Photosensitive resin composition and method for producing patterned polyimide resin film

Abstract

The invention relates to a photosensitive resin composition and a method for producing a patterned polyimide resin film. The present invention addresses the problem of providing: a photosensitive resin composition capable of forming a polyimide resin film having excellent lithography characteristics and storage stability and excellent mechanical characteristics and chemical resistance; and a method for producing a patterned polyimide resin film using the photosensitive resin composition. [Solution] A photosensitive resin composition containing: a reactant (A) of a polyimide resin precursor (A1) having a structural unit of a specific structure and an isocyanate compound (A2) having a (meth) acryloyl group; a thermal base generator (B) that generates an imidazole by heating; and a photoradical polymerization initiator (C).

Description

TECHNICAL FIELD

[0001] The present application relates to a photosensitive resin composition, and a method for manufacturing a patterned polyimide resin film using the same. BACKGROUND

[0002] Polyimide resins and polyamide resins have excellent heat resistance, mechanical strength, and insulating properties, low dielectric constant, and the like, and thus have been widely used as insulating materials, protective materials in various electronic components, multilayer wiring substrates, and the like.

[0003] In recent years, high frequency is being promoted in communication devices such as mobile phones. Therefore, it is also required that the insulating portion in which the metal wiring of the communication device is insulated should cope with high frequency.

[0004] Here, the higher the frequency, the greater the increase in transmission loss, and if the transmission loss increases, the electrical signal attenuates. Therefore, for resins such as polyimide resins and polyamide resins, as a countermeasure against high frequency, in order to further reduce the transmission loss, further low dielectric loss tangentization and further low dielectric constant are required in the high frequency band.

[0005] In addition, when various components, electronic substrates, and the like are manufactured, in most cases, it is necessary to form an insulating material or a protective material only at a desired position. Therefore, it is required that a composition for forming an insulating material or a protective material can be applied to photolithography.

[0006] According to the above requirements, as a photosensitive resin composition capable of forming a patterned resin film with low dielectric loss tangent by applying photolithography, a photosensitive resin composition containing a resin and a photosensitive agent, and using at least one selected from the group consisting of a polyimide resin, a polyamide acid, a polyamide resin, a polybenzoxazole resin, and a polybenzoxazole resin precursor containing a structural unit derived from a specific structure having an aromatic group, has been proposed (Patent Document 1).

[0007] PRIOR ART DOCUMENTS

[0008] PATENT DOCUMENTS

[0009] Patent Document 1: Japanese Patent Application Publication No. 2022-190618 SUMMARY

[0010] PROBLEMS TO BE SOLVED BY THE INVENTION

[0011] When using the photosensitive resin composition described in Patent Document 1, a patterned resin film with a low dielectric loss tangent can be formed by photolithography. On the other hand, regarding the photosensitive resin composition described in Patent Document 1, further improvements are required in the photolithographic properties and storage stability, as well as the mechanical properties (mechanical strength) and chemical resistance of the formed patterned polyimide resin film.

[0012] The present invention was made in view of the above-mentioned problems, and its object is to provide a photosensitive resin composition with excellent photolithographic properties and storage stability and capable of forming a polyimide resin film with excellent mechanical properties and chemical resistance, and a method for manufacturing a patterned polyimide resin film using the photosensitive resin composition.

[0013] Methods for solving problems

[0014] The inventors of this application have discovered that the above-mentioned problems can be solved using the following photosensitive resin composition, which comprises: a reactant (A) of a polyimide resin precursor (A1) having a structural unit represented by the following formula (a1) and an isocyanate compound (A2) having a (meth)acryloyl group; a thermal alkali-generating agent (B) that generates imidazole by heating; and a photoradical polymerization initiator (C), thereby completing the present invention. More specifically, the present invention provides the following invention.

[0015] The first aspect of the present invention is a photosensitive resin composition comprising: a reactant (A) of a polyimide resin precursor (A1) having a structural unit represented by the following formula (a1) and an isocyanate compound (A2) having a (meth)acryloyl group; a thermal alkali-generating agent (B) that generates imidazole by heating; and a photoradical polymerization initiator (C).

[0016] [Chemical Formula 1]

[0017]

[0018] (In formula (a1), X) A1 Y is a tetravalent organic group with 4 to 40 carbon atoms. A1 Organic groups consisting of 4 to 40 carbon atoms.

[0019] R A1 and R A2 Each is an independent organic group consisting of a hydrogen atom or a carbon atom number between 1 and 30, R A1 and R A2 At least one of them is a hydrogen atom, as R A1 and R A2 The aforementioned organic groups are bonded to the oxygen atoms in the ester bond via CO bonds.

[0020] The second aspect of the present application is a method for producing a patterned polyimide resin film, which includes the following steps:

[0021] a step of applying the photosensitive resin composition according to the first aspect on a substrate to form an applied film;

[0022] a step of exposing the applied film in a position-selective manner;

[0023] a step of developing the exposed applied film to obtain a patterned resin film; and

[0024] a step of heating the patterned resin film to produce a polyimide resin from the reactant (A).

[0025] Effects of the Invention

[0026] According to the present application, it is possible to provide a photosensitive resin composition having excellent lithography properties and storage stability and capable of forming a polyimide resin film having excellent mechanical properties and chemical resistance, and a method for producing a patterned polyimide resin film using the same. DETAILED DESCRIPTION

[0027] Photosensitive resin composition

[0028] The photosensitive resin composition comprises a reactant (A) of a polyimide resin precursor (A1) having a structural unit represented by the following formula (a1) and an isocyanate compound (A2) having a (meth)acryloyl group; a thermal base generator (B) that generates imidazole by heating; and a photoradical polymerization initiator (C).

[0029] [Chemical Formula 2]

[0030]

[0031] (In formula (a1), X A1 is a 4-valent organic group having 4 to 40 carbon atoms, Y A1 is an organic group having 4 to 40 carbon atoms,

[0032] 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 at least one of which is a hydrogen atom, and the aforementioned organic group as R A1 and R A2 is bonded to the oxygen atom in the ester bond via a C-O bond.

[0033] As shown in the examples described later, the above-described photosensitive resin composition exhibits excellent photolithographic properties and storage stability, and is capable of forming a polyimide resin film with excellent mechanical properties and chemical resistance.

[0034] On the other hand, in the case of photosensitive resin compositions that are not as described above, for example, photosensitive resin compositions that do not contain reactant (A) (e.g., a photosensitive resin composition containing a polyimide resin precursor (A1) having a structural unit represented by formula (a1) that has not reacted with an isocyanate compound (A2) having a (meth)acryloyl group, but not containing reactant (A), or photosensitive resin compositions that do not contain a thermal alkali-generating agent (B) that generates imidazole by heating (e.g., a thermal alkali-generating agent that does not generate imidazole by heating, a photosensitive resin composition that does not contain a thermal alkali-generating agent (B) that generates imidazole by heating, or a photosensitive resin composition that does not contain a thermal alkali-generating agent), have poor photolithographic properties, storage stability, mechanical properties, and chemical resistance.

[0035] Furthermore, in the manufacture of semiconductor devices, when a polyimide resin film is fabricated on a substrate using an existing photosensitive resin composition containing a polyimide precursor, the polyimide precursor is cured by heating. Specifically, heating the polyimide precursor induces a ring-closing reaction (imidization reaction). In this case, there are concerns about substrate warping and damage to the semiconductor device caused by heating at high temperatures.

[0036] However, according to the above-described photosensitive resin composition, the reactant (A) can be cured at a low temperature (e.g., below 200°C), thus suppressing adverse effects caused by heating at high temperatures, such as substrate warping and damage to semiconductor elements.

[0037] The curing temperature can be below 200°C, or above 200°C depending on the type of substrate used.

[0038] It should be noted that, for the reactant (A) described above, its molecular chains crosslink due to exposure in the presence of the photoradical polymerization initiator (C) described later. Then, curing occurs by heating in the presence of the thermal alkali-generating agent (B) described later. It is presumed that prior to this heating, the isocyanate compound (A2) with (meth)acryloyl groups is in a bonded state to the polyimide resin precursor (A1), and through this heating, a portion of the isocyanate compound (A2) breaks away from the polyimide resin precursor (A1) and undergoes a ring-closure reaction.

[0039] The following describes the essential or optional components contained in the photosensitive resin composition.

[0040] <Reactant (A)>

[0041] The photosensitive resin composition comprises a reactant (A) of a polyimide resin precursor (A1) having a structural unit represented by formula (a1) and an isocyanate compound (A2) having a (meth)acryloyl group.

[0042] [Polyimide resin precursor (A1)]

[0043] The polyimide resin precursor (A1) has the structural unit represented by the above formula (a1).

[0044] In the polyimide resin precursor (A1), the structural units may consist only of the structural units represented by formula (a1) above, or they may have structural units other than those represented by formula (a1). In the latter case, a portion of the polyimide resin precursor (A1) may be imidized. That is, when the polyimide resin precursor (A1) has structural units other than those represented by formula (a1), the polyimide resin precursor (A1) may have structural units represented by formula (a1) and structural units with an imide structure (imide structural units).

[0045] When the polyimide resin precursor (A1) has structural units represented by the above formula (a1) and structural units other than those represented by formula (a1), the content of the structural units represented by formula (a1) in the polyimide resin precursor (A1) is not particularly limited, but is preferably 30 mol% or more and 95 mol% or less, and more preferably 50 mol% or more and 95 mol% or less.

[0046] When the polyimide resin precursor (A1) has a structural unit represented by formula (a1) and a structural unit having an imide structure (imide structural unit), the content of the imide structural unit in the polyimide resin precursor (A1) is not particularly limited, but is preferably 5 mol% or more and 70 mol% or less, more preferably 5 mol% or more and 50 mol% or less.

[0047] Typically, the polyimide resin precursor (A1) is a polymer of a diamine compound and a tetracarboxylic dianhydride, a polymer obtained by imidizing a portion of the polymer, or a polymer obtained by esterifying a portion of the carboxyl groups of these polymers. It should be noted that "the polymer obtained by esterifying a portion of the carboxyl groups of these polymers" refers to a polymer having the characteristics represented by the aforementioned formula (a1), and R... A1 and R A2 A portion of the polymer is a structural unit consisting of an organic group having 1 to 30 carbon atoms. Examples of such organic groups include unsaturated groups. Examples of unsaturated groups include chain-like aliphatic hydrocarbon groups having olefinic unsaturated double bonds and groups containing (meth)acryloyl groups.

[0048] The polyimide resin precursor (A1) is preferably a polymer of a diamine compound and a tetracarboxylic dianhydride, or a polymer obtained by imidizing a portion of the polymer.

[0049] The diamine compound and the tetracarboxylic dianhydride are selected in a manner that satisfies the above-mentioned requirements as a polyimide resin precursor (A1).

[0050] (Diamine compounds)

[0051] Diamine compounds are represented by the following formula (a1a).

[0052] H2N-Y A1 -NH2···(a1a)

[0053] (In formula (a1a), Y A1 This refers to a divalent organic group with 4 to 40 carbon atoms.

[0054] Y A1 It is a divalent organic group with 4 to 40 carbon atoms. A1 In addition to the two amino groups, it can also have one or more substituents.

[0055] Preferred examples of substituents include fluorine atoms, alkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, fluoroalkyl groups with 1 to 6 carbon atoms, fluoroalkoxy groups with 1 to 6 carbon atoms, carboxyl groups, or hydroxyl groups.

[0056] When the substituent is a fluoroalkyl or fluoroalkoxy group, perfluoroalkyl or perfluoroalkoxy group is preferred.

[0057] As Y A1 The lower limit for the number of carbon atoms in the organic group is 4, preferably 6, and the upper limit is 40, preferably 30.

[0058] Y A1 It can be an aliphatic group, but is preferably an organic group containing one or more aromatic rings.

[0059] In Y A1 In the case of an organic group containing one or more aromatic rings, the organic group can be a single aromatic group or a group consisting of two or more aromatic groups bonded together by aliphatic hydrocarbon groups and halogenated aliphatic hydrocarbon groups, or by heteroatoms including oxygen, sulfur, and nitrogen atoms. As Y A1The bonds contained therein, which include heteroatoms such as oxygen, sulfur and nitrogen atoms, can be categorized as -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, with -COO-, -O-, -CO-, and -S- being preferred.

[0060] Y bonded to amino groups A1 The aromatic ring in Y is preferably a benzene ring. A1 When the ring bonded to the amino group 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.

