alcohol represented by formula (a3a) will be described.

[0087] · Tetracarboxylic dianhydride As described above, the dicarboxylic acid that provides the structural unit (1) is obtained by reacting the tetracarboxylic dianhydride represented by the above formula (A3a) with the alcohol represented by the above formula (a3a).

[0088] 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 formula (A3a) may contain a carboxy group or 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, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group. The same applies to the above substituents and one or more substituents that the aromatic group described later may have on the aromatic ring.

[0089] X A1The number of carbon atoms constituting it is preferably 8 or more, more preferably 12 or more. Further, X A1 The number of carbon atoms constituting it is preferably 30 or less. X A1 X may be an aliphatic group, an aromatic group, or a group combining these structures. A1 X may contain, in addition to carbon atoms and hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. A1 When X 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-. X A1 X may be contained in X as a group selected from -O-, -CO-, -S-, and A1 It is more preferably contained in X.

[0090] The tetracarboxylic dianhydride represented by 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 an aromatic group. That is, X A1 The tetravalent organic group as X is preferably a residue obtained by removing two dicarboxylic anhydride groups from an aromatic tetracarboxylic dianhydride.

[0091] 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 (for example, Ricaid BT-100, manufactured by Shin Nippon Rika Co., Ltd.). Examples of the aliphatic tetracarboxylic dianhydride having an alicyclic structure include cyclobutanetetracarboxylic 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 (for example, Enhydride (registered trademark) CpODA, manufactured by NeoResins), 2,2-bis(2,3-dicarboxyphenoxy)hexafluoropropane dianhydride, [5,5'-(1,4-phenylene)bisnorbornane]-2,2',3,3'-tetracarboxylic dianhydride (for example, Enhydride (registered trademark) BzDA, manufactured by NeoResins), 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione (for example, Rica Sid TD-100, manufactured by Shin Nippon Rika Co., Ltd.).

[0092] Examples of the aromatic tetracarboxylic dianhydride represented by the formula (A3a) and having two dicarboxylic anhydride groups bonded to an aromatic group include 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 (e.g., Ricacid TMEG100, manufactured by Shin Nippon Rika Co., Ltd.), and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane 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 preferred in that they easily form cured products with excellent electrical properties. α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride is a compound represented by the following formula (a1).

Chemical formula

[0093] 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.).

[0094] Also, in terms of suppressing the warping of the polyimide resin film formed using the photosensitive composition containing the polyimide resin precursor and having good photolithography characteristics of the 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.

[0095] Examples of the aromatic tetracarboxylic dianhydride may also be compounds represented by the following general formulas (a3-2) to (a3-4).

Chemical formula

[0096] 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.

[0097] 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.

[0098] · Alcohol As described above, the dicarboxylic acid that provides the structural unit (1) can be obtained by reacting a tetracarboxylic dianhydride represented by the following formula (A3a) with an alcohol represented by the above formula (a3a). Hereinafter, the alcohol represented by the formula (a3a) will be described. R A2 -R A1 -OH ··· (a3a)

[0099] R A1 is an alkylene group. The structure of the alkylene group as R A1 may be chain-like, straight-chain, or branched-chain.

[0100] R A1 The number of carbon atoms of the alkylene group as R

[0101] is 1 or more, preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 6 or less. A1 Preferable examples of the alkylene group as R Among these groups, an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,2-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a butane-2,3-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group are preferable, and an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,2-diyl group, a butane-1,3-diyl group, and a butane-1,4-diyl group are more preferable.

[0102] In formula (a3a), R A2 is an aryl group, a heteroaryl group, an aryloxy group, an arylthio group, an arylamino group, or an N-alkyl-N-arylamino group substituted with a group selected from an alkoxy group, a mercapto group, an alkylthio group, an amino group, an alkylamino group, and a dialkylamino group.

[0103] R A2 As the above groups, there are π-electron-rich sites. Therefore, when a photosensitive composition containing a polyimide resin precursor having the above groups as R A2 , a photoacid generator described later, and a methylol type crosslinking agent is exposed, crosslinking with the methylol type crosslinking agent by an electrophilic substitution reaction using the π-electron-rich site as a reaction point proceeds with respect to the above groups as R A2 .

[0104] Preferable specific examples of the aryl group in the aryl group substituted with a group selected from an alkoxy group, a mercapto group, an alkylthio group, an amino group, an alkylamino group, and a dialkylamino group include a phenyl group, a naphthalene-1-yl group, a naphthalene-2-yl group, a 4-phenylphenyl group, a 3-phenylphenyl group, and a 2-phenylphenyl group.

[0105] The number of carbon atoms of the alkoxy group as a substituent is not particularly limited. The number of carbon atoms of the alkoxy group is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less. Preferable examples of the alkoxy group 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.

[0106] The number of carbon atoms of the alkylthio group as a substituent is not particularly limited. The number of carbon atoms of the alkylthio group is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less. Preferable examples of the alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, and a tert-butylthio group.

[0107] The number of carbon atoms of the alkyl group in the alkylamino group as a substituent is not particularly limited. The number of carbon atoms of the alkyl group in the alkylamino group is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less. Preferable examples of the alkylamino group include a methylamino group, an ethylamino group, an n-propylamino group, an isopropylamino group, an n-butylamino group, an isobutylamino group, a sec-butylamino group, and a tert-butylamino group.

[0108] The number of carbon atoms of the alkyl group in the dialkylamino group as a substituent is not particularly limited. The number of carbon atoms of the alkyl group in the dialkylamino group is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less. Preferable examples of the dialkylamino group include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a diisobutylamino group, a di-sec-butylamino group, and a di-tert-butylamino group, a methylethylamino group, a methyl(n-propyl)amino group, and an ethyl(n-propyl)amino group.

[0109] Preferable specific examples of the heteroaryl group include a group obtained by removing one hydrogen atom from an aromatic heterocyclic ring such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, an indole ring, a dibenzothiophene ring, a dibenzofuran ring, a carbazole ring, a thiazole ring, a benzothiazole ring, an oxazole ring, a benzoxazole ring, an imidazole ring, a benzimidazole ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, a benzothiadiazole ring, and a phenanthridine ring.

