Negative photosensitive resin composition, method for producing resin film, method for producing patterned resin film, method for producing patterned polyimide resin film, and polyimide resin precursor

Abstract

To provide a negative photosensitive resin composition superior in resolution; methods for producing a resin film, a patterned resin film, and a patterned polyimide resin film employing the negative photosensitive resin composition; and a polyimide resin precursor that can be used in the negative photosensitive resin composition.SOLUTION: A negative photosensitive resin composition comprises a polyimide resin precursor (A) and a photoradical polymerization initiator (C), wherein the polyimide resin precursor (A) comprises a specific structural unit comprising: an organic group of 6 to 40 carbon atoms having two alicyclic groups linked by an alkylene group, an oxygen atom, or a sulfur atom; and an unsaturated group of 3 to 30 carbon atoms having one or more ethylenically unsaturated double bonds.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a negative-tone photosensitive resin composition containing a polyimide resin precursor, a resin film using the negative-tone photosensitive resin composition, a patterned resin film, and a method for producing a patterned polyimide resin film, and a polyimide resin precursor that can be used in the negative-tone photosensitive resin composition. [Background technology]

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

[0003] For example, a technology has been proposed in which, in a photosensitive resin composition containing a resin (A) and a photopolymerization initiator (B), the resin (A) is a polyamide resin that contains a specific saturated alicyclic skeleton and a structural unit in which at least one of the carboxy groups is esterified with a unit containing a polymerizable group of a predetermined structure (see Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-045230 Summary of the Invention [Problem to be solved by the invention]

[0005] When the photosensitive resin composition described in Patent Document 1 is used, it is possible to form a cured film that has good adhesion to a substrate and excellent transparency. On the other hand, the photosensitive resin composition described in Patent Document 1 requires improvement in resolution.

[0006] The present invention has been made in consideration of the above-mentioned problems, and an object of the present invention is to provide a negative-tone photosensitive resin composition having excellent resolution, a method for producing a resin film, a patterned resin film, and a patterned polyimide resin film using the negative-tone photosensitive resin composition, and a polyimide resin precursor that can be used in the negative-tone photosensitive resin composition. [Means for solving the problem]

[0007] The present inventors have found that the above-mentioned problems can be solved by a negative-type photosensitive resin composition containing a polyimide resin precursor (A) having a structural unit represented by the following formula (A1) and a photoradical polymerization initiator (C), and have thus completed the present invention. More specifically, the present invention provides the following.

[0008] [1] A negative photosensitive resin composition comprising a polyimide resin precursor (A) containing a structural unit represented by the following formula (A1) and a photoradical polymerization initiator (C): [ka] (In formula (A1), X A1 is a tetravalent organic group having 4 to 40 carbon atoms, Y A1 is an organic group having 6 to 40 carbon atoms and having a structure in which two alicyclic groups are connected by an alkylene group, an oxygen atom, or a sulfur atom, R A1 , and R A2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R A1 , and R A2 The organic group represented by R is bonded to the oxygen atom in the ester bond via a C-O bond. A1 and R A2 At least one of the groups is an unsaturated group having 3 to 30 carbon atoms and one or more ethylenically unsaturated double bonds.

[0009] [2] The above Y A1 -A 01 -R 01 -A 02is an organic group represented by the formula: A 01 and A 02 are each independently an alicyclic group, and R 01 is an alkylene group, an oxygen atom, or a sulfur atom.

[0010] [3] R 01 is a methylene group.

[0011] [4] A 01 and A 02 and each independently represent a cycloalkylene group.

[0012] [5] The negative photosensitive resin composition according to any one of the above [1] to [4], wherein the polyimide resin precursor (A) contains 5 mol % or more and 50 mol % or less of the structural unit represented by the formula (A1).

[0013] [6] X A1 The negative photosensitive resin composition according to any one of the above [1] to [5], wherein the tetravalent organic group as is a residue obtained by removing two dicarboxylic acid anhydride groups from an aromatic tetracarboxylic acid dianhydride.

[0014] [7] The negative photosensitive resin composition according to any one of the above [1] to [6], wherein the polyimide resin precursor (A) contains a structural unit represented by the following formula (A2): [ka] (In formula (A2), X A1 , R A1 , and R A2 is X in formula (A1) A1 , R A1 , and R A2 is the same as Y A11 is an organic group containing an aromatic ring and having 6 to 40 carbon atoms.

[0015] [8] A method for producing a resin film, comprising applying the negative photosensitive resin composition according to any one of the above [1] to [7] onto a substrate to form a coating film.

[0016] [9] Applying the negative photosensitive resin composition according to any one of [1] to [7] above onto a substrate to form a coating film; exposing the coating film to position-selective light; developing the exposed coating film; A method for producing a patterned resin film, comprising:

[0017]

[10] A method for producing a patterned polyimide resin film, comprising heating the patterned resin film produced by the production method described in [9] above to produce a polyimide resin derived from the polyimide resin precursor.

[0018]

[11] A polyimide resin precursor containing a structural unit represented by the following formula (A1): [ka] (In formula (A1), X A1 is a tetravalent organic group having 4 to 40 carbon atoms, Y A1 is an organic group having 6 to 40 carbon atoms and having a structure in which two alicyclic groups are connected by an alkylene group, an oxygen atom, or a sulfur atom, R A1 , and R A2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R A1 , and R A2 The organic group represented by R is bonded to the oxygen atom in the ester bond via a C-O bond. A1 and R A2 At least one of the groups is an unsaturated group having 3 to 30 carbon atoms and one or more ethylenically unsaturated double bonds. [Effects of the Invention]

[0019] According to the present invention, it is possible to provide a negative-type photosensitive resin composition having excellent resolution, a method for producing a resin film, a patterned resin film, and a patterned polyimide resin film using the negative-type photosensitive resin composition, and a polyimide resin precursor that can be used in the negative-type photosensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0020] <Negative-type photosensitive resin composition> The negative photosensitive resin composition (hereinafter also simply referred to as "photosensitive resin composition") contains a polyimide resin precursor (A) containing a structural unit represented by the following formula (A1), and a photoradical polymerization initiator (C). Furthermore, the polyimide resin precursor (A) preferably contains a structural unit represented by the following formula (A2) in addition to the structural unit represented by the following formula (A1). [ka] (In formula (A1), X A1 is a tetravalent organic group having 4 to 40 carbon atoms, Y A1 is an organic group having 6 to 40 carbon atoms and having a structure in which two alicyclic groups are connected by an alkylene group, an oxygen atom, or a sulfur atom, R A1 , and R A2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R A1 , and R A2 The organic group represented by R is bonded to the oxygen atom in the ester bond via a C-O bond. A1 and R A2 At least one of the groups is an unsaturated group having 3 to 30 carbon atoms and one or more ethylenically unsaturated double bonds.

[0021] [ka] (In formula (A2), X A1 , R A1 , and R A2 is X in formula (A1) A1 , RA1 , and R A2 is the same as Y A11 is an organic group containing an aromatic ring and having 6 to 40 carbon atoms.

[0022] In the polyimide resin precursor (A), R A1 , and R A2 The molar ratio of the unsaturated groups (unsaturated groups having 3 to 30 carbon atoms and one or more ethylenically unsaturated double bonds) to the molar ratio of the organic groups as the copolymer is preferably 60 mol % or more.

[0023] The polyimide resin precursor (A) described above provides a photosensitive resin composition with excellent resolution, as will be shown in the examples described later.

[0024] The polyimide resin precursor (A) preferably contains 5 mol % or more and 50 mol % or less of the structural unit represented by formula (A1), and more preferably contains 10 mol % or more and 40 mol % or less of the structural unit represented by formula (A1).

[0025] Furthermore, when the polyimide resin precursor (A) contains a structural unit represented by formula (A1) and a structural unit represented by formula (A2), the ratio of the structural unit represented by formula (A1) to the total of the structural units represented by formula (A1) and formula (A2) in the polyimide resin precursor (A) is preferably 5 mol% or more and 50 mol% or less, and more preferably 10 mol% or more and 40 mol% or less. That is, when the polyimide resin precursor (A) contains a structural unit represented by formula (A1) and a structural unit represented by formula (A2), in the polyimide resin precursor (A), Y A1 and Y A11 Y relative to the total number of moles of groups represented by A1 The ratio of the number of moles of groups represented by the formula (I) is preferably 5 mol % or more and 50 mol % or less, and more preferably 10 mol % or more and 40 mol % or less.

[0026] The polyimide resin precursor (A) may contain, in addition to the structural unit represented by formula (A1) and the structural unit represented by formula (A2), other structural units that do not fall under the structural units represented by formula (A1) and the structural units represented by formula (A2). Hereinafter, in the specification of the present application, "other structural units" refer to structural units that do not fall under the category of structural units represented by formula (A1) and structural units represented by formula (A2). The other structural units are not particularly limited as long as they are structural units that do not fall under the category of structural units represented by formula (A1) and structural units represented by formula (A2). The ratio of the total number of moles of the structural units represented by formula (A1) and the structural units represented by formula (A2) to the number of moles of all structural units constituting the polyimide resin precursor (A) is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and particularly preferably 100 mol%.

[0027] The polyimide resin precursor (A) containing the structural unit represented by the formula (A1) is a novel resin precursor. The polyimide resin precursor (A) containing the structural unit represented by the formula (A1) can be incorporated into photosensitive resin compositions other than the above-mentioned negative-type photosensitive resin composition, and can also be used for applications other than photosensitive resin compositions.

[0028] The polyimide resin precursor (A) is typically a polymer of a diamine compound and a dicarboxylic acid which is a reaction product of a tetracarboxylic dianhydride and an alcohol. However, the diamine compound, dicarboxylic acid, tetracarboxylic dianhydride, and alcohols are selected so that the polyimide resin precursor (A) satisfies the above-mentioned predetermined requirements.

[0029] [Diamine Compound] The diamine compound that provides the structural unit represented by the above formula (A1) is represented by the following formula (A1a). H2N-Y A1 -NH2···(A1a) (In formula (A1a), Y A1 is Y in formula (A1)A1 is the same as

[0030] Y A1 is an organic group having 6 to 40 carbon atoms and having a structure in which two alicyclic groups are linked by an alkylene group, an oxygen atom, or a sulfur atom. Y A1 The two alicyclic groups in may be the same or different. Y A1 The alicyclic group in may be a monocyclic group or a polycyclic group. Also, Y A1 The alicyclic group in is preferably an alicyclic hydrocarbon group having 3 or more and 18 or less carbon atoms. Examples of the monocyclic alicyclic group include cycloalkylene groups such as a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group. Examples of polycyclic alicyclic groups include groups in which one hydrogen atom has been removed from an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, or a tetracyclododecyl group.

[0031] Y A1 Examples of the alkylene group in the formula (I) 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 Examples of the alkyl group include a 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, and an icosane-1,20-diyl group. A1 The alkylene group in is preferably a methylene group.

[0032] Y A1 In the above, structures other than the structure in which two alicyclic groups are connected by an alkylene group, an oxygen atom, or a sulfur atom are represented by Y A1 There are no particular limitations on the organic group as long as it is an organic group having 6 to 40 carbon atoms. Y A1 In the above, the structure in which two alicyclic groups are connected by an alkylene group, an oxygen atom, or a sulfur atom is represented by -A 01 -R 01 -A 02 - is the structure of an organic group represented by A 01 and A 02 are each independently an alicyclic group, and R 01 is an alkylene group, an oxygen atom, or a sulfur atom. A 01 and A 02 The alicyclic group as Y A1 The alicyclic group is the same as the alicyclic group in R 01 The alkylene group as Y A1 The alkylene group is the same as that in the above.

[0033] Y A1 When two alicyclic groups have a structure in which they are connected by an alkylene group, an oxygen atom, or a sulfur atom, and other structures, Y A1 is preferably a group represented by the following formula: -A 03 -(X 01 ) t1 -A 01 -R 01 -A 02 -((X 02 ) t2 -A 04 ) t3 -

[0034] In the above formula, A 03 , and A 04 are each independently a divalent organic group. 01 , and X 02 are each independently a divalent inorganic group. t1, t2, and t3 are each independently 0 or 1. A 03 , and A 04 The divalent organic group as may be an aromatic group, an aliphatic group, or a combination of an aromatic group and an aliphatic group. X 01 , and X 02 The divalent inorganic group as is not particularly limited. Examples of the divalent inorganic group include -O-, -S-, -NH-, -SO-, -SO2-, and -N=N-, as well as combinations thereof.