[0061] In addition, Y A1 The aromatic rings contained therein can also be aromatic heterocycles.

[0062] In Y A1 In the case of an organic group containing an aromatic ring, from the viewpoint of improving the electrical and mechanical properties of the polyimide resin formed using the polyimide resin precursor (A1), the organic group is preferably at least one of the groups represented by the following formulas (21) to (24).

[0063] [Chemical Formula 3]

[0064]

[0065] In (21)~(24), R 111 It represents one of the following groups: hydrogen atom, fluorine atom, carboxyl group, sulfonic acid group, hydroxyl group, alkyl group with 1 to 4 carbon atoms, and haloalkyl group with 1 to 4 carbon atoms. In formula (24), Q 1 Representing 9,9'-fluoreneyl, or choosing the free form: -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 One of the groups represented by -O-.

[0066] Q 1In the example, -C6H4- is a phenylene, preferably m-phenylene or p-phenylene, more preferably p-phenylene. Additionally, -C 10 H6- is naphthyldiyl, preferably naphthalene-1,2-diyl, naphthalene-1,4-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, and naphthalene-2,7-diyl, more preferably naphthalene-1,4-diyl and naphthalene-2,6-diyl.

[0067] Q 1 In the example, n is an integer greater than or equal to 1, preferably an integer greater than or equal to 1 and less than 20, more preferably an integer greater than or equal to 1 and less than 12, and even more preferably an integer greater than or equal to 1 and less than 6.

[0068] Regarding the group represented by formula (24) as Y A1 The diamine compound is preferably a compound represented by the following formula (a2). Regarding n in formula (a2), as with Q in formula (24) 1 As explained.

[0069] [Chemical Formula 4]

[0070]

[0071] R in equations (21) to (24) 111 From the viewpoint of improving the electrical properties of the formed resin film, hydrogen atoms, fluorine atoms, methyl, ethyl, or trifluoromethyl are more preferred, and hydrogen atoms or trifluoromethyl are particularly preferred.

[0072] Q in equation (24) 1 Considering the electrical and mechanical properties of the formed resin film, the preferred resin types are -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-, and -OC. 10 H6-O-, -O-C6H4-O-, -O-CH2-O-, -O-(CH2)2-O-, -O-(CH2)3-O-, -O-(CH2)4-O-, -O-(CH2)5-O-, and -O-(CH2)6-O-. Considering the improvement in the electrical and mechanical properties of the polyimide resin formed using the polyimide resin precursor, Q in formula (24) is... 1More preferably, it is -O-C6H4-C6H4-O-, -O-C6H4-C(CH3)2-C6H4-O-, or -O-, and particularly preferably it is represented by -O-C6H4-C6H4-O-, where -C6H4- is a group of p-phenylene, or -O-.

[0073] When using aromatic diamine compounds as diamine compounds represented by formula (a1a), for example, the aromatic diamine compounds shown below may be preferred.

[0074] That is, examples of aromatic diamine compounds include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (meta-toluidine), 3,3'-dimethyl-4,4'-diaminobiphenyl (o-toluidine), 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 9,10-diaminoanthracene, 9,10-bis(4-aminophenyl)anthracene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4 '-Diaminobenzophenone, 4,4'-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)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenyl)propane [-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfonyl-4,4'-diaminodiphenyl ether, 4,4'-diaminobenzoyl aniline, 3,3'-diaminobenzoyl aniline, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1, 4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, bis(3-amino-4-hydroxyphenyl)ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 4,4'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(4-aminophenoxy)biphenyl, 3,3'-Bis(4-aminophenoxy)biphenyl, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]one, 2,2-bis[4-{4-amino-2-(trifluoromethyl)phenoxy}phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-amino-3-methyl)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, Benzoxazolyl)benzene, 1,3-bis(6-amino-2-benzoxazolyl)benzene, 2,6-bis(4-aminophenyl)benzobisoxazole, 2,6-bis(3-aminophenyl)benzobisoxazole, bis[(3-aminophenyl)-5-benzoxazolyl], bis[(4-aminophenyl)-5-benzoxazolyl], bis[(3-aminophenyl)-6-benzoxazolyl], bis[(4-aminophenyl)-6-benzoxazolyl], N,N'-bis(3-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-4,4' -Diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'-[1,4-phenylenebis(1-methylethane-1,1-diyl)]diphenylamine, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 4-aminophenyl ester of 4-aminobenzoic acid, 1,3-bis(4-anilino)tetramethyldisiloxane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-toluidine sulfone, etc. Among them, considering the improvement of electrical and mechanical properties, 4,4'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(4-aminophenoxy)biphenyl and 3,3'-bis(4-aminophenoxy)biphenyl.

[0075] In addition, as Y A1 The silicon-containing groups that may have chain-like aliphatic groups and / or aromatic rings can be used. Typically, the groups shown below can be used as such silicon-containing groups.

[0076] [Chemical Formula 5]

[0077]

[0078] Specific examples of compounds having amino groups at both ends and silicon-containing groups include amino-terminated modified methylphenyl silicones (e.g., X-22-1660B-3 (number average molecular weight approximately 4,400) and X-22-9409 (number average molecular weight approximately 1,300) manufactured by Shin-Etsu Chemical Co., Ltd.), amino-terminated modified dimethyl silicones (e.g., X-22-161A (number average molecular weight approximately 1,600), X-22-161B (number average molecular weight approximately 3,000), and KF8012 (number average molecular weight approximately 4,400) manufactured by Shin-Etsu Chemical Co., Ltd.; BY16-835U (number average molecular weight approximately 900) manufactured by Down Corning Toray Co., Ltd.; and Silaplane FM3311 (number average molecular weight approximately 1,000) manufactured by JNC Co., Ltd.), etc.

[0079] Alternatively, as the diamine compound represented by formula (a1a), a diamine having an alkylene oxide may be preferred. Preferred examples of alkylene oxides include ethylene oxide, propylene oxide (-C(CH3)-CH2-O-, -CH2-C(CH3)-O-, or -CH2CH2CH2-O-).

[0080] Diamines having alkylene oxides can also contain two or more alkylene oxides. In the case where a diamine having alkylene oxides contains two or more alkylene oxides, the two or more alkylene oxides can be block-containing or random-containing in the diamine.

[0081] Diamines having alkylene oxides preferably do not contain cyclic groups, and more preferably do not contain aromatic groups.

[0082] Specific examples of diamines having alkylene oxides include Jeffamine KH-511, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2003, Jeffamine EDR-148, Jeffamine EDR-176, Jeffamine D-200, Jeffamine D-400, Jeffamine D-2000 and Jeffamine D-4000 manufactured by HUNTSUMA N, as well as 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine and 1-(1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, etc.

[0083] Considering factors such as the solubility of the polyimide resin precursor (A1) in organic solvents, the diamine compound preferably includes one or more diamine compounds selected from the group consisting of: compounds represented by formula (a1a) and Y A1 Diamine compounds containing the group represented by formula (24); represented by formula (a1a) and Y A1 A diamine compound (A-1) represented by the group indicated by formula (A1-1); represented by formula (a1a) and Y A1 The compounds include: a diamine compound (A-2) having a partial structure represented by formula (A2-1) described later, which is not a diamine compound (A-1); a diamine compound (A-3) having a partial structure represented by formula (A3) described later, which is not a diamine compound (A-1) or a diamine compound (A-2); and a dimer diamine compound (A-4). Among these, the compound represented by formula (a1a) and Y is preferred. A1 The diamine compound containing the group represented by formula (24), the diamine compound (A-1), and the diamine compound (A-2).

[0084] (Diamine compound (A-1))

[0085] The diamine compound (A-1) is represented by formula (a1a) and Y A1 A diamine compound having a group represented by the following formula (A1-1).

[0086] [Chemical Formula 6]

[0087]

[0088] (In formula (A1-1), X is an organic group with 1 to 100 carbon atoms, R) a1R is a hydroxyl, carboxyl, or halogen atom. a2 It consists of an aliphatic group, hydroxyl group, carboxyl group, sulfonic acid group, or halogen atom with 1 to 20 carbon atoms; Ar is a group that can be converted by R. a2 Substituted phenyl, or can be R a2 The substituted naphthyl group, where ma1 is an integer between 0 and 10, ma2 is an integer between 0 and 7, and ma3 is an integer between 1 and 10.

[0089] In equation (A1-1), Ar is a variable that can be generated by R. a2 Substituted phenyl, or can be R a2 Substituted naphthyl group. Ar is preferably phenyl or naphthyl. That is, in formula (A1-1), ma2 is preferably 0.

[0090] In equation (A1-1), R a2 It is an aliphatic group, hydroxyl group, carboxyl group, sulfonic acid group, or halogen atom with 1 to 20 carbon atoms. As R a2 The organic groups can also contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms.

[0091] As R a2 The aliphatic group preferably has 1 to 12 carbon atoms, more preferably 1 to 6.

[0092] Regarding R a2The aliphatic groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, and n-eicosyl, etc., as well as chain alkyl groups; vinyl, 1-propenyl, 2-n-propenyl (allyl), 1-n-butenyl, 2-n-butenyl, and 3-n-butenyl, etc., as well as chain alkenyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl, etc.; chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, etc. Halogenated chain alkyl groups such as difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, and perfluorodecyl; halogenated cycloalkyl groups such as 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2,4-dichlorocyclohexyl, 2-bromocyclohexyl, 3-bromocyclohexyl, and 4-bromocyclohexyl; hydroxyl chain alkyl groups such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxyn-propyl, and 4-hydroxyn-butyl; hydroxycycloalkyl groups such as 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, and 4-hydroxycyclohexyl; methoxy, ethoxy, n-propoxy, isopropoxy, n-butyloxy, isobutyloxy, sec-butyloxy, etc. Chain alkoxy groups including tert-butyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecanyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecanyloxy, and n-eicosyloxy; chain alkenyloxy groups including vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, 2-n-butenyloxy, and 3-n-butenyloxy; methoxymethyl, ethoxymethyl, n-propoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, and 2-n-propoxy. Alkoxyalkyl groups such as ethyl, 3-methoxy-n-propyl, 3-ethoxy-n-propyl, 3-n-propoxy-n-propyl, 4-methoxy-n-butyl, 4-ethoxy-n-butyl, and 4-n-propoxy-n-butyl; alkoxyalkyl groups such as methoxymethoxy, ethoxymethoxy, n-propoxymethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-n-propoxyethoxy, 3-methoxy-n-propoxy, 3-ethoxy-n-propoxy, 3-n-propoxy-n-propoxy, 4-methoxy-n-butyloxy, 4-ethoxy-n-butyloxy, and 4-n-propoxy-n-butyloxy; and aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, valeryl, hexanoyl, heptanyl, octanoyl, nonanoyl, and decanoyl.Chain alkyl oxycarbonyl groups including methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, and decyloxycarbonyl; aliphatic acyloxy groups including formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, hexanoyloxy, heptayloxy, octyloxy, nonanoyloxy, and decyloxy.

[0093] In formula (A1-1), ma3 is an integer between 1 and 10. The value of ma3 is not particularly limited as long as it is between 1 and 10, and can be appropriately selected according to the structure of X. The value of ma3 is preferably between 1 and 4, and more preferably 1 or 2.

[0094] In formula (A1-1), X is an organic group with 1 to 100 carbon atoms. Preferably, the organic group X has 2 to 80 carbon atoms, more preferably 6 to 50 carbon atoms. The organic group X may also contain heteroatoms such as O, N, S, P, B, Si, or halogen atoms. It should be noted that in the compound represented by formula (A1-1), the two amino groups are bonded to carbon atoms in the organic group X.

[0095] The organic group X can be an aliphatic group, an aromatic group, or a combination of aliphatic and aromatic groups. The organic group X can also be a group formed by bonds containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. Examples of heteroatoms in the organic group X include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, with -O-, -CO-, and -S- being preferred.

[0096] When the organic group X is an aliphatic group, it can be a saturated aliphatic group or an unsaturated aliphatic group. When the organic group X is an aliphatic group, it is preferably an aliphatic hydrocarbon group. When the organic group X is an aliphatic group, it can be chain-like, cyclic, or a combination of chain-like and cyclic aliphatic groups. Chain-like aliphatic groups can also have branches.