[0110] Preferable examples of the aryloxy group include a phenoxy group, a naphthalen-1-yloxy group, a naphthalen-2-yloxy group, a 4-phenylphenoxy group, a 3-phenylphenoxy group, and a 2-phenylphenoxy group.

[0111] Preferable examples of the arylthio group include a phenylthio group, a naphthalen-1-ylthio group, a naphthalen-2-ylthio group, a 4-phenylphenylthio group, a 3-phenylphenylthio group, and a 2-phenylphenylthio group.

[0112] Preferable examples of the arylamino group include a phenylamino group, a naphthalen-1-ylamino group, a naphthalen-2-ylamino group, a 4-phenylphenylamino group, a 3-phenylphenylamino group, and a 2-phenylphenylamino group.

[0113] The number of carbon atoms of the alkyl group in the N-alkyl-N-aryl amino group is not particularly limited. The number of carbon atoms of the alkyl group in the N-alkyl-N-aryl amino group is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and still more preferably 1 or 2.

[0114] Preferable examples of the N-alkyl-N-aryl amino group include an N-methyl-N-phenyl amino group, an N-methyl-N-naphthalen-1-yl amino group, an N-methyl-N-naphthalen-2-yl amino group, an N-methyl-N-4-biphenyl amino group, an N-methyl-N-3-biphenyl amino group, an N-methyl-N-2-biphenyl amino group, an N-ethyl-N-phenyl amino group, an N-ethyl-N-naphthalen-1-yl amino group, an N-ethyl-N-naphthalen-2-yl amino group, an N-ethyl-N-4-biphenyl amino group, an N-ethyl-N-3-biphenyl amino group, and an N-ethyl-N-2-biphenyl amino group.

[0115] Preferable specific examples of the alcohol represented by formula (a3a) include alkoxybenzyl alcohols such as 4-methoxybenzyl alcohol, 3-methoxybenzyl alcohol, 2-methoxybenzyl alcohol, 4-ethoxybenzyl alcohol, 3-ethoxybenzyl alcohol, and 2-ethoxybenzyl alcohol; mercaptobenzyl alcohols such as 4-mercaptobenzyl alcohol, 3-mercaptobenzyl alcohol, and 2-mercaptobenzyl alcohol; alkylthiobenzyl alcohols such as 4-methylthiobenzyl alcohol, 3-methylthiobenzyl alcohol, 2-methylthiobenzyl alcohol, 4-ethylthiobenzyl alcohol, 3-ethylthiobenzyl alcohol, and 2-ethylthiobenzyl alcohol; aminobenzyl alcohols such as 4-aminobenzyl alcohol, 3-aminobenzyl alcohol, and 2-aminobenzyl alcohol; alkylbenzyl alcohols such as 4-methylaminobenzyl alcohol, 3-methylaminobenzyl alcohol, 2-methylaminobenzyl alcohol, 4-ethylaminobenzyl alcohol, 3-ethylaminobenzyl alcohol, and 2-ethylaminobenzyl alcohol; Dialkylaminobenzyl alcohols such as 4-dimethylaminobenzyl alcohol, 3-dimethylaminobenzyl alcohol, 2-dimethylaminobenzyl alcohol, 4-diethylaminobenzyl alcohol, 3-diethylaminobenzyl alcohol, and 2-diethylaminobenzyl alcohol; 2-(2-Alkoxyphenyl)ethanol such as 2-(4-methoxyphenyl)ethanol, 2-(3-methoxyphenyl)ethanol, 2-(2-methoxyphenyl)ethanol, 2-(4-ethoxyphenyl)ethanol, 2-(3-ethoxyphenyl)ethanol, and 2-(2-ethoxyphenyl)ethanol; 2-(2-Mercaptophenyl)ethanol such as 2-(4-mercaptophenyl)ethanol, 2-(3-mercaptophenyl)ethanol, and 2-(2-mercaptophenyl)ethanol; 2-(2-Alkoxyphenyl)ethanol such as 2-(4-methylthiophenyl)ethanol, 2-(3-methylthiophenyl)ethanol, 2-(2-methylthiophenyl)ethanol, 2-(4-ethylthiophenyl)ethanol, 2-(3-ethylthiophenyl)ethanol, and 2-(2-ethylthiophenyl)ethanol; 2-(2-Aminophenyl)ethanol such as 2-(4-aminophenyl)ethanol, 2-(3-aminophenyl)ethanol, and 2-(2-aminophenyl)ethanol; 2-(2-Alkylaminophenyl)ethanol such as 2-(4-methylaminophenyl)ethanol, 2-(3-methylaminophenyl)ethanol, 2-(2-methylaminophenyl)ethanol, 2-(4-ethylaminophenyl)ethanol, 2-(3-ethylaminophenyl)ethanol, and 2-(2-ethylaminophenyl)ethanol; 2-(2-Dialkylaminophenyl)ethanol such as 2-(4-dimethylaminophenyl)ethanol, 2-(3-dimethylaminophenyl)ethanol, 2-(2-dimethylaminophenyl)ethanol, 2-(4-diethylaminophenyl)ethanol, 2-(3-diethylaminophenyl)ethanol, and 2-(2-diethylaminophenyl)ethanol; Heteroaryl alcohols such as furfuryl alcohol, thiophen-2-ylmethanol, and pyridin-2-ylmethanol; 2-aryloxyethanols such as 2-phenoxyethanol, 2-(naphthalen-1-yloxy)ethanol, 2-(naphthalen-2-yloxy)ethanol, 2-(4-phenylphenoxy)ethanol, 2-(3-phenylphenoxy)ethanol, and 2-(2-phenylphenoxy)ethanol; 2-arylthioethanols such as 2-phenylthioethanol, 2-(naphthalen-1-ylthio)ethanol, 2-(naphthalen-2-ylthio)ethanol, 2-(4-phenylphenylthio)ethanol, 2-(3-phenylphenylthio)ethanol, and 2-(2-phenylphenylthio)ethanol; 2-arylaminoethanols such as 2-phenylaminoethanol, 2-(naphthalen-1-ylamino)ethanol, 2-(naphthalen-2-ylamino)ethanol, 2-(4-phenylphenylamino)ethanol, 2-(3-phenylphenylamino)ethanol, and 2-(2-phenylphenylamino)ethanol; 2-(N-alkyl-N-aryl amino) ethanols such as 2-(N-methyl-N-phenylamino)ethanol, 2-(N-methyl-N-naphthalen-1-ylamino)ethanol, 2-(N-methyl-N-naphthalen-2-ylamino)ethanol, 2-(N-methyl-N-4-phenylphenylamino)ethanol, 2-(N-methyl-N-3-phenylphenylamino)ethanol, 2-(N-methyl-N-2-phenylphenylamino)ethanol, 2-(N-ethyl-N-phenylamino)ethanol, 2-(N-ethyl-N-naphthalen-1-ylamino)ethanol, 2-(N-ethyl-N-naphthalen-2-ylamino)ethanol, 2-(N-ethyl-N-4-phenylphenylamino)ethanol, 2-(N-ethyl-N-3-phenylphenylamino)ethanol, and 2-(N-ethyl-N-2-phenylphenylamino)ethanol may be mentioned.