[0035] Y A1 -A 01 -R 01 -A 02 Preferably, the organic group is represented by the formula:

[0036] Y A1 Specific examples of include the following divalent groups: In the following, * represents a bond. [ka]

[0037] The diamine compound that provides the structural unit represented by formula (A2) is represented by the following formula (A2a): In this specification, the diamine compound represented by formula (A1a) is not included in the diamine compound represented by formula (A2a). H2N-Y A11 -NH2···(A2a) (In formula (A2a), Y A11 is Y in formula (A2) A11 is the same as

[0038] Y A11 is an organic group containing an aromatic ring and having 6 to 40 carbon atoms. Y A11 The number of aromatic rings contained in the organic group as described above may be 1 or more, preferably 2 or more, and more preferably 2 to 10. Examples of aromatic rings include benzene rings and naphthalene rings.

[0039] Y A11The organic group Y may be an aromatic group itself, or may be a group in which two or more aromatic groups are bonded together via a bond containing an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, or a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. A11 Examples of bonds containing a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom included in the formula (I) include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, and -COO-, -O-, -CO-, and -S- are preferred.

[0040] Y bonded to amino group A11 The aromatic ring in Y is preferably a benzene ring. A11 When the ring bonded to the amino group in the fused ring is a fused ring containing two or more rings, the ring bonded to the amino group in the fused ring is preferably a benzene ring. Also, Y A11 The aromatic ring contained in may be an aromatic heterocycle.

[0041] Y A11 The organic group as the aryl group is preferably at least one of the groups represented by the following formulas (21) to (24), from the viewpoint of improving the electrical and mechanical properties of the polyimide resin formed using the polyimide resin precursor (A). [ka]

[0042] (21)~(24) Medium, 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 from 1 to 4 carbon atoms, and a halogenated alkyl group having from 1 to 4 carbon atoms. 1is a 9,9'-fluorenylidene group or a group of 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-, -OC 10 H6-O-, -O-C6H4-O-, -O-CH2-O-, and -O-(CH2) n This represents one kind selected from the group consisting of groups represented by -O-.

[0043] Q 1 In the examples, -C6H4- is a phenylene group, preferably an m-phenylene group or a p-phenylene group, more preferably a p-phenylene group. 10 H6- is a naphthalenediyl group, preferably a naphthalene-1,2-diyl group, a naphthalene-1,4-diyl group, a naphthalene-2,3-diyl group, a naphthalene-2,6-diyl group, or a naphthalene-2,7-diyl group, more preferably a naphthalene-1,4-diyl group or a naphthalene-2,6-diyl group. Q 1 In the examples, n is an integer of 1 or more, preferably an integer of 1 or more and 20 or less, more preferably an integer of 1 or more and 12 or less, and even more preferably an integer of 1 or more and 6 or less.

[0044] Y A11 As the diamine compound containing a group represented by formula (24), a compound represented by the following formula (a2) is preferred. 1 As explained above. [ka]

[0045] R in equations (21) to (24) 111From the viewpoint of improving the electrical properties of the resin film to be formed, a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group is more preferred, and a hydrogen atom or a trifluoromethyl group is particularly preferred.

[0046] Q in equation (24) 1 From the viewpoint of the electrical and mechanical properties of the resin film to be formed, the following are preferred: -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-, -OC 10 From the viewpoint of improving the electrical properties and mechanical properties of the polyimide resin formed using the polyimide resin precursor (A), Q in formula (24) is preferably 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-. 1 As the alkyl group, —O—C6H4—C6H4—O— and —O—C6H4—C(CH3)2—C6H4—O— are more preferred, and a group represented by —O—C6H4—C6H4—O— in which both —C6H4— are p-phenylene groups is particularly preferred.

[0047] Examples of the diamine compound represented by formula (A2a) include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 9,10-diaminoanthracene, 9,10-bis(4-aminophenyl)anthracene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diamino Aminobenzophenone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 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)methane bis[N-(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 phenyl 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-aminophenoxy) hydroxyphenyl) 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}phen nyl]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-amino Examples of suitable amines include N,N'-bis(4-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, and ortho-tolidine sulfone. Among these, 4,4'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(4-aminophenoxy)biphenyl, and 3,3'-bis(4-aminophenoxy)biphenyl are preferred from the viewpoint of improving electrical and mechanical properties.

[0048] Also, Y A11 As the silicon atom-containing group, a silicon atom-containing group having an aromatic ring can be adopted. As such a silicon atom-containing group, the following groups can be typically used. [ka]

[0049] The polyimide resin precursor (A) has excellent solubility in organic solvents, and the polyimide resin formed using the polyimide resin precursor (A) has excellent dielectric properties in the high frequency band. Therefore, the diamine compound that provides the structural unit represented by formula (A2) is represented by formula (A2a) and Y A11 is a group represented by the following formula (A1-1), a diamine compound (A-1) represented by formula (A2a), and Y A11 Preferably, the diamine compound (A-2) has a partial structure represented by formula (A2-1) described later and does not fall under the category of diamine compound (A-1), and preferably includes one or more selected from the group consisting of diamine compound (A-3) has a partial structure represented by formula (A3) described later and does not fall under the category of diamine compound (A-1) or diamine compound (A-2). Among these, diamine compound (A-1) and diamine compound (A-2) are preferred.

[0050] (Diamine compound (A-1)) The diamine compound (A-1) is represented by the formula (A2a) and Y A11 is a diamine compound represented by the following formula (A1-1). [ka] (In formula (A1-1), X is an organic group having 1 to 100 carbon atoms, and R a1 is a hydroxy group, a carboxy group, or a halogen atom, and 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, and Ar is R a2 a phenyl group optionally substituted with R a2 ma1 is an integer of 0 to 10, ma2 is an integer of 0 to 7, and ma3 is an integer of 1 to 10.

[0051] In formula (A1-1), Ar is R a2 a phenyl group optionally substituted with R a2Ar is preferably a phenyl group or a naphthyl group. That is, in formula (A1-1), ma2 is preferably 0.

[0052] In formula (A1-1), R a2 R is an aliphatic group having 1 to 20 carbon atoms, a hydroxy group, a carboxy group, a sulfonic acid group, or a halogen atom. a2 The organic group as may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms. R a2 The aliphatic group as the alkyl group preferably has 1 or more and 12 or less carbon atoms, and more preferably has 1 or more and 6 or less carbon atoms.

[0053] R a2Examples of the aliphatic group as the alkyl group 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-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and chain alkyl 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; chain alkenyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group; chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, halogenated chain alkyl groups such as a 2-chlorocyclohexyl group, a 3-chlorocyclohexyl group, a 4-chlorocyclohexyl group, a 2,4-dichlorocyclohexyl group, a 2-bromocyclohexyl group, a 3-bromocyclohexyl group, and a 4-bromocyclohexyl group; halogenated cycloalkyl groups such as a 2-chlorocyclohexyl group, a 3-chlorocyclohexyl group, a 4-chlorocyclohexyl group, a 2,4-dichlorocyclohexyl group, a 2-bromocyclohexyl group, a 3-bromocyclohexyl group, and a 4-bromocyclohexyl group; halogenated chain alkyl groups such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group; hydroxycycloalkyl groups such as a 2-hydroxycyclohexyl group, a 3-hydroxycyclohexyl group, and a 4-hydroxycyclohexyl group;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-nonyloxy group Chain alkoxy groups such as decyloxy and n-icosyloxy groups; chain alkenyloxy groups such as vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, 2-n-butenyloxy, and 3-n-butenyloxy groups; methoxymethyl, ethoxymethyl, n-propoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 3-methoxy-n-propyl, 3-ethoxy-n-propyl, 3-n-propoxy-n-propyl, 4- ...4-methoxymethyl, ethoxymethyl, n-propoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 3-methoxy-n-propyl, 3-ethoxy-n-propyl, 4-methoxymethyl, ethoxymethyl, n-propoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 3-methoxy-n-propyl, 2-methoxyethyl, 2-methoxyethyl, 2-propoxyethyl, 2-propoxyethyl, 2-propoxyethyl, 2-propoxyethyl, 2-propoxyethyl, 2-propoxyethyl, 2-propoxyethyl, 2-propoxyethyl, 2-propoxyethyl, 2-propoxyethyl, 2-propoxyethyl, 2-propoxyethyl, 2-propoxyethyl, 2-propoxyethyl, 2-propoxyethyl, 2-propoxyethyl, alkoxyalkyl groups such as an alkoxy-n-butyl group, a 4-ethoxy-n-butyl group, and a 4-n-propoxy-n-butyl group; and alkoxyalkoxy groups such as a methoxymethoxy group, an ethoxymethoxy group, an n-propoxymethoxy group, a 2-methoxyethoxy group, a 2-ethoxyethoxy group, a 2-n-propoxyethoxy group, a 3-methoxy-n-propoxy group, a 3-ethoxy-n-propoxy group, a 3-n-propoxy-n-propoxy group, a 4-methoxy-n-butyloxy group, a 4-ethoxy-n-butyloxy group, and a 4-n-propoxy-n-butyloxy group. aliphatic acyl groups such as formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, and decanoyl groups; chain alkyloxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butyloxycarbonyl, n-pentyloxycarbonyl, n-hexylcarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl, and n-decyloxycarbonyl groups;Aliphatic acyloxy groups such as formyloxy, acetyloxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, and decanoyloxy;

[0054] 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 depending on the structure of X. The value of ma3 is preferably 1 or more and 4 or less, and more preferably 1 or 2.

[0055] In formula (A1-1), X is an organic group having from 1 to 100 carbon atoms. The number of carbon atoms in the organic group represented by X is preferably from 2 to 80, and more preferably from 6 to 50. The organic group represented by X may contain a heteroatom such as O, N, S, P, B, Si, or a halogen atom. In the compound represented by formula (A1-1), the two amino groups are each bonded to a carbon atom in the organic group represented by X.

[0056] The organic group represented by X may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group. The organic group represented by X may be a group bonded via a bond containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Examples of the bond containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom contained in the organic group represented by X include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, with -O-, -CO-, and -S- being preferred.

[0057] When the organic group represented by X is an aliphatic group, the aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. When the organic group represented by X is an aliphatic group, the aliphatic group is preferably an aliphatic hydrocarbon group. When the organic group represented by 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 be branched.

[0058] When the organic group represented by X is an aliphatic group, the aliphatic group is preferably a group in which (ma1+ma3+2) hydrogen atoms have been removed from an alkylene group having 1 to 20 carbon atoms, more preferably a group in which (ma1+ma3+2) hydrogen atoms have been removed from an alkylene group having 1 to 16 carbon atoms, and even more preferably a group in which (ma1+ma3+2) hydrogen atoms have been removed from an alkylene group having 1 to 12 carbon atoms.

[0059] When the organic group represented by X is a group containing an aromatic group, X, Ar, R in formula (A1-1) a1 , and R a2 Examples of the group comprised of the above include groups represented by the following formulas (11) to (15). [ka]

[0060] In formulas (11) to (15), Ar, R a1 , R a2, ma1, ma2, and ma3 are the same as those in formula (A1). 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 between 0 and 5. The sum of ma16 and ma17 is between 1 and 8.

[0061] 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, and the sum of ma6 and ma7 is preferably 1 or more and 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, and the sum of ma11, ma12, and ma13 is preferably 1 or more and 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, and the sum of ma16 and ma17 is preferably 1 or more and 4 or less.

[0062] 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 aliphatic hydrocarbon groups having 1 to 20 carbon atoms, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, as well as groups combining two or more selected from these groups. The number of carbon atoms in 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 be branched, or may include a ring structure. Specific examples of the aliphatic hydrocarbon group as a 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, and an undecane-1,1 Examples of the alkyl group include 1-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, octadecane-1,18-diyl group, nonadecane-1,19-diyl group, icosane-1,20-diyl group, ethene-1,2-diyl group (vinylene group), propene-1,3-diyl group, ethyne-1,2-diyl group, and propyne-1,3-diyl group.