[0097] When the organic group X is an aliphatic group, the aliphatic group is preferably a group obtained by removing (ma1+ma3+2) hydrogen atoms from an alkylene group having 1 to 20 carbon atoms, more preferably a group obtained by removing (ma1+ma3+2) hydrogen atoms from an alkylene group having 1 to 16 carbon atoms, and even more preferably a group obtained by removing (ma1+ma3+2) hydrogen atoms from an alkylene group having 1 to 12 carbon atoms.

[0098] When the organic group X is a group containing an aromatic group, as in formula (A1-1) X, Ar, R a1 and R a2 The constituent groups can be represented by the groups represented by the following formulas (11) to (15).

[0099] [Chemical Formula 7]

[0100]

[0101] In equations (11) to (15), Ar and R a1 R a2 The symbols ma1, ma2, and ma3 are the same as those in equation (A1). In equation (13), ma4 and ma5 are each independent integers greater than or equal to 0 and less than 4. ma6 and ma7 are each independent integers greater than or equal to 0 and less than 4, and the sum of ma6 and ma7 is greater than or equal to 1 and less than 8. In equation (14), ma8, ma9, and ma10 are each independent integers greater than or equal to 0 and less than 4. The sum of ma8, ma9, and ma10 is greater than or equal to 0 and less than 10. ma11, ma12, and ma13 are each independent integers greater than or equal to 0 and less than 4. The sum of ma11, ma12, and ma13 is greater than or equal to 1 and less than 10. In equation (15), ma14 is an integer greater than or equal to 0 and less than 3. ma15 is an integer greater than or equal to 0 and less than 5. The sum of ma14 and ma15 is greater than or equal to 0 and less than 8. ma16 is an integer greater than or equal to 0 and less than 3. ma17 is an integer greater than or equal to 0 and less than 5. The sum of ma16 and ma17 is greater than 1 and less than 8.

[0102] In formula (11), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2.

[0103] In formula (12), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2.

[0104] 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 1 or more, preferably 4 or less.

[0105] 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 1 or more, preferably 6 or less.

[0106] 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 1 or more, preferably 4 or less.

[0107] In equations (11) to (15), R a3 The linking group is a single bond or a divalent linking group. However, the divalent linking group is not a group containing an aromatic group. Examples of divalent linking groups include aliphatic hydrocarbon groups with 1 to 20 carbon atoms, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, as well as groups composed of two or more of 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 have branches, and may contain a ring structure. Specific examples of aliphatic hydrocarbon groups as linking groups include methylene, ethane-1,2-diyl (ethylene), ethane-1,1-diyl, propane-1,3-diyl, propane-1,2-diyl, propane-1,1-diyl, and propane.

[0108] -2,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7

[0109] -Diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, octadecane-1,18-diyl, nonadecane-1,19-diyl, eicosane-1,20-diyl, ethylene-1,2-diyl (vinylene), propylene-1,3-diyl, acetylene-1,2-diyl, and propyne-1,3-diyl, etc.

[0110] Preferred examples of linking groups include alkylene groups with 1 to 6 carbon atoms, alkenyl groups with 2 to 6 carbon atoms, alkyneyl groups with 2 to 6 carbon atoms, alkyloxy groups with 1 to 6 carbon atoms, alkenyloxy groups with 2 to 6 carbon atoms, alkyneyloxy groups with 2 to 6 carbon atoms, alkylthio groups with 1 to 6 carbon atoms, alkenylthio groups with 2 to 6 carbon atoms, alkyneylthio groups with 2 to 6 carbon atoms, alkylamino groups with 1 to 6 carbon atoms, alkenylamino groups with 2 to 6 carbon atoms, alkyneamino groups with 2 to 6 carbon atoms, -CONH-, -NH-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, -OCONH-, and -OCOO-, etc.

[0111] Considering that the polyimide resin formed using the polyimide resin precursor (A1) exhibits low dielectric loss tangent and good mechanical properties, the divalent group represented by formula (A1-1) is preferably the divalent group represented by the following formula (A1-2).

[0112] [Chemical Formula 8]

[0113]

[0114] (In formula (A1-2), R) a1 R a2 Ar, ma1, ma2, and ma3 are the same as the symbols in equation (A1-1), Y a1 Y is an organic group with 1 to 20 carbon atoms, or a single bond. a2 For organic groups with 1 to 20 carbon atoms, na1 is either 0 or 1, and na2 is either 0 or 1. (When na1 is 1, Ya1 is not a single bond.)

[0115] In equation (A1-2), Y is used as... a1 The organic groups can also contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms. As Y... a1 The organic group is preferably a hydrocarbon group. As Y a1 The hydrocarbon group can be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of aliphatic and aromatic hydrocarbon groups. Regarding Y... a1 The hydrocarbon group is preferably an aromatic hydrocarbon group, more preferably a phenylene group or a naphthyl group. Regarding Y... a1Preferred examples of the aromatic hydrocarbon group include p-phenylene, m-phenylene, o-phenylene, 1,4-diyl naphthol, 1,2-diyl naphthol, 1,3-diyl naphthol, 1,5-diyl naphthol, 1,6-diyl naphthol, 1,7-diyl naphthol, 1,8-diyl naphthol, 2,6-diyl naphthol, 2,7-diyl naphthol, and 2,3-diyl naphthol. Among these aromatic hydrocarbon groups, p-phenylene and m-phenylene are preferred, and p-phenylene is more preferred.

[0116] In formula (A1-2), it is preferred that na2 is 1, more preferably that both na1 and na2 are 1, and Y a1 The group is an organic group. In this case, it is believed that due to the high degree of stereofreedom of the ether bond, the structural units of the diamine compound (A-1) with the divalent group represented by formula (A1-2) can be well stacked, and a polyimide resin precursor (A1) that can provide excellent mechanical, thermal and electrical properties can be easily obtained.

[0117] In formula (A1-2), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2.

[0118] As specific examples of the diamine compound (A-1) described above, the following compounds can be cited.

[0119] [Chemical Formula 9]

[0120]

[0121] [Chemical Formula 10]

[0122]

[0123] [Chemical Formula 11]

[0124]

[0125] [Chemical Formula 12]

[0126]

[0127] [Chemical Formula 13]

[0128]

[0129] [Chemical Formula 14]

[0130]

[0131] [Chemical Formula 15]

[0132]

[0133] [Chemical Formula 16]

[0134]

[0135] (Diamine compound (A-2))

[0136] Diamine compound (A-2) is a diamine compound that has a partial structure represented by the following formula (A2-1) and does not belong to diamine compound (A-1).

[0137] [Chemical Formula 17]

[0138]

[0139] (In formula (A2-1), R) a3 and R a4 Each of the following is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; ma4 and ma5 are each independently an integer having 0 to 4.

[0140] In equation (A2-1), regarding R a3 and R a4 Alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among these alkyl groups, methyl and ethyl are preferred, and methyl is more preferred.

[0141] In equation (A2-1), regarding R a3 and R a4 Examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy. Among these alkoxy groups, methoxy and ethoxy are preferred, and methoxy is more preferred.

[0142] In equation (A2-1), regarding R a3 and R a4 Halogen atoms can be fluorine, chlorine, bromine, and iodine. Among these halogen atoms, chlorine and bromine atoms are preferred.

[0143] In formula (A2-1), ma4 and ma5 are each independently an integer between 0 and 4. Considering the ease of obtaining the diamine compound (A-2), ma4 and ma5 are preferably integers between 0 and 2, and more preferably 0.

[0144] Regarding groups preferred as divalent groups having a partial structure represented by formula (A2-1), examples of divalent groups represented by the following formula (A2-2) can be cited.

[0145] [Chemical Formula 18]

[0146]

[0147] (In formula (A2-2), X) 1 and X 2 Each is an aromatic hydrocarbon group that can be substituted by one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and halogen atoms. R a3 R a4 The symbols ma4 and ma5 are the same as those in formula (A2-1). (Note that the upper limit for the number of carbon atoms in the divalent group represented by formula (A2-2) is 40.)

[0148] X in equation (A2-2) 1 and X 2 Each of the above is a divalent aromatic hydrocarbon group that can be substituted by one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and halogen atoms.

[0149] Examples of alkyl groups that are 1 to 4 carbon atoms and are used as substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among these alkyl groups, methyl and ethyl are preferred, and methyl is more preferred.

[0150] Examples of alkoxy groups with 1 to 4 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy. Among these alkoxy groups, methoxy and ethoxy are preferred, and methoxy is more preferred.

[0151] Examples of halogen atoms that can be used as substituents include fluorine, chlorine, bromine, and iodine atoms. Among these halogen atoms, chlorine and bromine atoms are preferred.

[0152] As X 1 and X 2 There is no particular limitation on the number of carbon atoms in the aromatic hydrocarbon group, as long as the number of carbon atoms in the divalent group represented by formula (A2-2) is 40 or less. It should be noted that the number of carbon atoms in the aforementioned aromatic hydrocarbon group does not include the number of carbon atoms in the substituents.

[0153] Regarding X 1 and X 2 The aromatic hydrocarbon group is preferably phenylene, m-phenylene, and p-phenylene, naphthyl-1,4-diyl, naphthyl-1,3-diyl, naphthyl-2,6-diyl, and naphthyl-2,7-diyl, biphenyl-4,4'-diyl, biphenyl-3,4'-diyl, and biphenyl-3,3'-diyl.

[0154] As X 1 and X 2 Preferably, it is p-phenylene, m-phenylene, naphthalene-1,4-diyl, and biphenyl-4,4'-diyl, more preferably p-phenylene and biphenyl-4,4'-diyl, and even more preferably p-phenylene.

[0155] As a specific example of the diamine compound (A-2) containing a divalent group having a partial structure represented by formula (A2-1) described above, the following compound can be cited.

[0156] [Chemical Formula 19]

[0157]

[0158] (Diamine compound (A-3))

[0159] Diamine compound (A-3) is a diamine compound having a partial structure represented by the following formula (A3) and not belonging to diamine compounds (A-1) and (A-2).

[0160] [Chemical Formula 20]

[0161]

[0162] (In formula (A3), R) a5 and R a6 Each is 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 integers having 0 to 4 carbon atoms; R a7 and R a8 Each is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a phenyl group, R a7 With R a8 They can bond together to form a ring.

[0163] In equation (A3), regarding R a5 and R a6 Alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among these alkyl groups, methyl and ethyl are preferred, and methyl is more preferred.

[0164] In equation (A3), regarding R a5 and R a6 Examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy. Among these alkoxy groups, methoxy and ethoxy are preferred, and methoxy is more preferred.

[0165] In equation (A3), regarding R a5 and R a6 Halogen atoms can be fluorine, chlorine, bromine, and iodine. Among these halogen atoms, chlorine and bromine atoms are preferred.

[0166] In formula (A3), ma6 and ma7 are each independently an integer between 0 and 4. Considering the ease of obtaining the diamine compound (A-3), ma6 and ma7 are preferably integers between 0 and 2, and more preferably 0.

[0167] In equation (A3), regarding R a7 and R a8 Alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0168] In equation (A3), regarding R a7 and R a8 Haloalkyl groups having 1 to 4 carbon atoms include chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, and 1,1,2,2,2-pentafluoroethyl.

[0169] As R in equation (A3) a7 and R a8 Considering the good solubility of the polyimide resin precursor (A1) in organic solvents and the ease of obtaining the diamine compound (A-3), hydrogen atoms, methyl, ethyl, trifluoromethyl, and phenyl are preferred.

[0170] In addition, R is preferred. a7 and R a8 They bond with each other to form cycloalkyl groups with 5 to 8 carbon atoms, such as cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene.

[0171] As a preferred example of the partial structure represented by formula (A3), the following structure can be cited.

[0172] [Chemical Formula 21]

[0173]

[0174] Regarding compounds suitable as diamine compounds (A-3), compounds represented by the following formula (A3-1) can be cited.

[0175] [Chemical Formula 22]

[0176]

[0177] (In formula (A3-1), X) 3 and X 4 Each is an aromatic hydrocarbon group that can be substituted by one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and halogen atoms. R a5 R a6 R a7 R a8 The symbols ma6 and ma7 are the same as those in equation (A3).

[0178] X in equation (A3-1) 3 and X 4 Each of the above is a divalent aromatic hydrocarbon group that can be substituted by one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and halogen atoms.

[0179] Examples of alkyl groups that are 1 to 4 carbon atoms and are used as substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among these alkyl groups, methyl and ethyl are preferred, and methyl is more preferred.