[0116] (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 groups to form carboxy groups and ester groups.

[0117] By reacting the above-described tetracarboxylic dianhydride with an alcohol represented by the formula (a3a) as the alcohol, a dicarboxylic acid that provides the structural unit (1) can be obtained. Hereinafter, the alcohol represented by the formula (a3a) is also referred to as R a21 -OH. R a21 is a group represented by -R A1 -R A2 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.

[0118] In the above dicarboxylic acid having two pairs of a carboxy group and a group represented by -CO-O-R a21 , there may exist isomers in which the position of the carboxy group and the position of the group represented by -CO-O-R a21 are different. 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 includes a plurality of types of structural units derived from a plurality of isomers of the dicarboxylic acid.

[0119] 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. Also, 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 formulas (a4-a1), (a4-a2), and (a4-b1) to (a4-b3), R a21 is as described above respectively.

[0120]

Chemical formula

[0121] 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), (a4-3a) to (a4-3c), and (a4-4a) to (a4-4c). In formulas (a4-2a) to (a4-2c), (a4-3a) to (a4-3c), and (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), (a4-3a) to (a4-3c), and (a4-4a) to (a4-4c), R a21 is as described above.

Chemical formula

[0122] 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), (a4-6a) to (a4-6c), (a4-7a), and (a4-7b). In formulas (a4-5a) to (a4-5c), (a4-6a) to (a4-6c), (a4-7a), and (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), (a4-6a) to (a4-6c), (a4-7a), and (a4-7b), R a21 is as described above.

[0123] [Chem.]

[0124] The reaction between tetracarboxylic dianhydride and alcohols is usually carried out in an organic solvent. The organic solvent used in the reaction between tetracarboxylic dianhydride and alcohols is not particularly limited as long as it can dissolve tetracarboxylic dianhydride and alcohols and does not react with tetracarboxylic dianhydride and alcohols. The organic solvent can be used alone or in a mixture of two or more.

[0125] Examples of organic solvents used in the reaction of tetracarboxylic dianhydrides with 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, etc. These organic solvents may be used alone or in combination of two or more.

[0126] 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.

[0127] When reacting a tetracarboxylic dianhydride with alcohols, the temperature is not particularly limited as long as the reaction proceeds well. Typically, the reaction temperature between 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 between 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.

[0128] For the purpose of preventing cross-linking between ethylenically unsaturated double bonds during the reaction between a tetracarboxylic dianhydride and 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 amount of the polymerization inhibitor used 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 bonds.

[0129] The reaction between 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.

[0130] The amount of the alcohols used 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.

[0131] 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 effect is not impaired, a dicarboxylic acid containing at least one selected from the above monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds can be used in the production of the polyimide resin precursor. When the dicarboxylic acid contains at least one selected from the above monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds as impurities, the content of at least one selected from the above monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds as impurities 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, based on the mass of the dicarboxylic acid including the mass of the impurities.

[0132] 〔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

[0133] In formula (2), when both 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

[0134] In formula (2), two Rs A3When both are monovalent organic groups, a structural unit (2) is formed by reacting a diamine compound with a dicarboxylic acid compound. The dicarboxylic acid compound that forms the structural unit (2) is a reaction product of the tetracarboxylic dianhydride represented by the above formula (A3b) and the alcohol represented by the following formula (a3b). R A3 -OH ···(a3b)

[0135] Two Rs A3 When both are monovalent organic groups, one R A3 is -R A1 -R A2 The organic group represented by, and the other R A3 is, -R A1 -R A2 It may be an organic group that does not correspond to the group represented by. R A1 , and R A2 are the same as R A1 , and R A2 in formula (1). The structural unit (2) is a structural unit that does not correspond to the structural unit (1). Therefore, the two Rs in formula (2) A3 are not both groups represented by -R A1 -R A2 .

[0136] Also, by reacting a product obtained by reacting an alcohol with only one of the dicarboxylic dianhydride groups in the tetracarboxylic dianhydride represented by the above formula (A3b) with a diamine, one R A3 is a hydrogen atom, and the other R A3 is a structural unit (2) in which a monovalent organic group is formed. The product obtained by reacting the alcohol represented by the formula (a3b) with only one of the dicarboxylic dianhydride groups in the tetracarboxylic dianhydride represented by the above formula (A3b) is represented by the following formula (A3c). In formula (A3c), X A2 , and R A3 are the same as X A2 , and R A3 in formula (2).

Chemical formula

[0137] The structural unit (2) is represented by formula (2), and the two Rs A3 are hydrogen atoms, or is a structural unit represented by formula (2) and the two Rs A3 are monovalent organic groups, which is preferred. Since it is easy to form a polyimide resin excellent in dielectric properties in a high frequency band, the structural unit (2) is a structural unit represented by formula (2) and the two Rs A3 are monovalent organic groups, which is more preferred.

[0138] Hereinafter, the diamine compound and the dicarboxylic acid that provide the structural unit (1) will be described.

[0139] (Diamine compound) The diamine compound that provides the structural unit (2) represented by formula (2) is represented by the following formula (A2b). H2N-Y A2 -NH2 ··· (A2b) (In formula (Ab), Y A2 represents a divalent organic group having 4 to 40 carbon atoms.)