[0063] Preferred examples of the linking group include alkylene groups having from 1 to 6 carbon atoms, alkenylene groups having from 2 to 6 carbon atoms, alkynylene groups having from 2 to 6 carbon atoms, alkyleneoxy groups having from 1 to 6 carbon atoms, alkenyleneoxy groups having from 2 to 6 carbon atoms, alkynyleneoxy groups having from 2 to 6 carbon atoms, alkylenethio groups having from 1 to 6 carbon atoms, alkenylenethio groups having from 2 to 6 carbon atoms, alkynylenethio groups having from 2 to 6 carbon atoms, alkyleneamino groups having from 1 to 6 carbon atoms, alkenyleneamino groups having from 2 to 6 carbon atoms, alkynyleneamino groups having from 2 to 6 carbon atoms, -CONH-, -NH-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, -OCONH-, and -OCOO-.

[0064] Of the divalent groups represented by formula (A1-1), the divalent group represented by the following formula (A1-2) is preferred, since the polyimide resin formed using the polyimide resin precursor exhibits a low dielectric tangent and good mechanical properties. [ka] (In formula (A1-2), R a1 , R a2 , Ar, ma1, ma2, and ma3 are the same as those in formula (A1-1), and Y a1 is an organic group having 1 to 20 carbon atoms or a single bond, and Y a2 represents an organic group having 1 to 20 carbon atoms, na1 is 0 or 1, and na2 is 0 or 1. When na1 is 1, Ya1 is not a single bond.

[0065] In formula (A1-2), Y a1 The organic group as Y may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms. a1 The organic group as Y is preferably a hydrocarbon group. a1 The hydrocarbon group as Y may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. a1The hydrocarbon group as Y is preferably an aromatic hydrocarbon group, more preferably a phenylene group or a naphthalenediyl group. a1 Specific preferred examples of the aromatic hydrocarbon group as include p-phenylene, m-phenylene, o-phenylene, naphthalene-1,4-diyl, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, and naphthalene-2,3-diyl. Among these aromatic hydrocarbon groups, p-phenylene and m-phenylene are preferred, and p-phenylene is more preferred.

[0066] In formula (A1-2), na2 is preferably 1, and both na1 and na2 are preferably 1, and Y a1 is more preferably an organic group. In this case, due to the high steric freedom of the ether bond, it is thought that the structural units derived from the diamine compound (A-1) having the divalent group represented by formula (A1-2) are likely to be well packed, and it is easy to obtain a polyimide resin precursor that gives a polyimide resin excellent in mechanical properties, thermal properties, electrical properties, etc.

[0067] In formula (A1-2), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2.

[0068] Specific examples of the diamine compound (A-1) described above include the following compounds. [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] (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 fall under the category of the diamine compound (A-1). [ka] (In formula (A2-1), R a3 and R a4 are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and ma4 and ma5 are each independently an integer of 0 to 4.

[0077] In formula (A2-1), R a3 and R a4Examples of the alkyl group having 1 to 4 carbon atoms as the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these alkyl groups, a methyl group and an ethyl group are preferred, and a methyl group is more preferred. In formula (A2-1), R a3 and R a4 Examples of the alkoxy group having 1 to 4 carbon atoms as 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. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred. In formula (A2-1), R a3 and R a4 Examples of the halogen atom as the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, a chlorine atom and a bromine atom are preferred.

[0078] In formula (A2-1), ma4 and ma5 each independently represent an integer of 0 or more and 4 or less. In view of the ease of availability of the diamine compound (A-2), ma4 and ma5 each preferably represent an integer of 0 or more and 2 or less, and more preferably 0.

[0079] Suitable divalent groups having a partial structure represented by formula (A2-1) include divalent groups represented by the following formula (A2-2). [ka] (In formula (A2-2), X 1 and X 2 R are each independently an aromatic hydrocarbon group which may be substituted with one or more groups selected from the group consisting of an alkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, and a halogen atom. a3 , R a4, ma4, and ma5 are the same as those in formula (A2-1). However, the upper limit of the number of carbon atoms in the divalent group represented by formula (A2-2) is 40.

[0080] X in formula (A2-2) 1 and X 2 are each independently a divalent aromatic hydrocarbon group optionally substituted with one or more groups selected from the group consisting of an alkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, and a halogen atom. Examples of the alkyl group having 1 to 4 carbon atoms as a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these alkyl groups, a methyl group and an ethyl group are preferred, and a methyl group is more preferred. Examples of the alkoxy group having 1 to 4 carbon atoms as a substituent include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred. Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, a chlorine atom and a bromine atom are preferred.

[0081] X 1 and X 2 The number of carbon atoms in the aromatic hydrocarbon group as is not particularly limited, as long as the number of carbon atoms in the divalent group represented by formula (A2-2) is 40 or less. Note that the number of carbon atoms in the aromatic hydrocarbon group does not include the number of carbon atoms in the substituent. X 1 , and X 2Preferred aromatic hydrocarbon groups as the aromatic hydrocarbon group include phenylene groups such as o-phenylene, m-phenylene, and p-phenylene; naphthalenediyl groups such as naphthalene-1,4-diyl, naphthalene-1,3-diyl, naphthalene-2,6-diyl, and naphthalene-2,7-diyl; and biphenyldiyl groups such as biphenyl-4,4'-diyl, biphenyl-3,4'-diyl, and biphenyl-3,3'-diyl.

[0082] X 1 , and X 2 As the alkyl group, a p-phenylene group, an m-phenylene group, a naphthalene-1,4-diyl group, and a biphenyl-4,4'-diyl group are preferred, a p-phenylene group and a biphenyl-4,4'-diyl group are more preferred, and a p-phenylene group is even more preferred.

[0083] Specific examples of the diamine compound (A-2) having a divalent group having the partial structure represented by formula (A2-1) explained above include the following compounds. [ka]

[0084] (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 category of the diamine compound (A-1) or the diamine compound (A-2). [ka] (In formula (A3), R a5 and R a6 are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; ma6 and ma7 are each independently an integer of 0 to 4; R a7 and R a8 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or a phenyl group; R a7 and Ra8 may be bonded to each other to form a ring.

[0085] In formula (A3), R a5 and R a6 Examples of the alkyl group having 1 to 4 carbon atoms as the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these alkyl groups, a methyl group and an ethyl group are preferred, and a methyl group is more preferred. In formula (A3), R a5 and R a6 Examples of the alkoxy group having 1 to 4 carbon atoms as 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. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred. In formula (A3), R a5 and R a6 Examples of the halogen atom as the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, a chlorine atom and a bromine atom are preferred.

[0086] In formula (A3), ma6 and ma7 each independently represent an integer of 0 or more and 4 or less. In view of the ease of availability of the diamine compound (A-3), ma6 and ma7 each preferably represent an integer of 0 or more and 2 or less, and more preferably 0.

[0087] In formula (A3), R a7 and R a8 Examples of the alkyl group having 1 to 4 carbon atoms as the alkyl group 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 halogenated alkyl group having 1 to 4 carbon atoms as the halogenated alkyl group include a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, and a 1,1,2,2,2-pentafluoroethyl group. R in formula (A3) a7 and R a8 As the alkyl group, a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group, and a phenyl group are preferred because the polyimide resin precursor has good solubility in organic solvents and the diamine compound (A-3) is easily available. Also, R a7 and R a8 and preferably combine with each other to form a cycloalkylidene group having 5 to 8 carbon atoms, such as a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, or a cyclooctylidene group.

[0088] Specific preferred examples of the partial structure represented by formula (A3) include the following structures. [ka]

[0089] A compound suitable as the diamine compound (A-3) is a compound represented by the following formula (A3-1). [ka] (In formula (A3-1), X 3 and X 4 R are each independently an aromatic hydrocarbon group which may be substituted with one or more groups selected from the group consisting of an alkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, and a halogen atom. a5 , R a6 , R a7 , R a8 , ma6, and ma7 are the same as those in formula (A3).

[0090] X in formula (A3-1) 3 and X 4 are each independently a divalent aromatic hydrocarbon group optionally substituted with one or more groups selected from the group consisting of an alkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, and a halogen atom. Examples of the alkyl group having 1 to 4 carbon atoms as a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these alkyl groups, a methyl group and an ethyl group are preferred, and a methyl group is more preferred. Examples of the alkoxy group having 1 to 4 carbon atoms as a substituent include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred. Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, a chlorine atom and a bromine atom are preferred.

[0091] X 3 and X 4 The number of carbon atoms in the aromatic hydrocarbon group as the aryl group is not particularly limited, and is, for example, preferably from 6 to 50, and more preferably from 6 to 20. The number of carbon atoms in the aromatic hydrocarbon group does not include the number of carbon atoms in the substituent. X 3 and X 4 Preferred aromatic hydrocarbon groups as the aromatic hydrocarbon group include phenylene groups such as o-phenylene, m-phenylene, and p-phenylene; naphthalenediyl groups such as naphthalene-1,4-diyl, naphthalene-1,3-diyl, naphthalene-2,6-diyl, and naphthalene-2,7-diyl; and biphenyldiyl groups such as biphenyl-4,4'-diyl, biphenyl-3,4'-diyl, and biphenyl-3,3'-diyl.

[0092] X 3 and X 4 As the alkyl group, a p-phenylene group, an m-phenylene group, a naphthalene-1,4-diyl group, and a biphenyl-4,4'-diyl group are preferred, a p-phenylene group and a biphenyl-4,4'-diyl group are more preferred, and a p-phenylene group is even more preferred.

[0093] Specific examples of the diamine compound (A-3) represented by the formula (A3) explained above include the following compounds. [ka]

[0094] [ka]

[0095] [Dicarboxylic acids obtained by reaction of tetracarboxylic dianhydrides with alcohols] Dicarboxylic acids are reaction products of tetracarboxylic dianhydrides and alcohols. In the polyimide resin precursor (A), R in the above formula (A1) or formula (A2) A1 , and R A2 At least one of R in the above formula (A1) or (A2) is an unsaturated group having one or more ethylenically unsaturated double bonds and having 3 to 30 carbon atoms. A1 , and R A2 cannot all be hydrogen atoms. In formula (A1) and formula (A2), R A1 , and R A2 The ratio of the number of moles of unsaturated groups having 3 to 30 carbon atoms and one or more ethylenically unsaturated double bonds to the number of moles of organic groups as the methyl group is preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0096] R in formula (A1) and formula (A2) A1 , and R A2Examples of the unsaturated group having 3 to 30 carbon atoms and one or more ethylenically unsaturated double bonds include an unsaturated group having 3 to 30 carbon atoms and one or more (meth)acryloyl groups (hereinafter simply referred to as a "(meth)acryloyl group-containing group") and an aliphatic hydrocarbon group having 3 to 30 carbon atoms and one or more ethylenically unsaturated double bonds. The unsaturated group is preferably an unsaturated group having 3 to 30 carbon atoms and one or more (meth)acryloyl groups.

[0097] R A1 , and R A2 The dicarboxylic acid having an organic group as the dicarboxylic acid can be obtained by reacting an alcohol having a structure corresponding to the structure of the organic group with a tetracarboxylic dianhydride. Hereinafter, in this specification, unless otherwise specified, the term "dicarboxylic acid" refers to a dicarboxylic acid that is a reaction product of a tetracarboxylic dianhydride and one of the above alcohols. The tetracarboxylic dianhydride and the alcohol will be described below.

[0098] (Tetracarboxylic acid dianhydride) The tetracarboxylic dianhydride is not particularly limited as long as the desired effect is not impaired. As the tetracarboxylic dianhydride, typically, tetracarboxylic dianhydrides that have been conventionally used in the production of polyamic acid and polyimide resins can be used. The tetracarboxylic dianhydride may be a compound represented by the following formula (A3). [ka] (In formula (A3), X A1 is a tetravalent organic group having 4 to 40 carbon atoms.

[0099] In formula (A3), X A1 is a tetravalent organic group having 4 to 40 carbon atoms, which may have one or more substituents in addition to the two acid anhydride groups represented by —CO—O—CO— in formula (A3). Preferred examples of the substituent include a fluorine atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a fluorinated alkyl group having from 1 to 6 carbon atoms, and a fluorinated alkoxy group having from 1 to 6 carbon atoms. The compound represented by formula (A3) 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-mentioned substituents and to one or more substituents that the aromatic group described below may have on the aromatic ring.

[0100] X A1 The number of carbon atoms constituting X is preferably 8 or more, more preferably 12 or more. A1 The number of carbon atoms constituting X is preferably 30 or less. A1 X may be an aliphatic group, an aromatic group, or a group that combines these structures. A1 X may contain halogen atoms, oxygen atoms, nitrogen atoms, and sulfur atoms in addition to carbon atoms and hydrogen atoms. A1 contains an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, the nitrogen atom, or the sulfur atom is preferably a group selected from a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, A1 X may be included as a group selected from -O-, -CO-, -S-, and A1 It is more preferred that the ion exchange coefficient be included in the formula (I).