[0180] Examples of alkoxy groups with 1 to 4 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy. Among these alkoxy groups, methoxy and ethoxy are preferred, and methoxy is more preferred.

[0181] Examples of halogen atoms that can be used as substituents include fluorine, chlorine, bromine, and iodine atoms. Among these halogen atoms, chlorine and bromine atoms are preferred.

[0182] As X 3 and X 4 The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited; for example, it is preferably 6 to 50, more preferably 6 to 20. It should be noted that the aforementioned number of carbon atoms in the aromatic hydrocarbon group does not include the number of carbon atoms in the substituents.

[0183] Regarding X 3 and X 4 The aromatic hydrocarbon group is preferably phenylene, m-phenylene, and p-phenylene, naphthyl-1,4-diyl, naphthyl-1,3-diyl, naphthyl-2,6-diyl, and naphthyl-2,7-diyl, biphenyl-4,4'-diyl, biphenyl-3,4'-diyl, and biphenyl-3,3'-diyl.

[0184] As X 3 and X 4Preferably, it is p-phenylene, m-phenylene, naphthalene-1,4-diyl, and biphenyl-4,4'-diyl, more preferably p-phenylene and biphenyl-4,4'-diyl, and even more preferably p-phenylene.

[0185] As specific examples of the diamine compound (A-3) represented by formula (A3) described above, the following compounds can be cited.

[0186] [Chemical Formula 23]

[0187]

[0188] [Chemical Formula 24]

[0189]

[0190] (Dimeric diamine compound (A-4))

[0191] From the perspective of readily obtaining a polyimide resin precursor (A1) that provides a low dielectric constant and low dielectric loss tangent at high frequencies, a dimer diamine compound (A-4) is also preferred as the diamine compound. The dimer diamine compound (A-4) is a diamine compound formed by replacing the two terminal carboxyl groups of a dimer acid with aminomethyl or amino groups. Dimer acids are known dicarboxylic acids obtained through intermolecular polymerization of unsaturated fatty acids. Industrial manufacturing processes for producing dimer acids have been largely standardized. Typically, dimer acids can be obtained by dimerizing unsaturated fatty acids with 11 to 22 carbon atoms in the presence of clay catalysts, etc. The main component of industrially obtained dimer acids is a 36-carbon dicarboxylic acid obtained by dimerizing unsaturated fatty acids with 18 carbon atoms, such as oleic acid, linoleic acid, and linolenic acid. Industrially obtained dimer acids can contain any amount of monomeric acids with 18 carbon atoms, trimeric acids with 54 carbon atoms, and other polymeric fatty acids with 20 to 54 carbon atoms, depending on the degree of purification.

[0192] As a dimerized diamine compound (A-4), the preferred diamine compound is one represented by the following formula (31).

[0193] [Chemical Formula 25]

[0194]

[0195] In equation (31), e, f, g, and h are each integers greater than or equal to 0. e+f is an integer between 6 and 17, and g+h is an integer between 8 and 19. In equation (31), the wavy line represents a carbon-carbon single bond or a carbon-carbon double bond.

[0196] From the viewpoint that it is easy to obtain a polyimide resin precursor (A1) that can form a polyimide resin with better elongation, the diamine compound represented by formula (31) is preferably the compound represented by the following formula (32).

[0197] [Chemical Formula 26]

[0198]

[0199] Commercially available examples of diamine compounds represented by formula (31) include Versamine 551 (manufactured by BASF) and PRIAMIN E1074 (manufactured by Claude Japan), which contain compounds represented by formula (33) below; and Versamine 552 (manufactured by BASF), PRIAMINE 1073 (manufactured by Claude Japan), and PRIAMINE 1075 (manufactured by Claude Japan), which contain compounds represented by formula (32) above. Such commercially available dimer diamine compounds (A-4) are generally mixtures containing multiple amine compounds.

[0200] [Chemical Formula 27]

[0201]

[0202] Alternatively, by reacting the diamine compound represented by formula (31) with an acyl halide from trimellitic anhydride, a tetracarboxylic dianhydride represented by formula (34) can be obtained. It is also preferable to use the tetracarboxylic dianhydride represented by formula (34) as a raw material for manufacturing polyimide resin precursor (A1).

[0203] In equation (34), i, j, k, and l are each integers greater than or equal to 0. i+j is an integer between 6 and 17, and k+l is an integer between 8 and 19. In equation (34), the wavy line represents a carbon-carbon single bond or a carbon-carbon double bond.

[0204] [Chemical Formula 28]

[0205]

[0206] The ratio of the molar number of one or more compounds selected from the group consisting of diamine compound (A-1), diamine compound (A-2), diamine compound (A-3), and dimerized diamine compound (A-4) to the total molar number of diamine compounds is preferably 10 mol% to 100 mol%, more preferably 15 mol% to 100 mol%, and even more preferably 20 mol% to 100 mol%.

[0207] (Tetracarboxylic acid dianhydride)

[0208] There are no particular limitations on the tetracarboxylic dianhydride used, as long as the desired effect is not compromised. Typically, tetracarboxylic dianhydrides that have been used in the manufacture of polyamic acids and polyimide resins can be used.

[0209] Examples of tetracarboxylic dianhydrides include compounds represented by the following formula (A3).

[0210] [Chemical Formula 29]

[0211]

[0212] (In formula (A3), X) A1 (A tetravalent organic group with 4 to 40 carbon atoms.)

[0213] In formula (A3), X A1 It is a tetravalent organic group with 4 to 40 carbon atoms, and in addition to the two anhydride groups represented by -CO-O-CO- in formula (A3), it may have one or more substituents.

[0214] Preferred examples of substituents are fluorine atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, fluoroalkyl groups having 1 to 6 carbon atoms, and fluoroalkoxy groups having 1 to 6 carbon atoms. Furthermore, the compound represented by formula (A3) may contain carboxyl groups or carboxylic acid ester groups in addition to anhydride groups.

[0215] When the substituent is a fluoroalkyl or fluoroalkoxy group, perfluoroalkyl or perfluoroalkoxy group is preferred.

[0216] The same applies to the substituents mentioned above, and to the aromatic groups described later, which may have one or more substituents on the aromatic ring.

[0217] Composition of X A1 The number of carbon atoms is preferably 8 or more, more preferably 12 or more. Furthermore, the constituent X... A1 The number of carbon atoms is preferably 30 or less. X A1 It can be an aliphatic group, an aromatic group, or a group composed of these structures. X A1 In addition to carbon and hydrogen atoms, it can also contain halogen atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. In X A1 When the X contains oxygen, nitrogen, or sulfur atoms, the oxygen, nitrogen, or sulfur atoms may be included in the form of a group selected from nitrogen-containing heterocyclic groups, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-. A1More preferably, it is contained in X in the form of a group selected from -O-, -CO-, -S-. A1 middle.

[0218] The tetracarboxylic dianhydride represented by formula (A3) can be an aliphatic tetracarboxylic dianhydride having two dicarboxylic anhydride groups bonded to aliphatic groups, or an aromatic tetracarboxylic dianhydride having at least one dicarboxylic anhydride group bonded to an aromatic group.

[0219] It should be noted that the aromatic tetracarboxylic dianhydride preferably has two dianboxylic anhydride groups bonded to aromatic groups. That is, as X A1 The tetravalent organic group is preferably a residue obtained by removing two dicarboxylic anhydride groups from an aromatic tetracarboxylic dianhydride.

[0220] Aliphatic tetracarboxylic dianhydrides can contain an alicyclic structure. This alicyclic structure can be polycyclic. Examples of aliphatic tetracarboxylic dianhydrides that do not have an alicyclic structure include 1,2,3,4-tetracarboxylic dianhydrides (e.g., RIKACIDBT-100, manufactured by Shin Nippon Rika Co., Ltd.).

[0221] Examples of alicyclic tetracarboxylic dianhydrides include cyclobutanetetracarboxylic dianhydrides, cyclopentane-1,2,3,4-tetracarboxylic dianhydrides, cyclohexane-1,2,4,5-tetracarboxylic dianhydrides, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydrides (e.g., ENEHYDE (registered trademark) CpODA, manufactured by ENEOS), and 2,2-bis(2,3-dicarboxyphenoxy)hexafluoropropane dianhydrides [5,5'-(1,4-phenylene)bisnorbornane]-2,2',3,3'-tetracarboxylic dianhydrides (e.g., ENEHYDE (registered trademark) BzDA, E NEOS Corporation), 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione (e.g., RIKACID TDA-100, manufactured by Shin Nippon Rika Co., Ltd.).

[0222] Examples of aromatic tetracarboxylic acid dianhydrides, represented by formula (A3) and having two dicarboxylic acid anhydride groups bonded to aromatic groups, include, for example, pyromellitic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phenyl dianhydride, 4,4'-oxobisphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic acid dianhydride, trimellitic acid (3,4-dicarboxyphenyl) dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3... 6,7-Naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis(2,3-dicarboxyphenyloxy)methane dianhydride, 1,1-bis(2,3-dicarboxyphenyloxy)ethane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride (bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) = 1,1'-biphenyl-4,4'-diyl ester), 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride, 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (e.g., RIKACID) TMEG100 (manufactured by Shin Nippon Rika Co., Ltd.), and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane Kasei Co., Ltd.), etc.

[0223] Among these aromatic tetracarboxylic acid 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 from the perspective of easily forming cured products with excellent electrical properties.

[0224] α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride is a compound represented by the following formula (a1).

[0225] [Chemical Formula 30]

[0226]

[0227] The number of carbon atoms of the straight-chain alkylene group in the α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride, i.e., n in formula (a1), is an integer of 1 or more, preferably 1 or more and 20 or less, more preferably 2 or more and 12 or less. Specific examples of preferred α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydrides include 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (e.g., RIKACID TMEG100, manufactured by Shin Nippon Rikka Co., Ltd.) and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane Kasei Co., Ltd.).

[0228] Furthermore, considering the suppression of warpage of the formed polyimide resin film and the better photolithographic properties of the photosensitive resin composition, biphenyl tetracarboxylic dianhydride is preferred.

[0229] Examples of biphenyltetracarboxylic dianhydrides include 3,3',4,4'-biphenyltetracarboxylic dianhydrides, 2,3,3',4'-biphenyltetracarboxylic dianhydrides, and 2,2',3,3'-biphenyltetracarboxylic dianhydrides, with 3,3',4,4'-biphenyltetracarboxylic dianhydrides being the most preferred.

[0230] Alternatively, it can be an aromatic tetracarboxylic acid dianhydride, for example, a compound represented by the following general formulas (a3-2) to (a3-4).

[0231] [Chemical Formula 31]

[0232]

[0233] In equations (a3-2) and (a3-3) above, R a01 R a02 and R a03 Each of these can be an aliphatic group that can be substituted with a halogen, an oxygen atom, a sulfur atom, or an aromatic group containing one or more divalent elements, or a divalent group composed of a combination of these. R a02 and R a03 They can be the same or different.

[0234] That is, R a01 R a02 and R a03It may contain carbon-carbon single bonds, carbon-oxygen-carbon ether bonds, or halogen elements (fluorine, chlorine, bromine, iodine). Examples of compounds 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)phenyl dianhydride.

[0235] In addition, in the above formula (a3-4), R a04 R a05 R represents any of the following: an aliphatic group that can be substituted by a halogen, an aromatic group containing one or more divalent elements, a halogen, or a monovalent substituent consisting of a combination of these. a04 and R a05 They can be the same or different. As compounds represented by formula (a3-4), difluoropyromellitic dianhydride and dichloropyromellitic dianhydride can also be used.

[0236] The polyimide resin precursor (A1) is also preferably a group containing a free radical polymerizable group on its molecular chain.

[0237] Therefore, the tetravalent organic group X in formula (A3) A1 It can also be a group represented by the following formulas (a3-5) to (a3-7).

[0238] [Chemical Formula 32]

[0239]

[0240] R in equations (a3-5) to (a3-7) a01 R a02 and R a03 R in the aforementioned equations (a3-2), (a3-3), and (a3-4) a01 R a02 and R a03 same.

[0241] R in equations (a3-5), (a3-6), and (a3-7) a06 It is a group containing a free radical polymerizable group.

[0242] (Method for manufacturing polyimide resin precursor (A1))

[0243] The polyimide resin precursor (A1) can be manufactured by reacting the aforementioned diamine compound with tetracarboxylic dianhydride.