[0140] Y in formula (A2b) A2 is the same as Y in formula (A2a) A1 . That is, the diamine compound represented by formula (A2b) is the same as the diamine compound represented by formula (A2a).

[0141] (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).

[0142] Hereinafter, the tetracarboxylic dianhydride represented by formula (A3b) and the alcohol represented by formula (a3b) will be described.

[0143] The tetracarboxylic dianhydride is represented by the above formula (a3b). X in formula (A3b) A2 is the same as X in formula (A3a) A1 That is, the tetracarboxylic dianhydride represented by formula (A3b) is the same as the tetracarboxylic dianhydride represented by formula (A3a).

[0144] As described above, as long as the constitutional unit (2) does not correspond to the constitutional unit (1), the alcohol represented by the above formula (a3b) may be the alcohol represented by the above formula (a3a). Preferable examples of the alcohol represented by formula (a3b) that does not correspond to the alcohol 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.

[0145] (Production of dicarboxylic acid) The method for producing the dicarboxylic acid that provides the constitutional unit (2) is the same as that described for the constitutional unit (1).

[0146] 〔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. In addition, within a range where the desired effect is not impaired, a compound capable of polymerizing with a diamine compound such as a tetracarboxylic dianhydride may be used together with the dicarboxylic acid.

[0147] A preferred method includes a method of condensing the aforementioned diamine compound and dicarboxylic acid in the presence of a condensing agent. If necessary, it is also preferable to use a condensation aid together with the condensing agent. The condensing agent and the condensation aid are not particularly limited as long as they are compounds conventionally used for the condensation of dicarboxylic acid and diamine compound.

[0148] 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 methotoluenesulfonate, 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.

[0149] 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 when 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 at its terminal, it is preferable to adjust the raw material ratio represented by (the number of moles of carboxy groups in the dicarboxylic acid) / (the number of moles of amino groups in the diamine compound) within the range of preferably 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 in the dicarboxylic acid) / (the number of moles of amino groups in the diamine compound), the less likely the molecular chain of the polyimide resin precursor is to elongate, and it is easier to obtain a low molecular weight polyimide resin precursor. When the polyimide resin precursor has a carboxy group at its terminal, it is preferable to adjust the raw material ratio represented by (the number of moles of amino groups in the diamine compound) / (the number of moles of carboxy groups in the dicarboxylic acid) within the range of preferably 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 amino groups in the diamine compound) / (the number of moles of carboxy groups in the dicarboxylic acid), the less likely the molecular chain of the polyimide resin precursor is to elongate, and it is easier to obtain a low molecular weight polyimide resin precursor.

[0150] Specifically, the dicarboxylic acid and the 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 0°C or higher and 50°C or lower, for 30 minutes or longer and 24 hours or shorter, preferably 1 hour or longer and 4 hours or shorter.

[0151] As the solvent used for polycondensation, the above-mentioned solvents that can be used in the reaction between the tetracarboxylic dianhydride and alcohols can be used. The amount of the solvent used is preferably 50 parts by mass or more and 10000 parts by mass or less, more preferably 100 parts by mass or more and 2000 parts by mass or less, and even more preferably 150 parts by mass or more and 1000 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.

[0152] When producing the polyimide resin precursor, the amounts of the dicarboxylic acid and the diamine compound used are not particularly limited, but it is preferable to use 0.8 mol or more and 1.2 mol or less of the diamine compound with respect to 1 mol of the dicarboxylic acid, 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.

[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, the polyimide resin precursor preferably contains a divalent aliphatic hydrocarbon group having 2 to 50 carbon atoms, more preferably 3 to 40 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 gives 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.

[0154] 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 photosensitive composition preferably 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

[0155] 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 in terms of the above polystyrene, preferably 15000 or more, and more preferably 250000000 or more 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 in terms of the above polystyrene, preferably 80000 or less, and more preferably 50000 or less from the viewpoint of solubility in organic solvents and the like. This weight average molecular weight may be adjusted to the above values by adjusting the blending amounts of the aforementioned dicarboxylic acid and diamine compound, and reaction conditions such as solvents and reaction temperatures.

[0156] For the purpose of improving the storage stability of the photosensitive composition containing the polyimide resin precursor, further improving the mechanical properties of the polyimide resin film, and improving the reproducibility of polymerization when producing the 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, and the like. Known compounds can be used as the monoamine used for terminal capping. 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 terminal blocking agents, 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. Regarding the introduction rate of the terminal blocking agent in the polyimide resin precursor, from the viewpoint of excellent mechanical properties of the formed polyimide resin film, it 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.

[0157] 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.

[0158] ≪Photosensitive Composition≫ The polyimide resin precursor described above can be preferably used as a component of the photosensitive composition. The photosensitive composition contains a polyimide resin precursor (A) which is the above-mentioned polyimide resin precursor, a photoacid generator (B), and a methylol type cross-linking agent (C). This photosensitive composition is a chemically amplified negative type photosensitive composition that cures upon exposure. Hereinafter, the essential or optional components that may be included in the chemically amplified negative type photosensitive composition will be described.

[0159] 〔Polyimide Resin Precursor (A)〕 The polyimide resin precursor (A) is the above-mentioned polyimide resin precursor.

[0160] 〔Photoacid Generator (B)〕 The photoacid generator (B) is not particularly limited, and the photoacid generators that have been compounded in photosensitive compositions can be used without particular limitation. Examples of the photoacid generator (B) 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 a photosensitive composition excellent in photolithography characteristics can be easily obtained. That is, it is preferable that the photoacid generator (B) contains a sulfonate type photoacid generator (B1) and / or an onium salt type photoacid generator (B2). Hereinafter, the sulfonate type photoacid generator (B1) and the onium salt type photoacid generator (B2) will be described.

[0161] [Sulfonate type photoacid generator (B1)] The sulfonate type photoacid generator (B1) 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), for example, a compound represented by the following formula (b0-1) is preferable.

[0162] [Chemical formula]

[0163] 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).