[0101] The tetracarboxylic acid dianhydride represented by formula (A3) may be an aliphatic tetracarboxylic acid dianhydride having two dicarboxylic acid anhydride groups bonded to an aliphatic group, or an aromatic tetracarboxylic acid dianhydride having at least one dicarboxylic acid anhydride group bonded to an aromatic group. The aromatic tetracarboxylic dianhydride preferably has two dicarboxylic anhydride groups bonded to the aromatic group. A1 The tetravalent organic group as is preferably a residue obtained by removing two dicarboxylic acid anhydride groups from an aromatic tetracarboxylic acid dianhydride.

[0102] The aliphatic tetracarboxylic dianhydride may contain an alicyclic structure. The alicyclic structure may be polycyclic. Examples of aliphatic tetracarboxylic dianhydrides that do not have an alicyclic structure include 1,2,3,4-tetracarboxylic dianhydride (e.g., Rikacid BT-100, manufactured by New Japan Chemical Co., Ltd.). Examples of the aliphatic tetracarboxylic dianhydride having an alicyclic structure include cyclobutane tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride (e.g., Enehyde (registered trademark) CpODA, manufactured by Eneos Corporation), 2,2-bis(2, 3-dicarboxyphenoxy)hexafluoropropane dianhydride [5,5'-(1,4-phenylene)bisnorbornane]-2,2',3,3'-tetracarboxylic dianhydride (for example, Enehyde (registered trademark) BzDA, manufactured by Eneos Corporation), 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione (for example, Rikacid TDA-100, manufactured by New Japan Chemical Co., Ltd.).

[0103] Examples of the aromatic tetracarboxylic dianhydride represented by formula (A3) and having two dicarboxylic acid 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 (3,4-dicarboxyphenyl) dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, Examples of suitable dianhydrides include carboxylic acid dianhydrides, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid 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., Rikacid TMEG100, manufactured by New Japan Chemical Co., Ltd.), and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane Chemical Co., Ltd.). Among these aromatic tetracarboxylic dianhydrides, 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride, 4,4'-bis(3,4-dicarboxyphenyloxy)biphenyl dianhydride, 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride, and α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride are preferred because 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). [ka]

[0104] In formula (a1), n, which represents the number of carbon atoms in the linear alkylene group in the α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride, 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. Specific examples of suitable α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydrides include 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (e.g., Rikacid TMEG100, manufactured by New Japan Chemical Co., Ltd.) and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane Chemical Co., Ltd.).

[0105] In addition, it is also preferable that the aromatic tetracarboxylic dianhydride is biphenyltetracarboxylic dianhydride, in terms of suppressing warping of a polyimide resin film formed using a photosensitive resin composition containing the polyimide resin precursor (A) and, when photosensitivity is imparted to a photosensitive resin composition, the composition has good photolithography properties. Examples of biphenyltetracarboxylic dianhydrides 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.

[0106] The aromatic tetracarboxylic dianhydride may also be, for example, a compound represented by the following general formulas (a3-2) to (a3-4). [ka]

[0107] In the above formula (a3-2) and formula (a3-3), R a01 , R a02 and R a03 R represents a divalent group that is an aliphatic group optionally substituted with halogen, an oxygen atom, a sulfur atom, an aromatic group connected via one or more divalent elements, or a combination thereof. 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 atom (fluorine, chlorine, bromine, iodine). Examples of the compound represented by 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.

[0108] In addition, in the above formula (a3-4), R a04 , R a05R represents a monovalent substituent that is an aliphatic group optionally substituted with halogen, an aromatic group substituted with one or more divalent elements, or a halogen, or a combination thereof. a04 , and R a05 may be the same or different. As the compound represented by formula (a3-4), difluoropyromellitic dianhydride, dichloropyromellitic dianhydride, and the like can also be used.

[0109] The polyimide resin precursor (A) preferably has a radical polymerizable group-containing group on its molecular chain in addition to the residue derived from the alcohol. Therefore, the tetravalent organic group X in formula (A3) A1 may be a group represented by the following formulae (a3-5) to (a3-7). [ka] R in formulas (a3-5) to (a3-7) a01 , R a02 , and R a03 is R in the above formulas (a3-2), (a3-3), and (a3-4). a01 , R a02 , and R a03 is the same as: R in formula (a3-5), formula (a3-6), and formula (a3-7) a06 is a radical polymerizable group-containing group. The radical polymerizable group-containing group will be described later.

[0110] (Alcohol) As described above, the dicarboxylic acid is a reaction product of a tetracarboxylic dianhydride and an alcohol. The alcohols include alcohols in which a hydroxyl group is bonded to the unsaturated group described above.

[0111] As mentioned above, in formula (A1) and formula (A2), R A1 , and R A2Examples of the unsaturated group having 3 to 30 carbon atoms and one or more ethylenically unsaturated double bonds include a (meth)acryloyl group-containing group and an aliphatic hydrocarbon group having 3 to 30 carbon atoms and one or more ethylenically unsaturated double bonds. The unsaturated group is preferably a (meth)acryloyl group-containing group. Hereinafter, alcohols will be described by referring to an aliphatic hydrocarbon group having 3 to 30 carbon atoms and one or more ethylenically unsaturated double bonds as an "unsaturated group G1," an alcohol having the unsaturated group G1 as an "alcohol AG1," a (meth)acryloyl group-containing group as an "(meth)acryloyl group-containing group G2," and an alcohol having the (meth)acryloyl group-containing group G2 as an "alcohol AG2."

[0112] Alcohol AG1 The alcohol AG1 is an alcohol in which a hydroxyl group is bonded to an unsaturated group G1, which is an aliphatic hydrocarbon group having 3 to 30 carbon atoms and does not contain a (meth)acryloyl group and has one or more ethylenically unsaturated double bonds. Therefore, the number of carbon atoms in the alcohol AG1 is also 3 to 30. The number of carbon atoms in the unsaturated group G1 is preferably from 3 to 30, more preferably from 4 to 30, even more preferably from 5 to 30, and particularly preferably from 5 to 25. Accordingly, the number of carbon atoms in the alcohol AG1 is also preferably from 3 to 30, more preferably from 4 to 30, even more preferably from 5 to 30, and particularly preferably from 5 to 25.

[0113] The alcohol AG1 and the unsaturated group G1 may have a linear or branched structure. The alcohol AG1 and the unsaturated group G1 may contain a cyclic group. The cyclic group may be an alicyclic group or an aromatic group. The unsaturated group G1 of the alcohol AG1 may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms, to the extent that the desired effect is not impaired.

[0114] The number of ethylenically unsaturated double bonds in the alcohol AG1 and the unsaturated group G1 is not particularly limited, and the number of ethylenically unsaturated double bonds is preferably 1 or more and 4 or less, and more preferably 1 or 2.

[0115] The unsaturated group G1 constituting the alcohol AG1 is preferably a chain unsaturated aliphatic hydrocarbon group, more preferably a straight-chain unsaturated aliphatic hydrocarbon group. The unsaturated aliphatic hydrocarbon group preferably has 5 to 30 carbon atoms.

[0116] Preferred specific examples of the alcohol AG1 include allyl alcohol; butenols such as but-3-en-1-yl alcohol and but-2-en-1-yl alcohol; pentenols such as pent-4-en-1-yl alcohol, pent-3-en-1-yl alcohol, and pent-2-en-1-yl alcohol; hexenols such as hex-5-en-1-yl alcohol, hex-4-en-1-yl alcohol, hex-3-en-1-yl alcohol, and hex-2-en-1-yl alcohol; hept-6-en-1-yl alcohol; heptenols such as oct-7-en-1-yl alcohol, oct-6-en-1-yl alcohol, oct-5-en-1-yl alcohol, oct-4-en-1-yl alcohol, oct-3-en-1-yl alcohol, and oct-2-en-1-yl alcohol; octenols such as non-8-en-1-yl alcohol, non-7-en-1-yl alcohol, nonanols such as dec-9-en-1-yl alcohol, dec-8-en-1-yl alcohol, dec-7-en-1-yl alcohol, dec-6-en-1-yl alcohol, dec-5-en-1-yl alcohol, dec-4-en-1-yl alcohol, dec-3-en-1-yl alcohol, and nonan-2-en-1-yl alcohol; Decenols such as dec-2-en-1-yl alcohol; undecenols such as undec-10-en-1-yl alcohol; dodecenols such as dodec-11-en-1-yl alcohol; tridecenols such as tridec-12-en-1-yl alcohol; tetradecenols such as tetradec-13-en-1-yl alcohol; pentadecenols such as pentadec-14-en-1-yl alcohol; hexadecenols such as hexadec-15-en-1-yl alcohol; heptadecenols such as heptadec-16-en-1-yl alcohol;Examples include octadecenols such as octadec-17-en-1-yl alcohol and octadec-9-en-1-yl alcohol (oleyl alcohol); nonadecenols such as nonadec-18-en-1-yl alcohol; icosenols such as icosan-19-en-1-yl alcohol; and octadienols such as octadeca-9,12-dien-1-yl alcohol (linoleyl alcohol);

[0117] Specific preferred examples of the unsaturated group G1 include an allyl group; butenyl groups such as but-3-en-1-yl and but-2-en-1-yl groups; pentenyl groups such as pent-4-en-1-yl, pent-3-en-1-yl, and pent-2-en-1-yl groups; hexenyl groups such as hex-5-en-1-yl, hex-4-en-1-yl, hex-3-en-1-yl, and hex-2-en-1-yl groups; hept-6-en-1-yl, hept-5-en-1-yl, hept-4-en-1-yl, and hept- heptenyl groups such as a 3-en-1-yl group and a hept-2-en-1-yl group; octenyl groups such as an oct-7-en-1-yl group, an oct-6-en-1-yl group, an oct-5-en-1-yl group, an oct-4-en-1-yl group, an oct-3-en-1-yl group, and an oct-2-en-1-yl group; non-8-en-1-yl group, a non-7-en-1-yl group, a non-6-en-1-yl group, a non-5-en-1-yl group, a non-4-en-1-yl group, a non-3-en-1-yl group, and a non-2-en-1-yl group; nonenyl groups such as the group; decenyl groups such as dec-9-en-1-yl, dec-8-en-1-yl, dec-7-en-1-yl, dec-6-en-1-yl, dec-5-en-1-yl, dec-4-en-1-yl, dec-3-en-1-yl, and dec-2-en-1-yl group; undecenyl groups such as undec-10-en-1-yl group; dodecenyl groups such as dodec-11-en-1-yl group; tridecenyl groups such as tridec-12-en-1-yl group; tetradecenyl groups such as tetradec-13-en-1-yl group; Examples of such groups include pentadecenyl groups such as pentadec-14-en-1-yl groups; hexadecenyl groups such as hexadec-15-en-1-yl groups; heptadecenyl groups such as heptadec-16-en-1-yl groups; octadecenyl groups such as octadec-17-en-1-yl groups and octadec-9-en-1-yl groups (oleyl groups); nonadecenyl groups such as nonadec-18-en-1-yl groups; icosenyl groups such as icosan-19-en-1-yl groups; and octadienyl groups such as octadeca-9,12-dien-1-yl groups (linoleyl groups).

[0118] Alcohol AG2 The alcohol AG2 is an alcohol in which a hydroxyl group is bonded to the (meth)acryloyl group-containing group G2. The structure and number of carbon atoms of the alcohol AG2 and the (meth)acryloyl group-containing group G2 are not particularly limited as long as the desired effect is not impaired. The number of carbon atoms in the (meth)acryloyl group-containing group G2 is preferably from 3 to 30, more preferably from 3 to 25, and even more preferably from 4 to 20. Accordingly, the number of carbon atoms in the alcohol AG2 is also preferably from 3 to 30, more preferably from 3 to 25, and even more preferably from 4 to 20.

[0119] The alcohol AG2 and the (meth)acryloyl group-containing group G2 may have a linear or branched structure. The alcohol AG2 and the (meth)acryloyl group-containing group G2 may contain a cyclic group. The cyclic group may be an alicyclic group or an aromatic group. The (meth)acryloyl group-containing group G2 of the alcohol AG2 may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms, to the extent that the desired effects are not impaired.