[0244] The reaction between diamine compounds and tetracarboxylic dianhydrides is usually carried out in a solvent. There are no particular limitations on the solvent used in this reaction, as long as it can dissolve both the diamine compound and the tetracarboxylic dianhydride without reacting with them. One solvent may be used alone, or two or more solvents may be used in combination.

[0245] Examples of solvents used in the reaction of diamine compounds with tetracarboxylic dianhydrides include 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; lactone-based polar solvents such as β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone; dimethyl sulfoxide; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosol acetate, and ethyl cellosol acetate; and phenolic solvents such as cresols and xylene-based mixed solvents.

[0246] The reaction temperature is typically between -10°C and 120°C, preferably between 5°C and 30°C. The reaction time varies depending on the composition of the raw materials used, and is usually between 3 hours and 24 hours.

[0247] When manufacturing the polyimide resin precursor (A1), there is no particular limitation on the amount of diamine compound and tetracarboxylic dianhydride used. It is preferable to use 0.8 moles to 1.2 moles of diamine compound relative to 1 mole of tetracarboxylic dianhydride, more preferably 0.9 moles to 1.1 moles of diamine compound, and particularly preferably 0.95 moles to 1.05 moles of diamine compound.

[0248] The polyimide resin precursor (A1) obtained by partial imidization can be manufactured, for example, by reacting a diamine compound with a tetracarboxylic dianhydride and then imidizing it by heating or the like, thereby producing a polymer having imide structural units, by reacting the polymer, the diamine compound, and the tetracarboxylic dianhydride. Alternatively, the polyimide resin precursor (A1) obtained by partial imidization can also be manufactured by reacting a diamine compound with a tetracarboxylic dianhydride and then partially imidizing it by heating or the like.

[0249] The polyimide resin precursor (A1) has the characteristics represented by formula (a1), and R A1 and R A 2When at least one of the structural units is an organic group, a polyimide resin precursor (A1) can be produced by condensing a compound formed by the ring-opening reaction of one of the dicarboxylic acid dianhydrides represented by formula (A3) with an alcohol and a diamine compound, in accordance with conventional methods.

[0250] In this case, the tetracarboxylic dianhydride and diamine compound represented by formula (A3) can also be condensed together with a compound formed by the ring-opening of one of the dicarboxylic anhydride groups of the tetracarboxylic dianhydride represented by formula (A3) after reaction with an alcohol.

[0251] The alcohols that react with the tetracarboxylic acid dianhydride represented by formula (A3) can be unsaturated alcohols with olefinic unsaturated double bonds or saturated alcohols.

[0252] Specific examples of unsaturated alcohols include allyl alcohol; butenols such as but-3-en-1-ol and but-2-en-1-ol; pentenols such as pent-4-en-1-ol, pent-3-en-1-ol and pent-2-en-1-ol; hexenols such as hex-5-en-1-ol, hex-4-en-1-ol, hex-3-en-1-ol and hex-2-en-1-ol; and heptenols such as heptenol, ... 1-ol, and heptenols such as hepten-2-en-1-ol; octenols such as octen-7-en-1-ol, octen-6-en-1-ol, octen-5-en-1-ol, octen-4-en-1-ol, octen-3-en-1-ol, and octen-2-en-1-ol; nonenols such as nonen-8-en-1-ol, nonen-7-en-1-ol, nonen-6-en-1-ol, nonen-5-en-1-ol, nonen-4-en-1-ol, nonen-3-en-1-ol, and nonen-2-en-1-ol; Decenols such as dec-9-en-1-ol, dec-8-en-1-ol, dec-7-en-1-ol, dec-6-en-1-ol, dec-5-en-1-ol, dec-4-en-1-ol, dec-3-en-1-ol, and dec-2-en-1-ol; undecenols such as undecane-10-en-1-ol; dodecenols such as dodecane-11-en-1-ol; tridecenols such as tridecane-12-en-1-ol; and tetradecenols such as tetradecane-13-en-1-ol. Alcohols; pentadecenols such as pentadecane-14-en-1-ol; hexadecenols such as hexadecane-15-en-1-ol; heptadecenols such as heptadecane-16-en-1-ol; octadecenols such as octadecane-17-en-1-ol and octadecane-9-en-1-ol (oleyl alcohol); nonadecanols such as nonadecanols such as nonadecanols; eicosenes such as eicosene-19-en-1-ol; octadecadienols such as octadecane-9,12-dien-1-ol (linoleyl alcohol).

[0253] Other specific examples of unsaturated alcohols include mono(meth)acrylates of diols such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxypropane-2-yl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2-(2-hydroxyethoxy)ethyl (meth)acrylate, and 1-(2-(meth)acryloyloxyethyl)2-(2-hydroxypropyl) phthalate; hydroxyalkyl-substituted (meth)acrylamides such as N-(2-hydroxyethyl)(meth)acrylamide; and ketones containing hydroxyl groups such as (hydroxymethyl)vinyl ketone and (2-hydroxyethyl)vinyl ketone.

[0254] In addition, the following compounds are also preferred as unsaturated alcohols.

[0255] [Chemical Formula 33]

[0256]

[0257] Specific examples of saturated alcohols 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; and monoethers of diols 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.

[0258] The weight-average molecular weight of the polyimide resin precursor (A1) can be appropriately set according to the intended use of the photosensitive resin composition. In this specification, the weight-average molecular weight can be determined as the weight-average molecular weight converted to polystyrene based on GPC (gel permeation chromatography). From the viewpoint of obtaining a resin film with better mechanical properties, the weight-average molecular weight of the polyimide resin precursor (A1) is, for example, 5000 or more based on the above-mentioned polystyrene conversion, preferably 15000 or more, and more preferably 250,000,000 or more. On the other hand, from the perspective of solubility in organic solvents, the weight-average molecular weight of the obtained polyimide resin precursor (A1) is, for example, 100,000 or less based on the above-mentioned polystyrene conversion, preferably 80,000 or less, and more preferably 50,000 or less.

[0259] For this weight-average molecular weight, the reaction conditions, such as the amount of tetracarboxylic acid dianhydride and diamine compound, solvent, and reaction temperature, can be adjusted.

[0260] The main chain ends of the polyimide resin precursor (A1) can also be blocked using end-capping agents. Examples of end-capping agents include monoamines, acid anhydrides, monocarboxylic acids, monoacyl halides, and monoactive ester compounds.

[0261] Known compounds can be used as the monoamines for end-capping. Examples of monoamines include aromatic monoamines such as aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 3-hydroxyaniline, 4-hydroxyaniline, 3-aminobenzylthiophenol, and 4-aminobenzylthiophenol; aliphatic monoamines with a branched structure such as hexylamine and octylamine, monoamines with an alicyclic structure such as cyclohexylamine, and aminosilanes such as trimethoxyaminopropylsilane and triethoxyaminopropylsilane.

[0262] Among the acid anhydrides, monoacyl halides, and monoactive ester compounds used as capping agents, acid anhydrides are preferred. Known acid anhydrides and their derivatives can be used as acid anhydrides. Examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and their derivatives.

[0263] From the viewpoint of producing a polyimide resin precursor (A1) with excellent mechanical properties, the introduction rate of the capping agent is preferably 40 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less, relative to the total number of monomers.

[0264] [Isocyanate compound (A2)]

[0265] The isocyanate compound (A2) has a (meth)acryloyl group. Therefore, the isocyanate compound (A2) is a compound having an isocyanate group (-N=C=O) and a (meth)acryloyl group.

[0266] The number of (meth)acryloyl groups in the isocyanate compound (A2) is not particularly limited; it may have one or more. The isocyanate compound (A2) preferably has one or two (meth)acryloyl groups.

[0267] The number of isocyanate groups in the isocyanate compound (A2) is not particularly limited; it may have one or more isocyanate groups. Preferably, the isocyanate compound (A2a) comprises an isocyanate compound having one isocyanate group.

[0268] As a preferred example of an isocyanate compound (A2), a compound represented by the following formula (a2) can be cited.

[0269] H2C = CR 01-C(=O)-OR 02 -Z 01 -R 03 -NCO···(a2)

[0270] (where R is in the formula) 01 It can be a hydrogen atom or a methyl group.

[0271] R 02 It is an alkylene group that can have substituents.

[0272] Z 01 It is a single bond or an oxygen atom.

[0273] R 03 (It is a single bond, or an alkylene group that may have substituents.)

[0274] In equation (a2), R is used as 02 The alkylene group can be linear or branched. Examples of linear alkylene groups include methylene, ethane-1,2-diyl (ethylene), propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5-diyl.

[0275] Examples of branched alkylene compounds include methyl ethylene, 1-methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl, 1,1-dimethyl ethylene, 1-methylbutane-1,4-diyl, 2-methylbutane-1,4-diyl, 1,2-dimethylpropane-1,3-diyl, 1,1-dimethylpropane-1,3-diyl, and 2,2-dimethylpropane-1,3-diyl.

[0276] Regarding R 02 The alkylene group may have substituents, such as (meth)acryloyloxy.

[0277] In equation (a2), regarding R 03 alkylene and as R 03 The alkylene group may have substituents, and as R 02 alkylene and as R 02 The alkylene group may have the same substituents.

[0278] The following compounds can be cited as specific examples of isocyanate compounds (A2).

[0279] [Chemical Formula 34]

[0280]

[0281] [Method for preparing reactant (A)]

[0282] The reactant (A) can be produced by reacting a polyimide resin precursor (A1) having a structural unit represented by formula (a1) with an isocyanate compound (A2) having a (meth)acryloyl group.

[0283] The reaction between the polyimide resin precursor (A1) and the isocyanate compound (A2) is typically carried out in a solvent. There are no particular limitations on the solvent used in the reaction, as long as it can dissolve both the polyimide resin precursor (A1) and the isocyanate compound (A2) and does not react with either. One solvent may be used alone, or two or more solvents may be used in combination.

[0284] Examples of solvents used in the reaction of polyimide resin precursor (A1) with isocyanate compound (A2) include 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; lactone-based polar solvents such as β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone; dimethyl sulfoxide; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosol acetate, and ethyl cellosol acetate; and phenolic solvents such as cresols and xylene-based mixed solvents.

[0285] The reaction temperature is, for example, 40°C to 120°C, preferably 70°C to 90°C. The reaction time is, for example, 1 hour to 24 hours, preferably 4 hours to 8 hours.

[0286] There is no particular limitation on the amount of polyimide resin precursor (A1) and isocyanate compound (A2) used in the manufacture of reactant (A). The amount of isocyanate groups in isocyanate compound (A2) is preferably 0.4 mol or more and 1.5 mol or less, more preferably 0.5 mol or more and 1.3 mol or less, relative to 1 mole of carboxyl groups in polyimide resin precursor (A1).

[0287] Here, reactant (A) can be obtained by reacting a polyimide resin precursor (A1) having a structural unit represented by formula (a1) with an isocyanate compound (A2) having a (meth)acryloyl group, as described above. It is presumed that in reactant (A), the isocyanate compound (A2) is bonded to the structural unit represented by formula (a1) of the polyimide resin precursor (A1). However, the bonding state cannot be determined by analysis based on NMR, etc., and the bonding state is unclear. Therefore, the structure of reactant (A) cannot be determined, or, to perform the determination, a significantly excessive amount of economic expenditure and time is required. Therefore, since the structure and physical properties of the above-mentioned reactant (A) cannot be determined, reactant (A) is determined by the specification of "a reactant (A) of a polyimide resin precursor (A1) having a structural unit represented by formula (a1) and an isocyanate compound (A2) having a (meth)acryloyl group".

[0288] It should be noted that, in this specification and claims, reactant (A) can be the reactant itself obtained by reacting a polyimide resin precursor (A1) having a structural unit represented by formula (a1) with an isocyanate compound (A2) having a (meth)acryloyl group, or it can be a substance obtained by further reacting it with a diamine compound and a tetracarboxylic dianhydride to add structural units of a polyimide resin precursor such as polyamic acid. The added structural unit of the polyimide resin precursor can be the structural unit represented by formula (a1) above, or it can be a structural unit other than the structural unit represented by formula (a1) above.

[0289] <Heat-generating alkali agent (B)>

[0290] The photosensitive resin composition contains a thermal alkali-generating agent (B) that produces imidazole upon heating.

[0291] The thermal alkali-producing agent (B) is preferably a compound that produces one imidazole by heating.