[0164] [Chemical formula]

[0165] In formula (b0-r-1), Rb 201 and Rb 202 are each independently an organic group. * indicates 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)-. * indicates a bond.

[0166] 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), an oxime sulfonate type photoacid generator (B1-a) and an imide sulfonate type photoacid generator (B1-b) 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.

[0167]

Chemical formula

[0168] In formula (b0-1-1), Rb 11 , and Rb 21 are each independently an aliphatic group.

[0169]

Chemical formula

[0170] In formula (b0-1-2), Rb 12 is an alkyl group or a halogenated alkyl group. Rb 22 is an aromatic group.

[0171]

Chemical formula

[0172] In formula (b0-1-3), Rb 13is a hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent. nb3 is 2 or 3. Ab is a divalent or trivalent organic group.

[0173]

Chemical formula

[0174] In formula (b0-1-4), Rb 14 is a polycyclic aromatic hydrocarbon group which may have a substituent, or a polycyclic aliphatic hydrocarbon group which may have a substituent and may have an unsaturated bond. Rb 24 is an inert organic group.

[0175]

Chemical formula

[0176] 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 aromatic group which may have a substituent. Xb 5 is a group which forms a cyclic group having a cyclic imide structure together with -(O=)C-N-C(=O)-.

[0177]

Chemical formula

[0178] In formula (b0-1-6), Rb 16 is 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.

[0179] In formula (b0-1-1), Rb 11 , and Rb21 Examples of the aliphatic group as such include an alkyl group, a halogenated alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a cycloalkoxy group, and an adamantyl group, etc.

[0180] Rb 11 and Rb 21 As the alkyl group as such, a linear or branched alkyl group having 1 to 12 carbon atoms is preferred. Specific examples of the alkyl group having 1 to 12 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 n-octyl group, and an n-dodecyl group, etc.

[0181] Rb 11 and Rb 21 The number of halogen atoms in the halogenated alkyl group as such is not particularly limited. The number of halogen atoms may be 1 or may be 2 or more. As the halogen atom, any of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom may be used. As the halogenated alkyl group, a halogenated alkyl group having 1 to 4 carbon atoms is preferred. Specific examples of the halogenated alkyl group having 1 to 4 carbon atoms include a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, and a 2-bromopropyl group, etc.

[0182] Rb 11 and Rb 21 As the alkenyl group as such, a linear or branched alkenyl group having 2 to 6 carbon atoms is preferred. As the alkenyl group having 2 to 6 carbon atoms, a vinyl group, a 1-propenyl group, an isopropenyl group, and a 2-butenyl group, etc. are preferred.

[0183] Rb 11 and Rb 21As 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, etc.

[0184] 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, etc.

[0185] 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, etc.

[0186] 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, etc.

[0187] 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. Rb 21 is preferably an alkyl group, a cycloalkyl group, or a cycloalkenyl group, and more preferably a cycloalkenyl group. In formula (b0-1-1), Rb 11 is an alkyl group having 1 to 4 carbon atoms, and it is particularly preferable that Rb 21 is a cyclopentenyl group.

[0188] Specific examples of the compound represented by the 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, etc.

[0189] Rb in the formula (b0-1-2) 12 Examples of the alkyl group as Rb 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, etc.

[0190] Rb 12Examples of the alkyl halide group as used herein 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.

[0191] In formula (b0-1-2), Rb 22 The aromatic group as used herein is a group that exhibits physical and chemical properties specific 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 used herein may have one or more substituents. Examples of the substituent include halogen atom, alkyl group, alkoxy group, and nitro group.

[0192] 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.

[0193] In formula (b0-1-3), Rb 13 Examples of the hydrocarbon group that may have a substituent as used herein include an aromatic hydrocarbon group that may have a substituent and an aliphatic hydrocarbon group that may have a substituent. The aromatic group is preferably a hydrocarbon group having 6 to 14 carbon atoms. 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.

[0194] Rb 13 The aliphatic hydrocarbon group as such 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, and 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, and a 1-cyclooctenyl group, respectively.

[0195] Rb 13 The heterocyclic group as such may be an aromatic heterocyclic group or an aliphatic heterocyclic group. The aromatic heterocyclic group is preferred as the heterocyclic group. Specific examples of the aromatic heterocyclic group include a furanyl group, a pyridyl group, and a quinolyl group.

[0196] Rb in formula (b0-1-3) 13The 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.

[0197] 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.

[0198] Specific examples of the compound represented by formula (b0-1-3) are shown below.

[0199]

Chemical formula

[0200]

Chemical formula

[0201] Rb in formula (b0-1-4) 14 Examples of the polycyclic aromatic hydrocarbon group as such include condensed polycyclic aromatic hydrocarbon groups such as a 2-indenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 2-anthryl group; and non-condensed polycyclic aromatic hydrocarbon groups such as a biphenyl group and a terphenyl group. The polycyclic aromatic hydrocarbon group may have substituents such as a halogen atom such as a chlorine atom, a bromine atom, and an iodine atom, a nitro group, an amino group, a hydroxyl group, an alkyl group, and an alkoxyl group. Specific examples of the polycyclic aromatic hydrocarbon group having a substituent include a 5-hydroxynaphthalen-1-yl group and a 4-aminonaphthalen-1-yl group.

[0202] Rb in formula (b0-1-4) 14 Examples of the polycyclic aliphatic hydrocarbon group which may have an unsaturated bond as such include a polycyclic terpene residue and an adamantyl group. 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 atoms, bromine atoms, and iodine atoms, nitro groups, amino groups, hydroxyl groups, alkyl groups, and alkoxyl groups.

[0203] Rb 14 In the polycyclic aliphatic hydrocarbon group as [Rb], 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.

[0204] Rb 14 Preferable examples of the polycyclic aliphatic hydrocarbon group as [Rb] include a camphor-3-yl group, a camphor-8-yl group, a camphor-10-yl group, and a 3-bromocamphor-10-yl group.

[0205] Among the groups described above, as Rb 14 a naphthyl group and a camphor-10-yl group are preferable, and a 1-naphthyl group is particularly preferable in terms of excellent resolution of the photosensitive composition.