[0120] The number of (meth)acryloyl groups in the alcohol AG2 and the (meth)acryloyl group-containing group G2 is not particularly limited. The number of (meth)acryloyl groups is preferably 1 or more and 4 or less, more preferably 1 or 2.

[0121] In terms of facilitating the formation of a polyimide resin with a low dielectric tangent, it is preferable that the alcohol AG2 be an alcohol having a secondary hydroxyl group and a (meth)acryloyl group in combination, or an alcohol having a methylol group and a (meth)acryloyl group in combination. Hereinafter, an alcohol having a secondary hydroxyl group and a (meth)acryloyl group in combination, and an alcohol having a methylol group and a (meth)acryloyl group in combination, will also be referred to as "alcohol AG2-1." An alcohol that falls under alcohol AG2 but does not fall under alcohol AG2-1 will also be referred to as "alcohol AG2-2."

[0122] In the specification of this application, a methylol group is defined as a hydroxymethyl group bonded to a secondary carbon atom, a tertiary carbon atom, a carbon atom bonded to one carbon atom and one heteroatom, a carbon atom bonded to two heteroatoms, or a carbon atom in an aromatic ring. For example, a hydroxyethyl group consists of a hydroxymethyl group and a methylene group. However, according to the above definition, in the specification and claims of this application, the hydroxymethyl group bonded to the primary carbon atom in the methylene group contained in the hydroxyethyl group does not fall under the category of a methylol group.

[0123] When producing alcohol AG2-1, a mixture containing alcohol AG2-2 together with alcohol AG2-1 may inevitably be produced due to the production method. For example, when a polyol having a secondary hydroxyl group or a methylol group and a primary hydroxyl group is reacted with a (meth)acrylic acid halide or the like to produce an alcohol AG2-1, an alcohol having a (meth)acryloyl group as well as a primary hydroxyl group may be by-produced. As long as a desired amount of dicarboxylic acid containing an ester group derived from the alcohol AG2-1 can be produced, a mixture containing the alcohol AG2-2 together with the alcohol AG2-1 produced by such a method can be used as the alcohol to be reacted with the tetracarboxylic dianhydride.

[0124] The alcohol AG2-1 may have two or more hydroxyl groups in combination. The alcohol AG2-1 may have a secondary hydroxyl group and a methylol group in combination. The alcohol AG2-1 preferably has one secondary hydroxyl group or one methylol group.

[0125] When the alcohol AG2-1 has two or more (meth)acryloyl groups, the alcohol AG2-1 is preferably, for example, a (meth)acrylate of glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, or the like. Specific examples of suitable alcohols AG2-1 having two or more (meth)acryloyl groups include glycerin-1,3-di(meth)acrylate, glycerin-1,2-di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate. These compounds may have a combination of acryloyl and methacryloyl groups.

[0126] When the alcohol AG2-1 has one (meth)acryloyl group, the alcohol AG2-1 is preferably at least one selected from the compounds represented by the following formula (I) and the compounds represented by the following formula (II). CH=CR 1 -CO-OR 2 -CHR 3 -OH (I) CH=CR 1 -CO-OR 4 -CH2-OH (II) (In formula (I), R 1 is a hydrogen atom or a methyl group, and R 2 is bonded to the oxygen atom in the ester bond by a CO bond, and R 3 is a divalent organic group bonded to the carbon atom to which R is bonded by a C—C bond, 3 is R 3 is a monovalent organic group bonded to the carbon atom to which R is bonded by a C—C bond, 2 and R 3 may be bonded to form a ring, In formula (II), R 1 is a hydrogen atom or a methyl group, and R 4 is a divalent organic group that is bonded to the oxygen atom in the ester bond via a C-C bond and to the methylol group in formula (II) via a C-C bond.

[0127] In the above formula (I), R 2 is bonded to the oxygen atom in the ester bond by a CO bond, and R 3is a divalent organic group bonded to the carbon atom to which the carbon atom is bonded by a C—C bond. The divalent organic group may be a group containing a halogen atom or a heteroatom such as O, S, or N. R in formula (I) 2 The number of carbon atoms in the divalent organic group is not particularly limited. The number of carbon atoms in the divalent organic group is, for example, preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and further preferably 1 or more and 8 or less.

[0128] R in formula (I) 2 The divalent organic group as R is preferably a divalent hydrocarbon group. The divalent hydrocarbon group may contain a cyclic group. The cyclic group may be an aliphatic ring, an aromatic ring, or a fused ring in which an aliphatic ring and an aromatic ring are fused. 2 The divalent hydrocarbon group as is preferably an alkylene group.

[0129] Suitable examples of the alkylene 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 butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, and an octane-1,8-diyl group. Of these, a methylene group, an ethane-1,2-diyl group (ethylene group), a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group are preferred.

[0130] In formula (I), R 3 is R 3 is a monovalent organic group bonded to the carbon atom to which the carbon atom is bonded by a C—C bond. The monovalent organic group may be a group containing a halogen atom or a heteroatom such as O, S, or N. R in formula (I) 3 The number of carbon atoms in the monovalent organic group is not particularly limited. The number of carbon atoms in the monovalent organic group is, for example, preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and further preferably 1 or more and 8 or less.

[0131] R in formula (I) 3 The monovalent organic group may be a chain aliphatic group, a cyclic group, or a group consisting of a chain aliphatic group and a cyclic group. The cyclic group may be an aliphatic ring, an aromatic ring, or a fused ring in which an aliphatic ring and an aromatic ring are fused.

[0132] R in formula (I) 3 Specific examples of the monovalent organic group as the aryl group include alkyl groups such as 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-hexyl group, an n-heptyl group, and an n-octyl group; a methoxymethyl group, an ethoxymethyl group, an n-propyloxymethyl group, an n-butyloxymethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2-n-propyloxyethyl group, a 2-n-butyloxyethyl group, a 3-methoxypropyl group, a 3-ethoxypropyl group, a 3-n-propyloxypropyl group, a 3-n-butyloxypropyl group, a 4-methoxybutyl group, a 4-ethoxybutyl group, a 4-n-propyloxybutyl group, and a 4-n-propyloxybutyl group. aryloxyalkyl groups such as a phenoxymethyl group, a 2-phenoxyethyl group, a 3-phenoxypropyl group, and a 4-phenoxybutyl group; and cycloalkyloxyalkyl groups such as a cyclopentyloxymethyl group, a 2-cyclopentyloxyethyl group, a 3-cyclopentyloxypropyl group, a 4-cyclopentyloxybutyl group, a cyclohexyloxymethyl group, a 2-cyclohexyloxyethyl group, a 3-cyclohexyloxypropyl group, a 4-cyclohexyloxybutyl group, a cycloheptyloxymethyl group, a 2-cycloheptyloxyethyl group, a 3-cycloheptyloxypropyl group, and a 4-cycloheptyloxybutyl group.

[0133] In formula (I), -R 2 -CHR 3Specific preferred examples of the divalent group represented by - include the following groups. In the following specific examples, * represents the end of the bond bonding to the oxygen atom in the ester bond in formula (I). ** represents the end of the bond bonding to the hydroxyl group in formula (I). In addition, since the polyimide resin formed using the polyimide resin precursor exhibits a low dielectric tangent value and is excellent in chemical resistance, -R 2 -CHR 3 The divalent group represented by - preferably contains a cyclic group. Such a cyclic group may be an aromatic group, an alicyclic group, or a fused cyclic group in which an aromatic ring and an aliphatic ring are fused. [ka]

[0134] Preferable specific examples of the compound represented by formula (I) include the following compounds. [ka]

[0135] In the above formula (II), R 4 is a divalent organic group bonded to the oxygen atom in the ester bond via a C-C bond and to the methylol group in formula (II) via a C-C bond. The divalent organic group may be a group containing a halogen atom or a heteroatom such as O, S, or N. R in formula (II) 4 The number of carbon atoms in the divalent organic group is not particularly limited. The number of carbon atoms in the divalent organic group is, for example, preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and further preferably 1 or more and 8 or less.

[0136] R in formula (II) 4 The divalent organic group may be a chain aliphatic group, a cyclic group, or a group consisting of a chain aliphatic group and a cyclic group. The cyclic group may be an aliphatic ring, an aromatic ring, or a fused ring in which an aliphatic ring and an aromatic ring are fused.

[0137] In formula (II), R 4 Specific preferred examples of the divalent group represented by the formula (II) include the following groups. In the specific examples below, * denotes the end of the bond bonding to the oxygen atom in the ester bond in formula (II). ** denotes the end of the bond bonding to the methylol group in formula (II). [ka]

[0138] Preferable specific examples of the compound represented by formula (II) include the following compounds: [ka]

[0139] Suitable examples of alcohol AG2-2, which corresponds to alcohol AG2 but does not correspond to alcohol AG2-1, include mono(meth)acrylates of diols such as 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 5-hydroxypentyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, and 2-(2-hydroxyethoxy)ethyl(meth)acrylate; N-hydroxyalkyl-substituted (meth)acrylamides such as N-(2-hydroxyethyl)(meth)acrylamide and N-(3-hydroxypropyl)(meth)acrylamide; and hydroxyl group-containing ketones such as (hydroxymethyl)vinyl ketone and (2-hydroxyethyl)vinyl ketone.

[0140] Alcohol AG3 Alcohol AG3 is an alcohol that does not fall under Alcohol AG1 or Alcohol AG2. The alcohols may contain Alcohol AG3 to the extent that the desired effect is not impaired. Therefore, the polyimide resin precursor (A) is R A1 , and R A2The organic group as the unsaturated group G1 and the (meth)acryloyl group-containing group G2 may contain an organic group G3, which is an organic group that does not fall under the category of the unsaturated group G1 and the (meth)acryloyl group-containing group G2.

[0141] The structure of the alcohol AG3 is not particularly limited as long as the desired effect is not impaired.

[0142] Examples of alcohols AG3 include alkane monools 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; 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; and alcohols having a radically polymerizable group that do not fall under the category of alcohols AG1 and alcohols AG2.

[0143] (Production of dicarboxylic acids) Dicarboxylic acids can be obtained by reacting the tetracarboxylic dianhydrides described above with alcohols. The alcohols react with the carboxylic anhydride groups to produce carboxy groups and ester groups.

[0144] The above-mentioned tetracarboxylic dianhydride is a21 Dicarboxylic acids can be obtained by reacting alcohols represented by -OH. R a21 is a residue obtained by removing the hydroxyl group from the aforementioned alcohols. Such dicarboxylic acids have carboxy groups and -CO-OR groups located on adjacent carbon atoms in the dicarboxylic acid. a21The compound has two pairs of groups represented by the formula:

[0145] Carboxy group and -CO-OR a21 The above dicarboxylic acid has two pairs of groups represented by -CO-OR. a21 As the dicarboxylic acid, one of such isomers may be used alone, or two or more of such isomers may be used in combination. In the specification and claims of the present application, it is permitted that the polyimide resin precursor (A) contains a plurality of types of structural units derived from a plurality of isomers of a dicarboxylic acid.

[0146] For example, the dicarboxylic acid corresponding to pyromellitic dianhydride has isomers represented by the following formula (a4-a1) and the following formula (a4-a2): The dicarboxylic acid corresponding to 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride has isomers represented by the following formula (a4-b1), the following formula (a4-b2), and the following formula (a4-b3): In the following formulas (a4-a1), (a4-a2), and (a4-b1) to (a4-b3), R a21 are as described above.

[0147] [ka]

[0148] Dicarboxylic acids corresponding to the tetracarboxylic dianhydrides represented by the above formulae (a3-2) to (a3-4) include compounds represented by the following formulae (a4-2a) to (a4-2c), (a4-3a) to (a4-3c), and (a4-4a) to (a4-4c). In formulae (a4-2a) to (a4-2c), (a4-3a) to (a4-3c), and (a4-4a) to (a4-4c), R a01 ~R a05are the same as those in formulas (a3-2) to (a3-4). In formulas (a4-2a) to (a4-2c), formulas (a4-3a) to (a4-3c), and formulas (a4-4a) to (a4-4c), R a21 is as mentioned above. [ka]

[0149] Dicarboxylic acids corresponding to the tetracarboxylic dianhydrides represented by the above formulae (a3-5) to (a3-7) include compounds represented by the following formulae (a4-5a) to (a4-5c), (a4-6a) to (a4-6c), (a4-7a), and (a4-7b). In formulae (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 those in formulas (a3-5) to (a3-7). In formulas (a4-5a) to (a4-5c), formulas (a4-6a) to (a4-6c), formulas (a4-7a), and formulas (a4-7b), R a21 is as mentioned above.