[0292] The imidazole produced by the heat-generating alkali agent (B) upon heating may have substituents. Examples of such substituents include alkyl, halogen, hydroxyl, mercapto, thioether, silyl, silanol, nitro, nitroso, phosphono, sulfonato group, phosphono group, and phosphonato group. Examples of alkyl groups include those with 1 to 8 carbon atoms, such as methyl, ethyl, and isopropyl.

[0293] As a thermal alkali-generating agent (B), a thermal alkali-generating agent (B1) having the structure represented by the following formula (b1) is preferred.

[0294] -R B1 -C(=O)-Imd(b1)

[0295] (In formula (b1), R) B1 (It is a single bond or an oxygen atom; Imd is an imidazole-1-yl group that may have substituents.)

[0296] In formula (b1), the substituents that can be present in the imidazole-1- group include alkyl, halogen atom, hydroxyl, mercapto, thioether, silyl, silanol, nitro, nitroso, phosphono, sulfonate, oxophosphono, and phosphonate. As for the alkyl group, alkyl groups with 1 to 8 carbon atoms can be included; specific examples include methyl, ethyl, and isopropyl.

[0297] In equation (b1), R B1 Oxygen atoms are preferred.

[0298] For the heat-generating alkali agent (B1), it is preferred that R in formula (b1) is... B1 It contains oxygen atoms and is a tertiary or secondary ester.

[0299] The heat-generating alkali agent (B1) preferably has a structure represented by a formula (b1).

[0300] The following compounds can be cited as specific examples of heat-generating alkali agents (B1).

[0301] [Chemical Formula 35]

[0302]

[0303] The content of the thermal alkali-generating agent (B) in the photosensitive resin composition is not particularly limited. Typically, the content of the thermal alkali-generating agent (B) in the photosensitive resin composition is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, and particularly preferably 3 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of reactant (A).

[0304] <Photoradical polymerization initiator (C)>

[0305] The photosensitive resin composition contains a photoradical polymerization initiator (C).

[0306] As a photoradical polymerization initiator (C), there are no particular limitations, and any previously known photopolymerization initiator can be used.

[0307] As photoradical polymerization initiators (C), examples include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)-benzyl]phenyl}-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butane-1-one, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-2-(benzoyloximeimino)-1-propanone, 1-phenyl-1,2-butanedione Irgacure-2-(o-methoxycarbonyl) oxime, 1,3-diphenyltrione-2-(o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)ethyl oxime, 1-phenyl-3-ethoxytrione-2-(O-benzoyl) oxime, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazole-3-yl]ethyl oxime (Irgacure) OXE02 (manufactured by BASF Japan), (9-ethyl-6-nitro-9H-carbazole-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl] methyl ketone O-acetyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (I rgacure OXE01, manufactured by BASF Japan), NCI-831 (manufactured by ADEKA), NCI-930 (manufactured by ADEKA), OXE-03 (manufactured by BASF Japan), OXE-04 (manufactured by BASF Japan) (Manufactured by Japan Corporation), 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-Trimethylpentylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isopentyl 4-dimethylaminobenzoate, ethyl 4-diethylbenzoate, benzyl-β-methoxyethoxyacetal, benzoyladium dimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, methyl benzoylformate, ethyl benzoylformate, 2,4-diethylthioxanone, 2-chlorothioxanone, 2,4-dimethylthioxanone, 1-chloro-4-propoxythioxanone, thioxanone, 2-chlorothioxanone 2,4-Diethylthioxanthone, 2-Methylthioxanthone, 2-Isopropylthioxanthone, Anthraquinone, 2-Ethylanthraquinone, 2-tert-butylanthraquinone, Octamethylanthraquinone, 2-Aminoanthraquinone, β-Chloroanthraquinone, 1,2-Benzanthraquinone, 2,3-Diphenylanthraquinone, Anthraquinone, Benzoanthraquinone, Dibenzocycloheptanone, Methyleneanthraquinone, Azobisisobutyronitrile, Benzoyl peroxide, Cumene hydroperoxide, 2-Mercaptobenzimidazole, 2-Mercaptobenzimidazole, 2-Mercaptobenzimidazole, 2-Mercaptobenzimidazole, 2-(o-chlorophenyl)-4,5-Di(m-methoxyphenyl)-imidazolyl dimer, Benzophenone, 2-Chlorobenzophenone, p,p'-bis(dimethylaminobenzophenone), 4,4'-bis(diethylaminobenzophenone), 4,4'-dichlorobenzophenone, 3,3-Dimethyl-4-methyl 4-Hydroxybenzophenone, 4-Phenylenebenzophenone, Fluorenone, Benzoin, Benzoin, Benzoin Methyl Ether, Benzoin Ethyl Ether, Benzoin Isopropyl Ether, Benzoin n-Butyl Ether, Benzoin Isobutyl Ether, Acetophenone, 2,2-Diethoxyacetophenone, p-Dimethylacetophenone, p-Dimethylaminoacetophenone, 2-Hydroxy-2-Methylacetophenone, Dichloroacetophenone, Trichloroacetophenone, p-T-Butylacetophenone, 2-Phenyleneacetophenone, p-Dimethylaminoacetophenone, p-T-Butyltrichloroacetophenone, p-T-Butyldichloroacetophenone, α,α-Dichloro-4-phenoxyacetophenone, Thioxanone, 2-Methylthioxanone, 2-Isopropylthioxanone, 2,4-Dimethylthioxanone, 2,4-Diethylthioxanone, 2-Chlorothioxanone, 2,4-Di... Chlorthoxanone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thixan-2-yloxy)-N,N,N-trimethyl-1-propanediamine chloride, 4-azidobenzylacetophenone, 2,6-bis(p-azidobenzyl)cyclohexane, 2,6-bis(p-azidobenzyl)-4-methylcyclohexanone, dibenzocycloheptanone, pentyl 4-dimethylaminobenzoate, 9-phenylacridinium, 1,7-bis(9-acridyl)heptane, 1,5-bis(9-acridyl)pentane, 1,3-bis(9-acridyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)triazine, 2-methyl-4,6-bis(trichloromethyl)triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-Bis(trichloromethyl)triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)triazine, 2-(4-methoxyphenyl)-4,6 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)triazine, 2-(4-butoxyphenyl)-4,6-bis(trichloromethyl)triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyltriazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyltriazine, 2,4-bis-trichloromethyl- 6-(3-bromo-4-methoxy)styrylphenyltriazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyltriazine, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 4-benzoyl-N Examples of photoradical polymerization initiators (C) include N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzylammonium bromide, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propenylammonium chloride monohydrate, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzothiazole disulfide, triphenylphosphine, carbon tetrabromide, and tribromophenyl sulfone. These photoradical polymerization initiators (C) can be used alone or in combination of two or more.

[0308] From the perspective of good sensitivity, oxime ester-based photopolymerization initiators (C) are preferred as photoradical polymerization initiators.

[0309] Among the photoradical polymerization initiators (C), oxime ester compounds are preferred from the perspective of the sensitivity of the photosensitive resin composition.

[0310] As an oxime ester compound, a compound having a partial structure represented by the following formula (c1) is preferred.

[0311] [Chemical Formula 36]

[0312]

[0313] (in formula (c1),)

[0314] n1 is either 0 or 1.

[0315] R c2 It is a monovalent organic group.

[0316] Rc3 It can be a hydrogen atom, an aliphatic hydrocarbon group with 1 to 20 carbon atoms that may have substituents, or an aryl group that may have substituents.

[0317] * indicates a connection key.

[0318] 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 photolithographic properties. Typically, the content of the photoradical polymerization initiator (C) in the photosensitive resin composition is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 15 parts by mass or less, and even more preferably 1 part by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the reactant (A).

[0319] Solvent (S)

[0320] For purposes such as adjusting coatability, photosensitive resin compositions typically include a solvent (S). The type of solvent (S) is not particularly limited, as long as the reactants (A) and other components dissolve well. Organic solvents are commonly used as the solvent (S).

[0321] Considering the good solubility of reactant (A), specific examples of solvents (S) include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolinone, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylpropionamide, N,N-dimethylisobutyramide, N,N-dimethylethyleneurea, N,N-dimethylpropyleneurea, and N,N,N',N'-tetramethyl... Nitrogen-containing polar solvents such as methyl urea, 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; ketones such as 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, isoamyl acetate, n-amyl formate, n-butyl propionate, isopropyl butyrate, ethyl butyrate, n-butyl butyrate, methyl methoxyacetate, ethyl methoxyacetate Ester, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, methyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, methyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Esters such as esters, 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.

[0322] The amount of solvent (S) used is not particularly limited, as long as a homogeneous liquid photosensitive resin composition can be prepared. The photosensitive resin composition can be a suspension or a solution, preferably a solution. Typically, the solvent (S) is used in such a way that the concentration of the solid component 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.

[0323] <Other Ingredients>

[0324] The photosensitive resin composition may contain various additives other than those described above, as needed. Examples of additives include colorants, dispersants, sensitizers, adhesion promoters, polymerization inhibitors, antioxidants, ultraviolet absorbers, anti-coagulants, defoamers, surfactants, imidization promoters, nitrogen-containing heterocyclic compounds as adhesion enhancers, and silane coupling agents. Furthermore, the photosensitive resin composition may include various fillers or reinforcing materials, as needed.

[0325] Known compounds can be used as sensitizers. Examples of sensitizers include bis(dimethylamino)benzophenone, bis(diethylamino)benzophenone, diethylthioxanthone, N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-4-methylcoumarin, N-phenylmorpholine, and their derivatives.

[0326] Known compounds can be used as polymerization inhibitors. Examples of polymerization inhibitors include compounds having phenolic hydroxyl groups, nitroso compounds, N-oxide compounds, quinone compounds, N-oxygen compounds, and phenothiazine compounds. More specifically, preferred polymerization inhibitors are Irganox 1010, Irganox 1035, Irganox 1098, Irganox 1135, Irganox 245, Irganox 259, Irganox 3114 (all manufactured by BASF Japan), 2,6-di-tert-butyl-p-cresol, and 4-methoxyphenol, with Irganox 1010, 2,6-di-tert-butyl-p-cresol, and 4-methoxyphenol being more preferred.

[0327] From the viewpoint of simultaneously achieving excellent developability and good antioxidant effect of the photosensitive resin composition, the amount of 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 reactant (A).

[0328] Nitrogen-containing heterocyclic compounds can coordinate to and stabilize metal surfaces, thereby improving the adhesion between the resin film formed using the photosensitive resin composition and the metal surface. Known compounds can be used as nitrogen-containing heterocyclic compounds. Examples of nitrogen-containing heterocyclic compounds include pyrazoles, indazoles, carbazoles, triazoles, pyrazolines, pyrazolidines, tetrazolium, pyridines, piperidines, pyrimidines, pyrazines, triazines, cyanuric acid, isocyanuric acid, and their derivatives. From the viewpoint of coordination with metals, preferred examples of nitrogen-containing heterocyclic compounds 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.

[0329] From the viewpoint of simultaneously achieving excellent developability of the photosensitive resin composition and improved adhesion between the polyimide resin film formed using the photosensitive resin composition and the substrate, the amount of nitrogen-containing heterocyclic compound used is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 3% by mass or less, relative to the mass of reactant (A).

[0330] By incorporating a silane coupling agent into a photosensitive resin composition, the adhesion between the resin film formed using the photosensitive resin composition and the substrate, etc., can be improved. Known compounds can be used as silane coupling agents. Examples of silane coupling agents include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, 2-(epoxycyclohexyl)ethyltrimethoxysilane, 2-(epoxycyclohexyl)triethoxysilane, tris(3-trimethoxysilylpropyl) isocyanurate, tris(3-triethoxysilylpropyl) isocyanurate, reactants of 3-aminopropyltrimethoxysilane with acid anhydrides, and reactants of 3-aminopropyltriethoxysilane with acid anhydrides.

[0331] Examples of acid anhydrides that react 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'-benzophenone tetracarboxylic dianhydride, and 4,4'-oxobisphthalic dianhydride.

[0332] The amount of silane coupling agent used is preferably 0.01% by mass or more and 10% by mass or less relative to the mass of reactant (A).

[0333] By incorporating a surfactant into the photosensitive resin composition, the coatability of the photosensitive resin composition is improved, and the wettability of the photosensitive resin composition to the substrate is also improved. Known compounds can be used as surfactants. Examples of surfactants include fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.

[0334] The amount of surfactant used is preferably 0.001% by mass or more and 1% by mass or less relative to the mass of reactant (A).