[0206] In formula (b0-1-4), the inert organic group as Rb 24 is not particularly limited as long as it is an organic group that is inert to the coexisting components under the use conditions. As the inert organic group, an aromatic group is preferable from the viewpoint of sensitivity to excimer lasers, electron beams, and X-rays. Examples of the aromatic group include a phenyl group, a naphthyl group, a furyl group, and a thienyl group. The aromatic group may have inert substituents such as halogen atoms such as chlorine atoms, bromine atoms, and iodine atoms, alkyl groups, alkoxy groups, and nitro groups.

[0207] 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.

[0208] 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 [it] 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, a nitro group, an acetylamino group, an alkoxy group, and a 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 [it] 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, an alkyl group, an alkoxy group, and a halogen atom, etc. is preferable.

[0209] 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, a maleimide ring, a glutarimide ring, a phthalimide ring, and a 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.

[0210] 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 compounds described in paragraphs

[0089] -

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

[0211] In the formula (b0-1-6), Rb 16As the alkyl group, a linear or branched alkyl group having 1 to 18 carbon atoms is preferred, a linear or branched alkyl group having 1 to 10 carbon atoms is more preferred, and a linear or branched alkyl group having 1 to 5 carbon atoms is even more preferred. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, and an n-octadecyl group.

[0212] In formula (b0-1-6), Rb 16 As the cycloalkyl group, a cycloalkyl group having 3 to 18 carbon atoms is preferred. Rb 16 Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a cyclododecyl group.

[0213] Rb 16 The alkyl group and the cycloalkyl group as Rb 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.

[0214] 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.

[0215] 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.

[0216] 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.

[0217]

Chemical formula

[0218] Other specific examples of the sulfonate-type photoacid generator (B1) other than the sulfonate-type photoacid generator (B1) 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.

[0219] Among the sulfonate-type photoacid generators (B1) 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.

[0220] As the sulfonate-type photoacid generator (B1), the compounds represented by the following formulas (B0-1) to (B0-3) are particularly preferable.

[0221] [Chemical formula]

[0222] [Onium salt type photoacid generator (B2)] As the onium salt type photoacid generator (B2), conventionally known onium salt type photoacid generators such as iodonium salts and sulfonium salts can be used without particular limitation.

[0223] Examples of the onium salt type photoacid generator (B2) include onium salts having a naphthalene ring in the cationic part. The phrase "having a naphthalene ring" means having a structure derived from naphthalene, which means having at least a structure of two rings and maintaining their aromaticity. This naphthalene ring may have a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or the like as a substituent. The structure derived from the naphthalene ring may be a monovalent group (having one free valence) or a divalent group (having two or more free valences) or more, but it is preferably a monovalent group (however, in this case, the free valence is counted excluding the part bonded to the above substituent). The number of naphthalene rings is preferably 1 to 3.

[0224] As the cationic part of such an onium salt having a naphthalene ring in the cationic part, a structure represented by the following formula (b1) is preferable.

[0225] [Chemical formula]

[0226] In the above formula (b1), at least one of R 1b , R 2b , R 3b 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, R1b and R 2b and 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 and R 2b and R 3b Specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms as R R 1b and R 2b and R 3b Specific examples of the linear or branched alkoxy group having 1 to 6 carbon atoms as R R 1b and R 2b and R 3b When R

[0227]

Chemical formula

[0228] In the above formula (b2), R 4b and R 5b each independently represent 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 6brepresents a linear or branched alkylene group having 1 to 6 carbon atoms, which may have a single bond or 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, R 4b When there are a plurality of them, they may be the same as or different from each other. Also, R 5b When there are a plurality of them, 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 R 4b , and R 5b 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. R 6b Specific examples of the linear or branched alkylene group having 1 to 6 carbon atoms as R

[0229] The above R 1b R 2b R 3bAmong them, the number of the groups represented by the above formula (b2) is preferably 1 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.

[0230] 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.

[0231] 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.

[0232] Examples of those suitable as these cation moieties include those represented by the following formulas (b3), (b4-1), and (b4-2), and in particular, the structures represented by the following formulas (b4-1) and (b4-2) are preferable.

[0233]

Chemical formula

[0234] 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.

[0235] 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.

[0236] 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.

[0237] In the fluoroalkylsulfonic acid 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, since they can be synthesized inexpensively, examples of preferred ones include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and the like.

[0238] In the arylsulfonic acid 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, since it can be synthesized inexpensively, 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, and the like.

[0239] In the above fluoroalkylsulfonic acid ion or arylsulfonic acid 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 substituted with fluorine atoms are preferred because the acid strength becomes stronger. Specific examples of such ones include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, perfluorobenzenesulfonate, and the like.

[0240] Among these, as a preferred anion part, one represented by the following formula (b5) can be mentioned.

[0241]

Chemical formula

[0242] In the above formula (b5), R 7b is a group represented by the following formulas (a10), (a11), and (a12).

[0243]

Chem.

[0244] 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.

[0245] Further, as the anion part, those containing nitrogen represented by the following formulas (b9) and (b10) can also be used.

[0246]

Chem.

[0247] 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 number of carbon atoms of the alkylene group is 2 or more and 6 or less, preferably 3 or more and 5 or less, 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 number of carbon atoms of the alkyl group is 1 or more and 10 or less, preferably 1 or more and 7 or less, and more preferably 1 or more and 3 or less.

[0248] X b The smaller the number of carbon atoms of the alkylene group of, or Y a , Z a the smaller the number of carbon atoms of the alkyl group of, the better the solubility in the organic solvent, which is preferable.

[0249] Further, X bThe alkylene group or Y b and Z b In the alkyl group, the larger the number of hydrogen atoms substituted with 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 with fluorine atoms.

[0250] Preferred examples of the onium salt having a naphthalene ring in such a cationic part include compounds represented by the following formulas (b11-1), (b11-2), and (b12).

[0251]

Chemical formula

[0252] In the photosensitive composition, the photoacid generator (B) may be used alone or in combination of two or more. The content of the photoacid generator (B) in the 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-type photosensitive composition having particularly good photolithography characteristics.

[0253] 〔Methylol-type crosslinking agent (C)〕 The methylol-type crosslinking agent (C) is a crosslinking agent having two or more crosslinkable groups selected from a methylol group and an alkoxymethyl group.