[0150] [ka]

[0151] The reaction between a tetracarboxylic dianhydride and an alcohol is usually carried out in an organic solvent. The organic solvent used in the reaction between a tetracarboxylic dianhydride and an alcohol is not particularly limited as long as it can dissolve the tetracarboxylic dianhydride and the alcohol and does not react with the tetracarboxylic dianhydride and the alcohol. The organic solvent can be used alone or in combination of two or more kinds.

[0152] Examples of organic solvents that can be 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 acid amide, methoxy-N,N-dimethylpropionamide, butoxy-N,N-dimethylpropionamide, N-methylcaprolactam, N,N'-dimethylpropyleneurea, N,N,N',N'-tetramethylurea, and pyridine; dimethyl sulfoxide; sulfolane; γ-butyrolactone; γ-valerolactone; δ-valerolactone; Examples of suitable solvents include lactones such as 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; and hexane, heptane, benzene, toluene, and xylene. These organic solvents may be used alone or in combination of two or more.

[0153] 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.

[0154] The temperature at which the tetracarboxylic dianhydride is reacted with the alcohol is not particularly limited as long as the reaction proceeds smoothly. Typically, the reaction temperature between the tetracarboxylic dianhydride and the alcohol 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 time for reacting the tetracarboxylic dianhydride with the alcohol varies depending on the reaction temperature, but is typically preferably 30 minutes or higher and 20 hours or lower, more preferably 1 hour or higher and 8 hours or lower, and particularly preferably 2 hours or higher and 6 hours or lower.

[0155] A small amount of a polymerization inhibitor may be used to prevent crosslinking between ethylenically unsaturated double bonds during the reaction between the tetracarboxylic dianhydride and the alcohol. Examples of the polymerization inhibitor include phenols such as hydroquinone, 4-methoxyphenol, tert-butylpyrocatechol, and bis-tert-butylhydroxytoluene, as well as phenothiazine. The amount of the polymerization inhibitor used is preferably, for example, 0.01 mol % or more and 5 mol % or less based on the number of moles of the ethylenically unsaturated double bond.

[0156] The reaction of the tetracarboxylic dianhydride with the alcohol may be carried out in the presence of an organic base such as pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, 1,4-azabicyclo[2.2.2]octane, etc. These bases may be used alone or in combination of two or more.

[0157] The amount of the alcohol used is preferably 1.8 moles or more and 2.2 moles or less, and more preferably 2 moles or more and 2.1 moles or less, per mole of the tetracarboxylic dianhydride.

[0158] In the production of dicarboxylic acids, depending on the production conditions, only one of the dicarboxylic anhydride groups may react with an alcohol to produce 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 produce 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-mentioned monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds can be used in the production of the polyimide resin precursor (A). When the dicarboxylic acid contains at least one selected from the monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds as an impurity, the content of the at least one selected from the monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds as an impurity in the dicarboxylic acid is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 1% by mass or less, relative to the mass of the dicarboxylic acid including the mass of the impurities.

[0159] [Method for producing polyimide resin precursor (A)] The method for producing the polyimide resin precursor (A) is not particularly limited as long as it is a method that can polycondense the above-mentioned diamine compound and dicarboxylic acid until the weight average molecular weight of the polyimide resin precursor (A) increases to a desired level. A preferred method is to condense the diamine compound with a 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 condensation aid are not particularly limited as long as they are compounds that have been conventionally used for condensation of dicarboxylic acids and diamine compounds.

[0160] 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.

[0161] The amount of the condensing agent used is not particularly limited as long as a polyimide resin precursor (A) having a desired molecular weight can be obtained. The amount of the condensing agent used is typically preferably 1 mole or more and 5 moles or less, more preferably 2 moles or more and 4 moles or less, and even more preferably 2 moles or more and 3 moles or less, per mole of dicarboxylic acid. Furthermore, the ratio between the amount of dicarboxylic acid and the amount of diamine compound when producing the polyimide resin precursor (A) is not particularly limited as long as the polyimide resin precursor (A) having the desired molecular weight can be produced. When the polyimide resin precursor (A) has a terminal amino group, the raw material ratio expressed as (the number of moles of carboxy groups in the dicarboxylic acid) / (the number of moles of amino groups in the diamine compound) is preferably adjusted within the range of 0.5 / 1 to 0.95 / 1, more preferably 0.55 / 1 to 0.80 / 1. The smaller the value of (the number of moles of carboxy groups 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 (A) to elongate, making it easier to obtain a polyimide resin precursor (A) with a low molecular weight. When the polyimide resin precursor (A) has a terminal carboxy group, the raw material ratio expressed as (the number of moles of amino groups in the diamine compound) / (the number of moles of carboxy groups in the dicarboxylic acid) is preferably adjusted within the range of 0.5 / 1 to 0.95 / 1, more preferably 0.55 / 1 to 0.80 / 1. The smaller the value of (the number of moles of 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 (A) to elongate, making it easier to obtain a polyimide resin precursor (A) with a low molecular weight.

[0162] Specifically, a dicarboxylic acid and a diamine compound are reacted in the presence of the condensing agent in an organic solvent, for example, at a temperature of from -20°C to 150°C, preferably from 0°C to 50°C, for 30 minutes to 24 hours, preferably from 1 hour to 4 hours.

[0163] As the solvent used in carrying out the polycondensation, the above-mentioned solvents which can be used in the reaction between the tetracarboxylic dianhydride and the alcohol can be used. The amount of the solvent used is preferably 50 parts by mass or more and 10,000 parts by mass or less, more preferably 100 parts by mass or more and 2,000 parts by mass or less, and even more preferably 150 parts by mass or more and 1,000 parts by mass or less, relative to 100 parts by mass of the total of the mass of the dicarboxylic acid and the mass of the diamine compound.

[0164] When producing the polyimide resin precursor (A), 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 per 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.

[0165] In order to easily obtain a polyimide resin precursor (A) that provides a polyimide resin that exhibits excellent dielectric properties in the high frequency band, the polyimide resin precursor (A) preferably contains a divalent aliphatic hydrocarbon group having from 2 to 50 carbon atoms, more preferably from 3 to 40 carbon atoms. The position of such a divalent aliphatic hydrocarbon group in the molecular chain of the polyimide resin precursor (A) is not particularly limited. Examples of the monomer that provides a divalent aliphatic hydrocarbon group having 2 to 50 carbon atoms in the molecular chain include the above-mentioned α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride.

[0166] From the viewpoint of facilitating the production of a polyimide resin precursor (A) that provides a polyimide resin exhibiting excellent dielectric properties in the high frequency band, the photosensitive resin 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 formula (a1) and the diamine compound represented by formula (a2) are as described above. [ka] (In formulas (a1) and (a2), n is an integer of 1 or more.)

[0167] The weight-average molecular weight of the polyimide resin precursor (A) may be appropriately determined depending on the intended use. The weight-average molecular weight of the polyimide resin precursor (A) can be measured as a weight-average molecular weight converted into polystyrene by GPC (gel permeation chromatography). For example, from the viewpoint of obtaining a resin film with good mechanical properties, the weight-average molecular weight of the polyimide resin precursor (A) is, in terms of the polystyrene equivalent, 5,000 or more, preferably 15,000 or more, and more preferably 250,000,000 or more. On the other hand, from the viewpoint of solubility in organic solvents, the weight-average molecular weight of the resulting polyimide resin precursor (A) is, in terms of the polystyrene equivalent, 100,000 or less, preferably 80,000 or less, and more preferably 50,000 or less. The weight average molecular weight can be adjusted to the above value by adjusting the amounts of the dicarboxylic acid and diamine compound mixed together, and reaction conditions such as the solvent and reaction temperature.

[0168] The main chain terminals of the polyimide resin precursor (A) may be capped with a terminal capping agent for the purposes of improving the storage stability of the photosensitive resin composition containing the polyimide resin precursor (A), further improving the mechanical properties of the polyimide resin film, improving the reproducibility of polymerization when producing the polyimide resin precursor (A), etc. Examples of the terminal capping agent include monoamines, acid anhydrides, monocarboxylic acids, monoacid halides, and monoactive ester compounds. Known compounds can be used as the monoamine used for end-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 3 to 20 carbon atoms and which may have a branched structure, 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 end-capping agents, acid anhydrides are preferred. Known acid anhydrides and their derivatives can be used as the acid anhydride. Examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, xo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and derivatives thereof. The introduction rate of the terminal blocking agent in the polyimide resin precursor (A) is preferably 40 mol % or less, more preferably 20 mol % or less, and even more preferably 10 mol % or less, based on the number of moles of all monomers, from the viewpoint of excellent mechanical properties of the polyimide resin film to be formed.

[0169] The polyimide resin precursor (A) produced as described above is used for producing a photosensitive resin composition in the form of a solution or suspension, or after being separated and recovered from the reaction solution by a known method.

[0170] <Monomer compound (B)> The negative photosensitive resin composition may contain a monomer compound (B). The monomer compound (B) may contain a monomer compound having an ethylenically unsaturated double bond as a radical polymerizable group. Such a monomer compound (B) may be a monofunctional monomer compound or a polyfunctional monomer compound, and a polyfunctional monomer compound is preferred.

[0171] Examples of the monofunctional monomer compound include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, Examples of the photopolymerizable monomer include 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylamino (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylates of phthalic acid derivatives. These monofunctional photopolymerizable monomers can be used alone or in combination of two or more.

[0172] Examples of polyfunctional monomer compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-Decanediol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(3-(meth)acryloyloxypropyl)ether, glycerin di(meth)acrylate, tri(meth)acrylate of glycerin ethylene oxide (EO) adduct, tri(meth)acrylate of glycerin propylene oxide (PO) adduct, glycerin Tri(meth)acrylate of serine EO / PO co-adduct, Tri(meth)acrylate of trimethylolpropane ethylene EO adduct, Tri(meth)acrylate of trimethylolpropane PO adduct, Tri(meth)acrylate of trimethylolpropane EO / PO co-adduct, Tri(meth)acrylate of trimethylolethane EO adduct, Tri(meth)acrylate of trimethylolethane PO adduct, Tri(meth)acrylate of trimethylolethane EO / PO co-adduct, Pentaerythritol di(meth)acrylate, Pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentaerythritol undeca(meth)acrylate, pentaerythritol dodeca(meth)acrylate, dimethicone Tyrol-tricyclodecane di(meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 1,3,5-adamantanetriol di(meth)acrylate, 1,3,5-adamantanetriol tri(meth)acrylate, 1,4-cyclohexanedimethanol di(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, 9,9-Bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-(meth)acryloyloxypropoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)-3,5-dimethylphenyl]fluorene, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycerin Examples of suitable polyfunctional monomer compounds include ricidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), a reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and 2-hydroxyethyl (meth)acrylate, tri((meth)acryloyloxyethyl) isocyanurate, methylene bis(meth)acrylamide, (meth)acrylamido methylene ether, and a condensation product of a polyhydric alcohol and N-methylol (meth)acrylamide, as well as triacryl formal. These polyfunctional monomer compounds can be used alone or in combination of two or more.

[0173] Also, urethane (meth)acrylates described in JP-B-48-41708, JP-B-50-6034, and JP-A-51-37193; polyester (meth)acrylates described in JP-A-48-64183, JP-B-49-43191, and JP-A-52-30490; epoxy (meth)acrylates which are reaction products of epoxy resins and (meth)acrylic acid; compounds described in paragraphs

[0254] to

[0257] of JP-A-2008-292970; polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds having an epoxy group and an ethylenically unsaturated group, such as glycidyl (meth)acrylate, Preferred examples of the compounds that can be used include: fluorene rings and compounds having two or more groups with ethylenically unsaturated bonds, such as those described in JP-A-2010-160418, JP-A-2010-129825, and Japanese Patent No. 4364216; cardo resins; unsaturated compounds described in JP-B-43946, JP-B-1-40337, and JP-B-1-40336; vinylphosphonic acid compounds described in JP-A-2-25493; compounds containing a perfluoroalkyl group, such as those described in JP-A-61-22048; and photopolymerizable monomers and oligomers described in the Journal of the Japan Adhesion Association, Vol. 20, No. 7, pp. 300-308 (1984).