[0335] The amount of various additives used is not particularly limited to the extent that it does not impede the purpose of the present invention. The amount of additives not described above may be suitably adjusted within, for example, a range of 0.001% by mass to 60% by mass relative to the mass of the solid component of the photosensitive resin composition, preferably 0.01% by mass to 5% by mass.

[0336] <Preparation Method of Photosensitive Resin Composition>

[0337] The essential components described above, along with optional components to be used as needed, can be uniformly mixed in the desired amounts to prepare a photosensitive resin composition. 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 using a filter.

[0338] Photosensitive dry film

[0339] The photosensitive dry film has a substrate film and a photosensitive layer formed on the surface of the substrate film, the photosensitive layer being a layer formed from the aforementioned photosensitive resin composition.

[0340] As the substrate film, a film with light transmittance is preferred. Specifically, polyethylene terephthalate (PET) film, polypropylene (PP) film, and polyethylene (PE) film can be cited as examples, but considering the excellent balance between light transmittance and tensile strength, polyethylene terephthalate (PET) film is preferred.

[0341] The aforementioned photosensitive resin composition is coated onto a substrate film to form a photosensitive layer, thereby producing a photosensitive dry film.

[0342] When forming a photosensitive layer on a substrate film, a coating applicator, bar coater, wire bar coater, roller coater, curtain coating applicator, etc. are used to coat the photosensitive resin composition onto the substrate film in a manner that the dried film thickness is preferably 0.5 μm to 300 μm or less, more preferably 1 μm to 300 μm or less, and particularly preferably 3 μm to 100 μm or less, and then the film is dried.

[0343] Photosensitive dry films can further have a protective film on the photosensitive layer. Examples of such protective films include polyethylene terephthalate (PET) films, polypropylene (PP) films, and polyethylene (PE) films.

[0344] Method for manufacturing patterned polyimide resin films

[0345] A patterned polyimide resin film is formed using a method comprising the following steps:

[0346] The process of coating a substrate with the aforementioned photosensitive resin composition to form a coating film;

[0347] A process of exposing a coated film in a position-selective manner;

[0348] The process of developing the exposed coated film to obtain a patterned resin film; and

[0349] The process of heating a patterned resin film to generate polyimide resin from reactant (A).

[0350] There are no particular limitations on the substrate; conventionally known substrates can be used, such as substrates for electronic components or substrates on which a prescribed wiring pattern is formed. Silicon substrates, glass substrates, etc., can also be used as substrates.

[0351] The thickness of the coating film is not particularly limited, but it is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, particularly preferably 1 μm or more and 150 μm or less, and most preferably 3 μm or more and 100 μm or less.

[0352] Methods for coating a photosensitive resin composition onto a substrate include spin coating, slot coating, roller coating, screen printing, and applicator methods.

[0353] A photosensitive resin composition coated onto a substrate is typically formed into a coating film by drying. The method for drying the photosensitive resin composition coated onto the substrate is not particularly limited. Drying by heating is preferred. The heating conditions during drying vary depending on the type and proportion of the components in the photosensitive resin composition, the thickness of the coating film, etc., and are generally between 70°C and 200°C, preferably between 80°C and 150°C, for approximately 2 minutes to 120 minutes.

[0354] The coated film formed as described above is exposed by irradiating it with active light or radiation in a position-selective manner. Position-selective exposure is usually performed by irradiating the film with active light or radiation, such as ultraviolet light or visible light with wavelengths of 300 nm to 500 nm, through a mask with a prescribed pattern in a position-selective manner.

[0355] As sources of radiation, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon lasers can be used. In addition, radiation includes microwaves, infrared radiation, visible light, ultraviolet radiation, X-rays, gamma rays, electron beams, proton beams, neutron beams, and ion beams. The radiation dose also varies depending on the composition of the photosensitive resin composition and the thickness of the coating film; for example, when using an ultra-high-pressure mercury lamp, it is 100 mJ / cm². 2 Above 10000mJ / cm 2 the following.

[0356] Next, the exposed coated film is developed using conventional methods to dissolve and remove unwanted portions, thereby forming a resin film patterned into a predetermined shape. At this time, a developer solution corresponding to the components contained in the photosensitive resin composition is used. The aforementioned solvent (S) can be used as the developer solution. If the aforementioned reactant (A) is a resin having an alkali-soluble group such as a carboxyl group, an alkaline aqueous solution can be used as the developer solution.

[0357] As an alkaline developer, for example, aqueous solutions of bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl diethylamine, 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 can be used. Alternatively, an aqueous solution obtained by adding appropriate amounts of water-soluble organic solvents such as methanol or ethanol, or surfactants, to the above-mentioned alkaline aqueous solutions can also be used as a developer.

[0358] The development time varies depending on the composition of the photosensitive resin composition and the thickness of the coated film, and is generally between 1 minute and 30 minutes. The development method can be any of the following: liquid accumulation method, immersion method, spin-dip method, spray development method, etc.

[0359] Next, the patterned resin film is heated to generate polyimide resin from reactant (A). Thus, a patterned polyimide resin film is manufactured.

[0360] There are no particular restrictions on the heating conditions, as long as the reactant (A) does not decompose and solidifies well.

[0361] The preferred heating temperature is 80°C to 220°C, more preferably 100°C to 200°C, and particularly preferably 120°C to 180°C.

[0362] Here, due to the heating at high temperatures, there are concerns about substrate warping and damage to semiconductor components.

[0363] However, according to the above-described photosensitive resin composition, the reactant (A) can be cured at a low temperature (e.g., below 200°C), thus suppressing adverse effects caused by heating at high temperatures, such as substrate warping and damage to semiconductor elements.

[0364] The curing temperature can be below 200°C, or above 200°C depending on the substrate used.

[0365] The heating time also depends on the heating temperature, typically preferably 10 minutes to 24 hours, more preferably 30 minutes to 2 hours.

[0366] From the perspective of preventing the oxidation of the resin film and obtaining a resin film with better mechanical properties, heating is preferably carried out in an atmosphere of inactive gases such as nitrogen and argon.

[0367] After heating, wash for 30 to 90 seconds as needed, using an air gun, oven, etc., to dry the patterned polyimide resin film. There are no particular limitations on the washing solvent. As an example, water, alcohols, etc., can be used as washing solvents in cases where alkaline development has been performed. When development has been performed using solvent (S), solvent (S) can be used within a range that will not cause solvent shock.

[0368] The patterned polyimide resin film formed as described above can be suitably used as, for example, insulating films and protective films in semiconductor devices, interlayer insulating films for redistribution layers, touch panel displays, organic electroluminescent display panels, etc. Because the aforementioned photosensitive resin composition has good resolution, the patterned polyimide resin film formed as described above can be particularly preferably used as an interlayer insulating film for redistribution layers in three-dimensional mounting devices, etc.

[0369] In addition, the patterned polyimide resin film formed as described above can also be suitably used as a photoresist, electrolytic resist, etching resist, and top solder resist for electronic devices.

[0370] In addition, the patterned polyimide resin film formed as described above can also be used in the manufacture of printing plates such as offset printing plates or screen printing plates, the formation of etching masks when etching molded parts, and the manufacture of protective varnishes and dielectric layers in electronic components, especially microelectronic components.

[0371] As described above, the inventors of this application have provided the following [1] to [6].

[0372] [1] A photosensitive resin composition comprising: a reactant (A) of a polyimide resin precursor (A1) having a structural unit represented by the following formula (a1) and an isocyanate compound (A2) having a (meth)acryloyl group; a thermal alkali-generating agent (B) that generates imidazole by heating; and a photoradical polymerization initiator (C).

[0373] [Chemical Formula 37]

[0374]

[0375] (In formula (a1), X) A1 Y is a tetravalent organic group with 4 to 40 carbon atoms. A1 Organic groups consisting of 4 to 40 carbon atoms.

[0376] R A1 and R A2 Each is an independent organic group consisting of a hydrogen atom or a carbon atom number between 1 and 30, R A1 and R A2 At least one of them is a hydrogen atom, as R A1 and R A2 The aforementioned organic groups are bonded to the oxygen atoms in the ester bond via CO bonds.

[0377] [2] The photosensitive resin composition as described in [1] above, wherein the aforementioned thermal alkali-generating agent (B) comprises a thermal alkali-generating agent (B1) having a structure represented by the following formula (b1).

[0378] -R B1 -C(=O)-Imd(b1)

[0379] (In formula (b1), R) B1 (It is a single bond or an oxygen atom; Imd is an imidazole-1-yl group that may have substituents.)

[0380] [3] The photosensitive resin composition as described in [2] above, wherein the aforementioned R B1 It is an oxygen atom.

[0381] [4] The photosensitive resin composition as described in any one of [1] to [3] above, wherein the aforementioned isocyanate compound (A2) comprises an isocyanate compound (A2a) having one isocyanate group.

[0382] [5] The photosensitive resin composition as described in any one of [1] to [4] above, wherein, as the aforementioned X A1 The aforementioned tetravalent organic group is a residue obtained by removing two dicarboxylic anhydride groups from an aromatic tetracarboxylic dianhydride.

[0383] [6] A method for manufacturing a patterned polyimide resin film, comprising the following steps:

[0384] The process of coating a substrate with the photosensitive resin composition described in any one of [1] to [5] above to form a coating film;

[0385] The process of exposing the aforementioned coated film in a position-selective manner;

[0386] The process of developing the exposed coated film to obtain a patterned resin film; and

[0387] The process of heating the aforementioned patterned resin film to generate polyimide resin from the aforementioned reactant (A).

[0388] Example

[0389] The present invention will now be described in detail with reference to the embodiments, but the scope of the present invention is not limited to these embodiments.

[0390] [Examples 1-21 and Comparative Examples 1-28]

[0391] In the examples and comparative examples, DA-1 to DA-8 described below were used as diamine compounds.

[0392] [Chemical Formula 38]

[0393]

[0394] DA-5: Dimeric diamine (product name "PRIAMINE1075", manufactured by Claude Japan Co., Ltd.)

[0395] DA-6: Meta-toluidine

[0396] DA-7: 4,4'-Isopropylidene bis[(4-aminophenoxy)benzene]

[0397] DA-8: 1,4-bis(4-aminophenoxy)benzene

[0398] In the examples and comparative examples, TC-1 to TC-5 described below were used as tetracarboxylic dianhydrides.

[0399] [Chemical Formula 39]

[0400]

[0401] TC-5: Bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) = 1,1'-biphenyl-4,4'-dimethyl ester

[0402] In the examples and comparative examples, IS-1 to IS-4 described below were used as isocyanate compounds having (meth)acryloyl groups.

[0403] [Chemical Formula 40]

[0404]

[0405] In the examples and comparative examples, the following IM-1 to IM-3 (thermal alkali-generating agents (B) that generate imidazole by heating) and B1 to B6 were used as thermal alkali-generating agents. It should be noted that B1 to B6 are thermal alkali-generating agents that do not generate imidazole by heating.

[0406] [Chemical Formula 41]

[0407]

[0408] [Chemical Formula 42]

[0409]

[0410] In the examples and comparative examples, C1 described below was used as the photoradical polymerization initiator (C).

[0411] C1: 1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-(o-benzoyloxime)(1,2-Octanedione,1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime))

[0412] (Preparation of reactant (A) of a polyimide resin precursor (A1) having a structural unit represented by formula (a1) and an isocyanate compound (A2) having a (meth)acryloyl group, used in Examples 1-14 and Comparative Examples 1-17)

[0413] Disperse 0.0322 moles of tetracarboxylic acid dianhydrides of the types listed in Table 1 in 23.33 g of N-methyl-2-pyrrolidone (NMP) and cool the solution to 0 °C. Add dropwise a solution obtained by dissolving 0.0322 moles of diamine compounds of the types listed in Table 1 in 17.53 g of NMP to the cooled liquid.

[0414] After the addition is complete, the resulting reaction solution is heated to room temperature and stirred for 12 hours to obtain a liquid containing a polyimide resin precursor (a1) having a structural unit represented by formula (a1).

[0415] The obtained liquid containing the polyimide resin precursor was heated to 80°C, and 0.0700 mol of an isocyanate compound (A2) of the type listed in Table 1 was added dropwise, followed by stirring for 6 hours. Then, the solution was added to isopropanol, and after obtaining a powder precipitate, it was filtered to obtain a powder. The obtained powder was washed three times with isopropanol and dried under reduced pressure to obtain a reaction product (A) of the polyimide resin precursor (A1) having the structural unit represented by formula (a1) and the isocyanate compound (A2) having a (meth)acryloyl group, used in the examples and comparative examples for preparing photosensitive resin compositions.