[0254] Examples of the methylol-type 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, and the like. In the following, "lower" means having 1 to 5 carbon atoms.

[0255] Examples of the melamine-based crosslinking agent include compounds obtained by reacting melamine with formaldehyde to substitute a hydrogen atom of an amino group with a hydroxymethyl group, compounds obtained by reacting melamine with formaldehyde and a lower alcohol to substitute a hydrogen atom of an amino group with a lower alkoxymethyl group, and the like. Specifically, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, and the like can be mentioned. Among them, hexamethoxymethylmelamine is preferable.

[0256] Examples of the urea-based crosslinking agent include compounds obtained by reacting urea with formaldehyde to substitute a hydrogen atom of an amino group with a hydroxymethyl group, compounds obtained by reacting urea with formaldehyde and a lower alcohol to substitute a hydrogen atom of an amino group with a lower alkoxymethyl group, and the like. 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.

[0257] Examples of the alkyleneurea-based crosslinking agent include compounds represented by the following formula (CA-1).

[0258] [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.)

[0259] Rc 1 and Rc 2When it is a lower alkoxy group, it is preferably an alkoxy group having 1 to 4 carbon atoms, which may be linear or branched. Rc 1 and Rc 2 may be the same as each other or may be different from each other, and it is more preferable that they are the same. Rc 3 and Rc 4 When it is a lower alkoxy group, it is preferably an alkoxy group having 1 to 4 carbon atoms, which may be linear or branched. Rc 3 and Rc 4 may be the same as each other or may be 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.

[0260] 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.

[0261] 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.

[0262] Examples of glycoluril-based crosslinking agents 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 further 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.

[0263] The phenolic crosslinking agent is not particularly limited as long as it is a compound having a plurality of phenolic nuclear structures in the same molecule, and can be arbitrarily selected and used. By having a plurality of phenolic nuclear structures, the crosslinking reactivity is improved. The number of phenolic 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.

[0264] Specific examples suitable as the glycoluril-based crosslinking agent or the phenolic crosslinking agent are shown below.

[0265]

Chemical formula

[0266] In the photosensitive composition, the methylol type crosslinking agent (C) may be used alone or in combination of two or more. The content of the methylol type crosslinking agent (C) in the 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 still 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 methylol type crosslinking agent (C) is within the above range, it is easy to obtain a photosensitive composition that gives a polyimide resin excellent in chemical resistance.

[0267] 〔Solvent (S)〕 The 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).

[0268] 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, etc. 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, etc. 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; sulfoxides such as dimethyl sulfoxide may be mentioned.;

[0269] The amount of the solvent (S) used is not particularly limited as long as a uniform liquid photosensitive composition can be prepared. The 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 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.

[0270] 〔Other Components〕 The photosensitive composition may contain various additives other than the components described above, if necessary. Examples of the additives include colorants, dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, anti - agglomeration agents, defoaming agents, surfactants, imidization promoters, nitrogen - containing heterocyclic compounds as adhesion improvers, and silane coupling agents. Further, the photosensitive composition may contain various fillers or reinforcing materials, if necessary.

[0271] The nitrogen - containing heterocyclic compound improves the adhesion of the resin film formed using the 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 their derivatives. 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.

[0272] From the viewpoint of achieving both excellent developability of the photosensitive composition and improved adhesion of the polyimide resin film formed using the 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).

[0273] By blending a silane coupling agent into the photosensitive composition, the adhesion of the resin film formed using the 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.

[0274] 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).

[0275] By incorporating a surfactant into the photosensitive composition, the coatability of the photosensitive composition is improved, and the wettability of the 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.

[0276] 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).

[0277] The polyimide resin precursor (A) can be converted into a polyimide resin by heating. Therefore, the photosensitive composition may contain a cyclization accelerator. The cyclization accelerator promotes the formation of a polyimide resin by the 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 photosensitive composition contains a cyclization accelerator, the mechanical properties and weather reliability of the resin film formed while producing a polyimide resin by cyclization using the photosensitive composition are improved. As the cyclization accelerator, known thermal base generators and thermal acid generators are used.

[0278] 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 photosensitive composition, and preferably 0.01% by mass or more and 5% by mass or less.

[0279] [Preparation method of photosensitive composition] The photosensitive composition can be prepared by uniformly mixing the essential components and the optional components as described above in desired amounts. The mixing method is not particularly limited. For the purpose of removing foreign matters in the photosensitive composition, it is preferable to filter the photosensitive composition through a filter.

[0280] <<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.

[0281] 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.

[0282] The photosensitive dry film is manufactured by applying the aforementioned photosensitive composition on the base film to form a photosensitive layer. When forming the photosensitive layer on the 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 on 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, and then dried.

[0283] The photosensitive dry film may further have a protective film on the photosensitive layer. Examples of this protective film include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, etc.

[0284] ≪Method for manufacturing polyimide resin film≫ Applying the aforementioned photosensitive composition on a substrate to form a coating film, Heating the coating film to imidize the polyimide resin precursor (A) contained in the coating film, and a polyimide resin film can be manufactured by a method including these steps.

[0285] In the above method, the coating film is selectively exposed, the exposed coating film is developed with a developer, and the developed coating film is heated to imidize the polyimide resin precursor (A) contained in the coating film, whereby a patterned polyimide resin film can be produced.

[0286] The substrate is not particularly limited, and a conventionally known substrate can be used. For example, substrates for electronic components and those with a predetermined wiring pattern formed thereon can be exemplified. As the substrate, a silicon substrate, a glass substrate, or the like can also be used.

[0287] 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.

[0288] As a method for applying the photosensitive composition onto the substrate, methods such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, and an applicator method can be adopted.

[0289] 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 performed by heating. The heating conditions during drying vary depending on the types of components, blending ratios, coating film thickness, etc. in the photosensitive composition, but are usually 70°C or higher and 200°C or lower, preferably 80°C or higher and 150°C or lower, and about 2 minutes or more and 120 minutes or less.