[0174] Among these monomer compounds (B) having an ethylenically unsaturated double bond, polyfunctional monomer compounds having three or more functionalities are preferred, polyfunctional monomer compounds having four or more functionalities are more preferred, and polyfunctional monomer compounds having five or more functionalities are even more preferred, as they tend to improve the adhesion of the polyimide resin film to the substrate and the strength of the polyimide resin film.

[0175] The content of the monomer compound (B) in the photosensitive resin composition is not particularly limited as long as it does not impair the object of the present invention. The content of the monomer compound (B) in the photosensitive resin composition is preferably 0.1 parts by mass or more and 50 parts by mass or less, more preferably 0.5 parts by mass or more and 40 parts by mass or less, and particularly preferably 1 part by mass or more and 25 parts by mass or less, relative to 100 parts by mass of the photosensitive resin composition excluding the mass of the solvent (S) described below.

[0176] <Photoradical polymerization initiator (C)> The negative-type photosensitive resin composition contains a photoradical polymerization initiator (C). The molecular chains of the polyimide resin precursor (A) can be crosslinked (polymerized) by exposure to light in the presence of the photoradical polymerization initiator (C). The photoradical polymerization initiator (C) is not particularly limited, and any conventionally known photopolymerization initiator can be used.

[0177] Specific examples of the photoradical polymerization initiator (C) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl -propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) ketone, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-2-(benzoyloximiimino)-1-propanone, 1-phenyl-1,2-butadione-2-(o -methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, ethanone, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime (Irgacure OXE02, BASF Japan), (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime), 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (Irgacure OXE01, BASF Japan), NCI-831 (ADEKA), NCI-930 (ADEKA), OXE-03 (BASF Japan), OXE-04 (BASF Japan), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethyla Aminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, ethyl 4-diethylbenzoate, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, methyl benzoylformate, ethyl benzoylformate, 2,4-diethyl Thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone anthrone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-Dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, 4-hydroxybenzophenone, 4-phenylbenzophenone, fluorenone, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, 2-hydroxy-2-methylpropiophenone, dichloroacetophenone acetophenone, trichloroacetophenone, p-tert-butylacetophenone, 2-phenylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3-(3,4-diphenyl)- ...-hydroxy-3-(3,4-diphenyl)-2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2-hydroxy-3-(3,4-diphenyl)-2-methylthioxanthone, 2-hydroxy-3-(3,4-diphenyl)-2-methylthioxanthone, 2-hydroxy-3-(3,4-diphenyl)-2-methylthioxanthone, 2-hydroxy-3-(3,4-diphenyl)-2-methylthioxanthone, 2-hydroxy-3-(3,4-diphenyl)-2-methylthioxanthone, 2-hydroxy-3-(3,4-diphenyl)-2-methylthioxanthone, 2-hydroxy-3-(3,4-diphenyl)-2-methylthio Methyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 4-azidobenzalacetophenone, 2,6-bis(p-azidobenzylidene)cyclohexane, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxamine Citriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-Bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 4-benzoyl-4'- Examples of suitable photo-radical polymerization initiators (C) include methyl diphenyl ketone, dibenzyl ketone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propenaminium chloride monohydrate, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, and tribromophenyl sulfone. These photo-radical polymerization initiators (C) can be used alone or in combination of two or more. In view of good sensitivity, the photoradical polymerization initiator (C) is preferably an oxime ester photopolymerization initiator.

[0178] Among the photoradical polymerization initiators (C), oxime ester compounds are preferred in terms of the sensitivity of the photosensitive resin composition. The oxime ester compound is preferably a compound having a partial structure represented by the following formula (c1).

[0179] [ka] (In formula (c1), n1 is 0 or 1, R c2 is a monovalent organic group, R c3 represents a hydrogen atom, an aliphatic hydrocarbon group having from 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, * is a bond.)

[0180] The content of the photoradical polymerization initiator (C) in the photosensitive resin composition is not particularly limited as long as the photosensitive resin composition has the desired photolithography properties. The content of the photoradical polymerization initiator (C) in the photosensitive resin composition is typically preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total of the polyimide resin precursor (A) and the monomer compound (B).

[0181] <Solvent (S)> The negative photosensitive resin composition usually contains a solvent (S) for the purpose of adjusting the coating property, etc. The type of solvent (S) is not particularly limited as long as it dissolves the polyimide resin precursor (A) and other components well. An organic solvent is usually used as the solvent (S).

[0182] Specific examples of the solvent (S) that have good solubility for the polyimide resin precursor (A) include 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-dimethylisobutyric acid amide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N- Nitrogen-containing polar solvents such as dimethylpropionamide, N,N-dimethylisobutyramide, 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, Ethoxyethyl acetate, Methyl 3-methoxypropionate methyl 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 Examples of suitable solvents include esters such as ethanol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate; alcohols such as diacetone alcohol and 3-methyl-3-methoxybutanol; glycol ethers such as 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, and diethylene glycol dimethyl ether; aromatic ethers such as anisole; cyclic ethers such as dioxane and tetrahydrofuran; cyclic esters such as ethylene carbonate and propylene carbonate; aromatic solvents such as anisole, toluene, and xylene; aliphatic hydrocarbons such as limonene; and sulfoxides such as dimethyl sulfoxide.

[0183] The amount of solvent (S) used is not particularly limited as long as a uniform liquid photosensitive resin composition can be prepared. The photosensitive resin composition may be in the form of a suspension or a solution, and is preferably a solution. Typically, the solvent (S) is used so that the solids concentration of the photosensitive resin 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.

[0184] <Other ingredients> The photosensitive resin composition may contain various additives other than the components described above, as needed. Examples of additives include colorants, dispersants, sensitizers, adhesion promoters, polymerization inhibitors, antioxidants, UV absorbers, anti-aggregation agents, antifoaming agents, surfactants, imidization promoters, nitrogen-containing heterocyclic compounds as adhesion improvers, and silane coupling agents. The photosensitive resin composition may also contain various fillers or reinforcing materials, as needed.

[0185] Known compounds can be used as the sensitizer, such as bis(dimethylamino)benzophenone, bis(diethylamino)benzophenone, diethylthioxanthone, N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-4-methylcoumarin, N-phenylmorpholine, and derivatives thereof.

[0186] Known compounds can be used as the polymerization inhibitor. Examples of the polymerization inhibitor include compounds having a phenolic hydroxyl group, nitroso compounds, N-oxide compounds, quinone compounds, N-oxyl compounds, and phenothiazine compounds. More specifically, the polymerization inhibitor is preferably Irganox1010, Irganox1035, Irganox1098, Irganox1135, Irganox245, Irganox259, Irganox3114 (all manufactured by BASF Japan Ltd.), 2,6-di-tert-butyl-p-cresol, or 4-methoxyphenol, and more preferably Irganox1010, 2,6-di-tert-butyl-p-cresol, or 4-methoxyphenol.

[0187] From the viewpoint of achieving both excellent developability of the photosensitive resin composition and a good antioxidant effect, the amount of the polymerization inhibitor used is preferably 0.005% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.5% by mass or less, and even more preferably 0.03% by mass or more and 0.3% by mass or less, relative to the mass of the polyimide resin precursor (A).

[0188] Nitrogen-containing heterocyclic compounds coordinate to metal surfaces to stabilize them, thereby improving the adhesion of resin films formed using the photosensitive resin composition to metal surfaces. Known compounds can be used as nitrogen-containing heterocyclic compounds. Examples of nitrogen-containing heterocyclic compounds include imidazole, pyrazole, indazole, carbazole, triazole, pyrazoline, pyrazolidine, tetrazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid, and derivatives thereof. Specific examples of nitrogen-containing heterocyclic compounds that are preferred in terms 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, as well as triazoles such as 1H-tetrazole, 5-methyl-1H-tetrazole, and 5-phenyl-1H-tetrazole.

[0189] From the viewpoint of achieving both excellent developability of the photosensitive resin composition and improved adhesion of the polyimide resin film formed using the photosensitive resin 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, and more preferably 0.05% by mass or more and 3% by mass or less, based on the mass of the polyimide resin precursor (A).

[0190] By incorporating a silane coupling agent into a photosensitive resin composition, the adhesion of a resin film formed using the photosensitive resin composition to a substrate or the like can be improved. Known compounds can be used as the silane coupling agent. Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(epoxycyclohexyl)ethyltrimethoxysilane, 2-(epoxycyclohexyl)triethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, tris(3-triethoxysilylpropyl)isocyanurate, a reaction product of 3-aminopropyltrimethoxysilane with an acid anhydride, and a reaction product of 3-aminopropyltriethoxysilane with an acid anhydride. Examples of acid anhydrides that can 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.

[0191] 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).

[0192] The incorporation of a surfactant into a photosensitive resin composition improves the coatability of the photosensitive resin composition and also improves the wettability of the photosensitive resin composition with a substrate. Known compounds can be used as the surfactant. Examples of surfactants include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants.

[0193] 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).

[0194] The polyimide resin precursor (A) can be converted into a polyimide resin by heating. For this reason, the photosensitive resin composition may contain a cyclization accelerator. The cyclization accelerator accelerates the formation of a polyimide resin by cyclization of a polyamide resin containing structural units derived from a polyamic acid or a dicarboxylic acid compound that can be synthesized by reacting a tetracarboxylic dianhydride with an alcohol. When the photosensitive resin composition contains a cyclization accelerator, the mechanical properties and weather resistance reliability of the resin film formed by cyclization of the photosensitive resin composition to form a polyimide resin are improved. As the cyclization accelerator, a known thermal base generator or thermal acid generator is used.

[0195] The amounts of the various additives used are not particularly limited as long as they do not impair the object of the present invention. The amount of additives not specified above may be appropriately adjusted within a range of, for example, 0.001% by mass to 60% by mass, and preferably 0.01% by mass to 5% by mass, based on the mass of the solid content of the photosensitive resin composition.

[0196] <Method for preparing photosensitive resin composition> The photosensitive resin composition can be prepared by uniformly mixing the essential components and optional components as described above in desired amounts. The mixing method is not particularly limited. For the purpose of removing foreign matter from the photosensitive resin composition, it is preferable to filter the photosensitive resin composition.

[0197] <Photosensitive dry film> The photosensitive dry film has a substrate film and a photosensitive layer formed on the surface of the substrate film, and the photosensitive layer is made of the above-mentioned negative photosensitive resin composition.

[0198] The substrate film is preferably a light-transmitting film, specifically, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, etc., but a polyethylene terephthalate (PET) film is preferred because of its excellent balance between light transmittance and breaking strength.

[0199] A photosensitive dry film is produced by applying the above-mentioned photosensitive resin composition onto a substrate film to form a photosensitive layer. When forming a photosensitive layer on a substrate film, the photosensitive resin composition is applied to the substrate film using an applicator, bar coater, wire bar coater, roll coater, curtain flow coater, or the like 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.

[0200] The photosensitive dry film may further have a protective film on the photosensitive layer, such as a polyethylene terephthalate (PET) film, a polypropylene (PP) film, or a polyethylene (PE) film.

[0201] <Method for manufacturing resin film> The resin film is formed by a method including a coating step of applying the photosensitive resin composition described above onto a substrate to form a coating film, The resin film contains the polyimide resin precursor (A) described above. The method may include a drying step of drying the coated film.

[0202] The substrate is not particularly limited, and any conventionally known substrate can be used, such as a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed. Examples of wiring include copper wiring. Silicon substrates, glass substrates, and the like can also be used as the substrate.

[0203] The thickness of the coating film is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm to 300 μm, particularly preferably 1 μm to 150 μm, and most preferably 3 μm to 100 μm.

[0204] The photosensitive resin composition can be applied to a substrate by a method such as spin coating, slit coating, roll coating, screen printing, or applicator method.

[0205] The method for drying the photosensitive resin composition coated on the substrate is not particularly limited. Preferably, drying is performed by heating. The heating conditions during drying vary depending on the types and blending ratios of the components in the photosensitive resin composition, the coating film thickness, etc., but are usually 70°C to 200°C, preferably 80°C to 150°C, for approximately 2 minutes to 120 minutes. In this manner, a resin film containing the polyimide resin precursor (A) is formed.