[0416] (Preparation of the polyimide resin precursor used in Comparative Examples 18-26)

[0417] Dissolve 0.0645 mol of the tetracarboxylic acid dianhydride of the type listed in Table 1 in 40.0 g of N-methyl-2-pyrrolidone (NMP). Add 0.135 mol of hydroxyethyl methacrylate and 0.135 mol of pyridine to the resulting solution. Stir the resulting solution at room temperature for 12 hours to obtain a dicarboxylic acid as a reaction product of the tetracarboxylic acid dianhydride and the alcohol (hydroxyethyl methacrylate).

[0418] The solution containing the obtained dicarboxylic acid was cooled to 0°C. A condensing agent solution obtained by dissolving 0.142 moles of dicyclohexylcarbodiimide in 8.5 g of NMP and a solution obtained by dissolving 0.0645 moles of a diamine compound of the type listed in Table 1 in 35.0 g of NMP were then added dropwise to the cooled solution.

[0419] After the addition is complete, the resulting reaction solution is stirred at 30°C for 6 hours to allow the dicarboxylic acid and diamine compound to condense.

[0420] After the reaction was complete, 15.0 g of methanol was added to the reaction solution. After removing the precipitated byproducts by filtration, the filtrate containing the polyimide resin precursor was added dropwise to a large volume of isopropanol aqueous solution. After addition, the polyimide resin precursor precipitated in the isopropanol aqueous solution was recovered by filtration. The recovered precipitate was washed three times with isopropanol. The washed precipitate was dried under reduced pressure to obtain the polyimide resin precursor used in the comparative examples for preparing the photosensitive resin compositions.

[0421] (Preparation of reactant (A) of polyimide resin precursor (A1) having structural units represented by formula (a1) and isocyanate compound (A2) having (meth)acryloyl groups used in Example 15)

[0422] The reaction product (A) of a polyimide resin precursor (A1) having a structural unit represented by formula (a1) and an isocyanate compound (A2) having a (meth)acryloyl group was manufactured through the following steps 1 to 4.

[0423] <Step 1> Synthesis of imide structural units

[0424] 130.0 g (0.25 mol) of TC-4, 751.3 g of diethylene glycol dimethyl ether, and 132.6 g of methylcyclohexane were added to a reaction vessel equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet. The reaction vessel was heated to 80–85 °C. After reaching 80–85 °C and the anhydride had dissolved, 101.1 g (0.187 mol) of DA-5 was added. A Dean-Stark tube / condenser was installed and filled with methylcyclohexane. The temperature was then slowly increased, and water generated by imidization was collected using the Dean-Stark tube for dehydration until a specified amount of water was produced or the temperature reached 140 °C. The water and solvent were removed from the Dean-Stark tube, and the reaction vessel was heated to 150 °C while removing volatile components. This temperature was maintained for 1 hour.

[0425] <Process 2>

[0426] The mixture was cooled to 60°C, and 300g of dimethylacetamide was mixed with 220.4g (0.749mol) of TC-2 to form a slurry, which was then added. 156.6g (0.738mol) of DA-6, which had been mixed with 261.2g of dimethylacetamide to form a slurry, was added at 55–60°C for 30 minutes. The mixture was then cooled to 50°C and held at that temperature for 1 hour. Finally, it was cooled to room temperature and stirred for 12 hours.

[0427] <Step 3> Reaction of isocyanate compound (A2) with (meth)acryloyl group

[0428] The reaction vessel was heated to 80°C, and 229.6 g (1.480 mol) of IS-1 was added, with the reaction proceeding for 7 hours. After two purifications via redeposition using 4 times the weight of isopropanol relative to the post-reaction solution, the solution was dissolved in dimethylacetamide to a solid content of 30%, yielding a solution of a polyimide precursor containing (meth)acryloyl groups. The anhydride concentration, calculated from the amount of aniline reacting with the (meth)acryloyl-containing polyimide precursor, was 0.036 mmol / g.

[0429] <Step 4> Addition of polyamic acid structural units

[0430] 100.0 g of a polyimide precursor containing (meth)acrylamide groups and 4.5 g (0.0153 mol) of TC-2 were added, and the reaction vessel was heated to 40°C. 3.46 g (0.0163 mol) of DA-6, prepared as a slurry by mixing with 43.9 g of dimethylacetamide, was added at 40–45°C for 30 minutes. The mixture was then cooled to 40°C and held at this temperature for 1 hour. Afterward, it was cooled to room temperature and stirred for 12 hours to obtain a polyimide precursor containing (meth)acrylamide groups (reactant (A)) with chain extension by a polyfunctional amine.

[0431] (Preparation of reactant (A) of a polyimide resin precursor (A1) having a structural unit represented by formula (a1) and an isocyanate compound (A2) having a (meth)acryloyl group, used in Examples 16-21 and Comparative Examples 27-28)

[0432] Make the changes as shown in Table 2 below, except that the same operation is performed as described above in "Preparation of reactant (A) of polyimide resin precursor (A1) having structural unit represented by formula (a1) and isocyanate compound (A2) having (meth)acryloyl group used in Example 15".

[0433] (Preparation of photosensitive resin composition)

[0434] 100 parts by mass of reactant (A) obtained in Examples 1-21, Comparative Examples 1-17 and 27-28, or 100 parts by mass of polyimide resin precursor obtained in Comparative Examples 18-26, and 5 parts by mass of thermal alkali-generating agent, photoradical polymerization initiator C1 (of the types and parts listed in Tables 1 and 2), 0.05 parts by mass of surfactant (BYK333, manufactured by BYK-Chemie), and 0.05 parts by mass of polymerization inhibitor (pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)) were dissolved in 300 parts by mass of γ-butyrolactone as solvent (S) to obtain the photosensitive resin compositions of each example and each comparative example.

[0435] <Stability Evaluation>

[0436] The obtained photosensitive resin composition was left to stand at room temperature for 1 week, and its storage stability was evaluated according to the following criteria.

[0437] 〇: No gelation occurred.

[0438] ×: Gel formation has occurred.

[0439] <Evaluation of Photolithography Characteristics (Resolution)>

[0440] A photosensitive resin composition was coated onto a silicon wafer with a copper sputtered film using a spin coater. The film was then baked at 120°C for 300 seconds to obtain a coated film with a thickness of 10 μm. I-line exposure was performed on the coated film using a ghi-line exposure machine (manufactured by ULTRATECH) through a negative mask capable of forming via holes. Negative masks capable of forming via holes with opening diameters of 5 μm and 10 μm were used for exposure.

[0441] In terms of exposure, at 2000 J / m 2 ~10000J / m 2 Within the range, the exposure will be increased from 2000 J / m 2 Increase the exposure in stages and repeat multiple times with multiple exposures.

[0442] That is, exposure of the unexposed coating film is performed a number of times calculated by (the number of exposure conditions) × (the number of types of mask opening diameters (2)).

[0443] For the coated films exposed under various exposure conditions, a spin-dip development process was performed using cyclopentanone (CP) for 180 seconds. Then, the films were heated at 200°C for 1 hour under a nitrogen atmosphere.

[0444] The obtained patterned resin film was observed, and the resolution was evaluated based on the diameter of the through-holes that could be imaged as in mask size, according to the following criteria.

[0445] ◎: Capable of forming through holes with opening diameters of 5μm and 10μm.

[0446] 〇: It can form a through hole with an opening diameter of 10μm, but it cannot form a through hole with an opening diameter of 5μm.

[0447] ×: Failed to form through holes with opening diameters of 5μm and 10μm.

[0448] <Chemical Resistance Evaluation>

[0449] A photosensitive resin composition was coated onto a silicon wafer using a spin coater. The film formed from the photosensitive resin composition was baked at 120°C for 300 seconds to obtain a coated film with a thickness of 10 μm. A high-pressure mercury lamp with a flux of 2000 mJ / cm² was used. 2 The cumulative light intensity was used to expose the coated film. After exposure, the film was heated to 200°C at a rate of 5°C / min in an inert oven under a nitrogen atmosphere, and maintained at this temperature for 1 hour. When the temperature dropped to 100°C, the wafer was removed. The wafer was cut into 5 cm squares to obtain test pieces, which were then immersed in N-methyl-2-pyrrolidone (NMP) at 60°C for 2 hours. The appearance of the test pieces after immersion was checked to see if there was any change compared to the appearance before immersion. Cases with no change in appearance after 2 hours were marked as ◎, cases with no change in appearance at 1 hour but a change after 2 hours were marked as ○, and cases with a change in appearance at 1 hour were marked as ×.

[0450] Evaluation of Mechanical Properties (Tensive Elongation)

[0451] Rectangular test pieces with a width of 1 cm and a length of 5 cm were cut from the wafers obtained in the same manner as in the <Chemical Resistance Evaluation>. Using the obtained test pieces and a tensile testing machine (EZ-test, manufactured by Shimadzu Corporation), tensile tests were performed under conditions of a chuck spacing of 2 cm and a tensile speed of 1 mm / min, and the tensile elongation was measured. The tensile elongation was calculated according to the following formula.

[0452] Elongation at break (%) = (distance between chucks at break (cm) / 2 (cm) - 1) × 100

[0453] For tensile elongation, 50% or more is defined as 0, and less than 50% is defined as ×.

[0454] [Table 1]

[0455]

[0456] [Table 2]

[0457]

[0458] [Table 3]

[0459] Photolithography Storage stability Tensile elongation Chemical resistance Example 15 ◎ ○ ○ ◎ Example 16 ◎ ○ ○ ◎ Example 17 ◎ ○ ○ ◎ Example 18 ◎ ○ ○ ○ Example 19 ◎ ○ ○ ◎ Example 20 ◎ ○ ○ ◎ Example 21 ◎ ○ ○ ◎ Comparative Example 27 ◎ ○ × × Comparative Example 28 × × ○ ○

[0460] As can be seen from the examples, the photosensitive resin composition comprising a polyimide resin precursor (A1) having a structural unit represented by formula (a1) and a reactant (A2) having a (meth)acryloyl group, a thermal alkali-generating agent (B) that generates imidazole by heating, and a photoradical polymerization initiator (C) exhibits excellent photolithographic properties and storage stability, and is capable of forming a polyimide resin film with excellent mechanical properties and chemical resistance.

[0461] On the other hand, it is known that the photosensitive resin composition that does not contain reactant (A) or the thermal alkali-generating agent (B) that generates imidazole by heating has worse photolithographic properties, storage stability, mechanical properties, and chemical resistance than the example.

Claims

1. A photosensitive resin composition comprising: a reactant (A) of a polyimide resin precursor (Al) having a structural unit represented by the following formula (al) and an isocyanate compound (A2) having a (meth)acryloyl group; a thermal base generator (B) that generates an imidazole by heating; and a photoradical polymerization initiator (C), [Chemical Formula 1] In formula (a1), X A1 is a 4-valent organic group having 4 to 40 carbon atoms, Y A1 R is an organic group having 4 to 40 carbon atoms, R A1 and R A2 each independently is a hydrogen atom or an organic group having 1 to 30 carbon atoms, R A1 and R A2 at least one of which is a hydrogen atom, the organic group as R A1 and R A2 is bonded to the oxygen atom in the ester bond via a C-O bond.

2. The photosensitive resin composition according to claim 1, wherein The thermal base generator (B) comprises a thermal base generator (Bl) having a structure represented by the following formula (bl), -R B1 -C(=O)-Imd(b1) In formula (b1), R B1 is a single bond or an oxygen atom, and Imd is an imidazol-1-yl group which can have a substituent.

3. The photosensitive resin composition according to claim 2, wherein The R B1 is an oxygen atom.

4. The photosensitive resin composition according to claim 1, wherein The isocyanate compound (A2) comprises an isocyanate compound (A2a) having one isocyanate group.

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

6. A method for producing a patterned polyimide resin film, comprising the following steps: a step of applying the photosensitive resin composition according to any one of claims 1 to 5 on a substrate to form an applied film; a step of exposing the applied film in a position-selective manner; a step of developing the exposed applied film, thereby obtaining a patterned resin film; and a step of heating the patterned resin film, thereby generating a polyimide resin from the reactant (A). ​

Images