[0290] 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 higher and 400°C or lower is preferable, and 200°C or higher and 350°C or lower is more preferable. The heating time depends on the heating temperature, but typically, it is preferably 1 hour or more and 24 hours or less, more preferably 2 hours or more and 12 hours or less. From the viewpoint of preventing oxidation of the resin film and obtaining a resin film with good mechanical properties, heating is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

[0291] Further, with respect to the coating film formed as described above, selective exposure is performed by selectively irradiating 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.

[0292] Selective exposure is usually performed by selectively irradiating actinic rays or radiation, such as ultraviolet rays or visible light with a wavelength of 300 nm or more and 500 nm or less, through a mask of a predetermined pattern.

[0293] 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.

[0294] Next, the exposed coating film is developed according to a conventionally known method to dissolve and remove unnecessary portions, thereby forming 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.

[0295] 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.

[0296] 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.

[0297] 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.

[0298] The patterned resin film thus formed is imidized by heating according to the above method to form a patterned polyimide resin film.

[0299] 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, or 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

[0300] 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.

[0301] 〔Examples 1 to 6 and Comparative Example 2〕 In the examples and the comparative examples, the following DA1 and DA2 were used as diamine compounds.

Chemical formula

[0302] In the examples and the comparative examples, the following TC1 and TC2 were used as tetracarboxylic dianhydrides.

Chemical formula

[0303] In the examples and comparative examples, the following A1 to A7 were used as the alcohols to react with the tetracarboxylic dianhydride. A1: 2-(4-aminophenyl)ethanol A2: 2-(N-methyl-N-phenylamino)ethanol A3: 2-phenoxyethanol A4: 2-(4-methoxyphenyl)ethanol A5: furfuryl alcohol A6: 2-(4-dimethylaminophenyl)ethanol A7: 2-hydroxyethyl methacrylate

[0304] In the examples and comparative examples, the following B1 was used as the photoacid generator (B), and the following B2 was used as the radical polymerization initiator (B’).

Chemical formula

[0305] In the examples and comparative examples, the following C1 was used as the methylol type crosslinking agent (C), and the compound C2 (pentaerythritol tetrakis(3-mercaptobutyrate)) was used as the thiol compound (C’).

Chemical formula

[0306] 〔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) to a concentration of 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. Subsequently, 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. Then, 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.

[0307] 〔Examples 1 to 6〕 The polyimide resin precursor (A) was dissolved in γ-butyrolactone to a concentration of 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 a photoacid generator (B). Further, to the resulting solution, 10% by mass of the above C1 with respect to the mass of the polyimide resin precursor (A) was dissolved as a methylol type crosslinking agent (C). In this way, the photosensitive compositions of Examples 1 to 9 were obtained.

[0308] 〔Comparative Examples 1 to 3〕 The polyimide resin precursor (A) was dissolved in N,N,N’,N’-tetramethylurea to a concentration of 30% by mass. To the resulting solution, 0.5% by mass of the above B2 with respect to the mass of the polyimide resin precursor (A) was dissolved as a radical polymerization initiator (B’). Further, to the resulting solution, 0.5% by mass of the above C2 with respect to the mass of the polyimide resin precursor (A) was dissolved as a thiol compound (C’) which is a crosslinking agent. In this way, the photosensitive compositions of Comparative Examples 1 to 3 were obtained. The polyimide resin precursor (A) contained in the photosensitive compositions of Comparative Examples 1 to 3 contains a (meth)acryloyl group in the side chain. Further, the above C2 is a polyfunctional thiol compound. When the photosensitive compositions of Comparative Examples 1 to 3 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 is cured.

[0309] Using the photosensitive compositions of each of the obtained Examples and Comparative Examples, the chemical resistance and the resolution of the cured film were evaluated by the following method. These evaluation results are shown in Table 1.

[0310] <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 Exposed at. The exposed coated film was heated in an inert oven under a nitrogen atmosphere at a rate of 5 °C / min to 230 °C. Next, the coated film was heated at the same temperature for 1 hour to imidize it. After the heating was completed, the inert oven was allowed to cool, and when the temperature inside 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 pieces were immersed in a 30 mass% sulfuric acid aqueous solution at 25 °C for 60 minutes. The polyimide resin film provided on the test pieces after immersion was visually observed. Based on the results of the visual observation, the chemical resistance of the polyimide resin film was evaluated according to the following criteria. A: There is no change in the appearance of the polyimide resin film after immersion. B: There is a change in the appearance of the polyimide resin film after immersion.

[0311] <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 by a spin coater. Subsequently, 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-line 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 cyclopentanone for development. As a result of the development, Table 1 shows the minimum via hole diameter at which a pattern could be formed at an exposure dose of 2000 mJ / cm2 or less. The smaller the via hole diameter, the better the resolution.

[0312]

Table 1

[0313] 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 side chain with a terminal consisting of a specific aromatic group, the photoacid generator (B), and the methylol type crosslinking agent (C) gives a polyimide resin film excellent in chemical resistance and excellent in resolution. On the other hand, the photosensitive composition of the comparative example containing the polyimide resin precursor (A) having a structural unit with a methacryloyl group in the side chain, the radical polymerization initiator (B'), and the thiol compound (C') gives 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 Formula 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, independently of one another, an alkylene group, R Ａ２ is, independently of each other, an aryl group, heteroaryl group, aryloxy group, arylthio group, arylamino group, or N-alkyl-N-arylamino group substituted with a group selected from an alkoxy group, mercapto group, alkylthio group, amino group, alkylamino group, and dialkylamino group. 【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 each other, a hydroxyl group or a monovalent organic group, Said R Ａ３ The organic group as such 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 above formula (1), X Ａ１ wherein the tetravalent organic group 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.

4. A photosensitive composition comprising a polyimide resin precursor (A), a photoacid generator (B), and a methylol type crosslinking agent (C), wherein the polyimide resin precursor (A) is the polyimide resin precursor according to any one of Claims 1 to 3, and the methylol type crosslinking agent (C) has two or more crosslinkable groups selected from a methylol group and an alkoxymethyl group.

5. A method for producing a polyimide resin film, comprising: coating the photosensitive composition according to Claim 4 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.

6. A method for producing a patterned polyimide resin film, comprising: coating the photosensitive composition according to Claim 4 on a substrate to form a coating film; 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. ​ ​ ​ ​

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