[0206] <Method for forming a patterned resin film> a coating step of coating the photosensitive resin composition on a substrate to form a coating film; an exposure step of exposing the coating film to actinic rays or radiation in a position-selective manner; and a developing step of developing the exposed coating film to obtain a patterned resin film. The patterned resin film contains the polyimide resin precursor (A).

[0207] The substrate and the method for applying the photosensitive resin composition are the same as those described above for the method for producing a resin film. The photosensitive resin composition coated on the substrate is usually dried to form a coating film. The method for drying the photosensitive resin composition coated on the substrate is not particularly limited. Preferably, drying is performed by heating. The heating conditions during drying vary depending on the types and blending ratios of the components in the photosensitive resin composition, the coating film thickness, etc., but are usually 70°C or higher and 200°C or lower, preferably 80°C or higher and 150°C or lower, and are for approximately 2 minutes or higher and 120 minutes or lower.

[0208] The coating film formed as described above is exposed to actinic rays or radiation in a position-selective manner. The position-selective exposure is usually carried out by irradiating the coating film with actinic rays or radiation, for example, ultraviolet rays or visible light having a wavelength of 300 nm or more and 500 nm or less, through a mask having a predetermined pattern.

[0209] Examples of radiation sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon gas lasers. Examples of radiation include microwaves, infrared rays, visible light, ultraviolet rays, X-rays, gamma rays, electron beams, proton beams, neutron beams, and ion beams. The radiation dose varies depending on the composition of the photosensitive resin forming the resin film and the film thickness of the photosensitive layer. For example, when an ultra-high-pressure mercury lamp is used, the radiation dose is 100 J / cm. 2 More than 10000J / cm 2 The following is the result.

[0210] The exposed coating film is then developed by a conventional method, and unnecessary portions are dissolved and removed to form a resin film patterned into a predetermined shape. A developer appropriate for the components contained in the photosensitive resin composition is used. When the 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. The solvent (S) described above can also be used as the developer.

[0211] Examples of alkaline developers that can be used include 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, and 1,5-diazabicyclo[4,3,0]-5-nonane. Alternatively, an aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above-mentioned aqueous solution of alkalis can also be used as a developer.

[0212] The development time varies depending on the composition of the photosensitive resin composition, the 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 puddle method, a spray development method, etc.

[0213] After development, washing is performed for 30 to 90 seconds as needed, and the patterned resin film is dried using an air gun, oven, or the like. In this way, a resin film patterned into the desired shape is formed on the surface of the substrate. The washing solvent is not particularly limited. For example, water, alcohols, etc. can be used as the washing solvent when alkaline development is performed. When development is performed with a solvent (S), the solvent (S) can be used as long as it does not cause solvent shock.

[0214] The polyimide resin precursor contained in the resin film can be imidized by heating. Therefore, after development, if necessary, the developed coating film can be baked to imidize the polyimide resin precursor in the resin film. That is, by heating the above-mentioned patterned resin film, a polyimide resin derived from the polyimide resin precursor can be produced, and a patterned polyimide resin film can be formed.

[0215] The heating conditions for imidization are not particularly limited as long as the polyimide resin precursor is not decomposed and the imidization proceeds satisfactorily. The heating temperature is preferably 80° C. or higher and 220° C. or lower, more preferably 100° C. or higher and 200° C. or lower, and particularly preferably 120° C. or higher and 180° C. or lower. When a solid polyimide resin precursor is heated, the heating temperature is typically preferably 180° C. or higher and 400° C. or lower, and more preferably 200° C. or higher and 350° C. or lower. The heating time varies depending on the heating temperature, but is typically preferably from 1 hour to 24 hours, more preferably from 2 hours to 12 hours. The heating is preferably carried out in an inert gas atmosphere such as nitrogen or argon, from the viewpoint of preventing oxidation of the resin film and obtaining a resin film with good mechanical properties.

[0216] The patterned polyimide resin film formed as described above is suitably used, for example, as an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, or an insulating film or protective film in a touch panel display, an organic electroluminescent display panel, etc. Since the above-described photosensitive resin composition has good resolution, the patterned resin film formed as described above can be particularly suitably used as an interlayer insulating film for a rewiring layer in a three-dimensional packaging device. Furthermore, the patterned resin film formed as described above can also be suitably used as a photoresist, galvanic (electrolytic) resist, etching resist, solder top resist, etc. for electronics. Furthermore, the patterned resin film formed as described above can also be used for producing printing plates such as offset printing plates or screen printing plates, for forming etching masks when etching molded parts, and for producing protective lacquers and dielectric layers for electronic parts, particularly microelectronic parts. [Example]

[0217] The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited to these examples.

[0218] [Examples 1 to 15 and Comparative Examples 1 to 7] In the examples and comparative examples, the following diamine compounds A1 to A5, B1 to B3, and C1 were used. [ka] [ka] [ka]

[0219] In the examples and comparative examples, the following P1 to P3 were used as the tetracarboxylic dianhydrides. [ka]

[0220] In the examples and comparative examples, the following H1 to H2 were used as alcohols to be reacted with tetracarboxylic dianhydrides. [ka]

[0221] In the examples and comparative examples, the following R1 was used as the photoradical polymerization initiator (C). [ka]

[0222] (Production of dicarboxylic acids) 0.0322 mol of a tetracarboxylic dianhydride of the type listed in Table 1 was dissolved in 23.33 g of N-methyl-2-pyrrolidone (NMP). To the resulting solution, 0.068 mol of an alcohol of the type listed in Table 1 and 0.068 mol of pyridine were added. The resulting solution was stirred at room temperature for 16 hours to obtain a dicarboxylic acid, which is a reaction product of the tetracarboxylic dianhydride and the alcohol.

[0223] (Production of polyimide resin precursor) The obtained solution containing dicarboxylic acid was cooled to 0° C. A condensing agent solution in which 0.068 mol of dicyclohexylcarbodiimide (DCC) was dissolved in 9.74 g of NMP, and a solution in which 0.0322 mol of a diamine compound of the type and ratio (ratio (mol %) relative to the total amount of diamine compounds) shown in Table 1 was dissolved in 17.53 g of NMP were added dropwise to the cooled solution.

[0224] After the dropwise addition was completed, the resulting reaction liquid was warmed to room temperature and stirred at room temperature for 4 hours to condense the dicarboxylic acid and the diamine compound.

[0225] After the reaction was completed, the reaction solution was poured into isopropyl alcohol (IPA) to obtain a white precipitate, which was then filtered to obtain a brown powder. The obtained powder was washed three times with IPA and dried under reduced pressure to obtain a polyimide resin precursor used in the preparation of the photosensitive resin composition in each Example and Comparative Example.

[0226] (Production of Photosensitive Resin Composition) The obtained polyimide resin precursor was dissolved in N,N,N',N'-tetramethylurea to a concentration of 30 mass %. 5 mass % of the photoradical polymerization initiator R1 relative to the mass of the polyimide resin precursor and 0.05 mass % of the polymerization inhibitor (Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)) relative to the mass of the polyimide resin precursor were uniformly dissolved in the obtained solution to obtain photosensitive resin compositions for each Example and Comparative Example.

[0227] The resolution of the resulting photosensitive resin composition was evaluated according to the following method, and the evaluation results are shown in Table 1.

[0228] <Resolution evaluation> The resolution of the photosensitive resin composition was confirmed by the following method. The photosensitive resin composition was applied using a spin coater onto a silicon wafer on which a copper sputtered film had been formed. The film made of the photosensitive resin composition was then baked at 100°C for 300 seconds to obtain a coating film with a thickness of 10 μm. The coating film was subjected to i-line exposure using a GHI-line exposure machine (manufactured by Ultratec) through a negative mask capable of forming via holes. The exposure was performed using a negative mask capable of forming via holes with opening diameters of 2 μm, 3 μm, 4 μm, and 5 μm. Exposure: 250J / m 2 ~10,000 J / m 2 Within this range, the exposure dose is 250 J / m 2 The exposure was increased stepwise from 1000 to 10000, and the exposure was repeated multiple times at multiple exposure doses. That is, exposure was performed on the unexposed coating film a number of times calculated by (number of exposure dose conditions) x (number of types of mask opening diameters (4)). The coating film exposed under each exposure condition was puddle developed with cyclopentanone for 45 seconds, and then heated at 230°C for 4 hours. The resulting patterned resin film was observed, and the resolution was evaluated according to the following criteria based on the minimum diameter of the via hole that could be resolved according to the mask size. A: Via holes with opening diameters of all sizes from 2 μm to 5 μm could be formed. B: Via holes with an opening diameter of 3 μm to 5 μm could be formed, but via holes with an opening diameter of 2 μm could not be formed. C: Via holes with an opening diameter of 4 μm to 5 μm could be formed, but via holes with an opening diameter of 2 μm to 3 μm could not be formed. D: A via hole with an opening diameter of 5 μm could be formed, but a via hole with an opening diameter of 2 μm to 4 μm could not be formed.

[0229] [Table 1]

[0230] According to the examples, it is clear that a photosensitive resin composition containing a polyimide resin precursor (A) containing a structural unit represented by the above formula (A1) and a photoradical polymerization initiator (B) has excellent resolution. On the other hand, it is clear that the photosensitive resin composition not containing the polyimide resin precursor (A) containing the structural unit represented by formula (A1) has poor resolution.

Claims

1. A negative photosensitive resin composition comprising: a polyimide resin precursor (A) containing a structural unit represented by the following formula (A1); and a photoradical polymerization initiator (C). 【Chemical 1】 (In formula (A1), X Ａ１ is a tetravalent organic group having from 4 to 40 carbon atoms, Y Ａ１ is an organic group having 6 to 40 carbon atoms and having a structure in which two alicyclic groups are connected via an alkylene group, an oxygen atom, or a sulfur atom, R Ａ１ , and R Ａ２ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, R Ａ１ , and R Ａ２ The organic group as R Ａ１ and R Ａ２ At least one of the groups is an unsaturated group having 3 to 30 carbon atoms and one or more ethylenically unsaturated double bonds.

2. The Y Ａ１ Is, -A ０１ -R ０１ -A ０２ is an organic group represented by -, A ０１ and A ０２ are each independently an alicyclic group, and R ０１ The negative photosensitive resin composition according to claim 1 , wherein is an alkylene group, an oxygen atom, or a sulfur atom.

3. The R ０１ The negative photosensitive resin composition according to claim 2 , wherein is a methylene group.

4. The above A ０１ and A ０２ The negative photosensitive resin composition according to claim 2 , wherein each of the groups independently represents a cycloalkylene group.

5. 2. The negative photosensitive resin composition according to claim 1, wherein the polyimide resin precursor (A) contains 5 mol % to 50 mol % of the structural unit represented by formula (A1).

6. The X Ａ１ 2. The negative photosensitive resin composition according to claim 1, wherein the tetravalent organic group as is a residue obtained by removing two dicarboxylic acid anhydride groups from an aromatic tetracarboxylic acid dianhydride.

7. 2. The negative photosensitive resin composition according to claim 1, wherein the polyimide resin precursor (A) contains a structural unit represented by the following formula (A2): 【Chemistry 2】 (In formula (A2), X Ａ１ , R Ａ１ , and R Ａ２ represents X in formula (A1). Ａ１ , R Ａ１ , and R Ａ２ is the same as Y Ａ１１ is an organic group containing an aromatic ring and having 6 to 40 carbon atoms.

8. A method for producing a resin film, comprising applying the negative photosensitive resin composition according to any one of claims 1 to 7 onto a substrate to form a coating film.

9. applying the negative photosensitive resin composition according to any one of claims 1 to 7 onto a substrate to form a coating film; exposing the coating film to position-selective light; developing the exposed coating film; A method for producing a patterned resin film, comprising:

10. A method for producing a patterned polyimide resin film, comprising heating the patterned resin film produced by the production method according to claim 9 to produce a polyimide resin derived from the polyimide resin precursor.

11. A polyimide resin precursor comprising a structural unit represented by the following formula (A1): 【Chemistry 3】 (In formula (A1), X Ａ１ is a tetravalent organic group having from 4 to 40 carbon atoms, Y Ａ１ is an organic group having 6 to 40 carbon atoms and having a structure in which two alicyclic groups are connected via an alkylene group, an oxygen atom, or a sulfur atom, R Ａ１ , and R Ａ２ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, R Ａ１ , and R Ａ２ The organic group as R Ａ１ and R Ａ２ At least one of the groups is an unsaturated group having 3 to 30 carbon atoms and one or more ethylenically unsaturated double bonds.

Images