Photosensitive resin composition and method for producing a patterned polyimide resin film

Abstract

To provide a photosensitive resin composition capable of forming a polyimide resin film with excellent photolithography properties and storage stability, as well as excellent mechanical properties and chemical resistance, and a method for manufacturing a patterned polyimide resin film using the photosensitive resin composition. [Solution] A photosensitive resin composition comprising a reaction product (A) of a polyimide resin precursor (A1) having a specific structural unit and an isocyanate compound (A2) having a (meth)acryloyl group, a thermobase generator (B) that generates imidazole upon heating, and a photoradical polymerization initiator (C).

Description

[Technical Field]

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

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

[0003] In recent years, communication devices such as mobile phones have been increasingly using higher frequencies. Therefore, the insulating parts that insulate the metal wiring in these devices also need to be able to handle these higher frequencies. Here, transmission loss increases with increasing frequency, and as transmission loss increases, electrical signals attenuate. Therefore, for resins such as polyimide resin and polyamide resin, further reduction of transmission loss is required in the high-frequency band, in order to cope with higher frequencies and to further reduce transmission loss.

[0004] Furthermore, when manufacturing various components and electronic circuit boards, it is often necessary to form insulating or protective materials only at desired locations. Therefore, there is a need to be able to apply photolithography to compositions for forming insulating and protective materials.

[0005] In response to the above requirements, a photosensitive resin composition has been proposed (Patent Document 1) that can form a patterned resin film with a low dielectric loss tangent by applying photolithography, comprising a resin and a photosensitive agent, wherein the resin is selected from the group consisting of polyimide resins, polyamic acid, polyamide resins, polybenzoxazole resins, and polybenzoxazole resin precursors, and the resin contains constituent units derived from diamine compounds with a specific structure having aromatic groups. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2022-190618 [Overview of the project] [Problems that the invention aims to solve]

[0007] 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 applying a photolithography method. On the other hand, further improvements are needed regarding the photosensitive resin composition described in Patent Document 1 in terms of its photolithography properties and storage stability, as well as the mechanical properties (mechanical strength) and chemical resistance of the formed patterned polyimide resin film.

[0008] The present invention has been made in view of the above problems, and aims to provide a photosensitive resin composition that can form a polyimide resin film that is excellent in photolithography properties and storage stability, and also excellent in mechanical properties and chemical resistance, and a method for producing a patterned polyimide resin film using the photosensitive resin composition. [Means for solving the problem]

[0009] The present inventors have discovered that the above problems can be solved by a photosensitive resin composition comprising a reaction product (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 thermobase generator (B) that generates imidazole upon heating, and a photoradical polymerization initiator (C), and have completed the present invention. More specifically, the present invention provides the following.

[0010] A first aspect of the present invention is a photosensitive resin composition comprising a reaction product (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 thermobase generator (B) that generates imidazole upon heating, and a photoradical polymerization initiator (C). [ka] (In formula (a1), X A1 This is a tetravalent organic group having 4 to 40 carbon atoms. Y A1 This is an organic group having 4 to 40 carbon atoms. R A1 , and R A2 Each is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R A1 , and R A2 At least one of them is a hydrogen atom, R A1 , and R A2 The aforementioned organic group is bonded to the oxygen atom in the ester bond via a CO bond.

[0011] A second aspect of the present invention involves applying a photosensitive resin composition according to the first aspect onto a substrate to form a coating film, The coated film is exposed to light in a positionally selective manner, By developing the exposed coating film, a patterned resin film is obtained. A method for producing a patterned polyimide resin film, comprising heating the patterned resin film to generate a polyimide resin derived from the reactant (A). [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a photosensitive resin composition that can form a polyimide resin film that is excellent in photolithography properties and storage stability, as well as excellent in mechanical properties and chemical resistance, and a method for producing a patterned polyimide resin film using the photosensitive resin composition. [Modes for carrying out the invention]

[0013] ≪Photosensitive Resin Composition≫ The photosensitive resin composition contains 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 photo radical polymerization initiator (C).

Chemical Formula

[0014] As shown in the examples described later, the above-mentioned photosensitive resin composition is excellent in photolithography characteristics and storage stability, and can form a polyimide resin film excellent in mechanical characteristics and chemical resistance.

[0015] On the other hand, if the photosensitive resin composition is not as described above, for example, a photosensitive resin composition that does not contain reactant (A) (for example, a photosensitive resin composition that contains a polyimide resin precursor (A1) having a constituent unit represented by formula (a1) that has not been reacted with an isocyanate compound (A2) having a (meth)acryloyl group, but does not contain reactant (A)), or a photosensitive resin composition that does not contain a thermobase generator (B) that generates imidazole upon heating (for example, a photosensitive resin composition that contains a thermobase generator that is not a thermobase generator (B) that generates imidazole upon heating, but does not contain a thermobase generator (B) that generates imidazole upon heating, or a photosensitive resin composition that does not contain a thermobase generator), then any of the following will be inferior in photolithography properties, storage stability, mechanical properties, or chemical resistance.

[0016] Furthermore, in the manufacturing of semiconductor devices, when a polyimide resin film is produced on a substrate using a conventional photosensitive resin composition containing a polyimide precursor, the polyimide precursor is cured by heating; specifically, the polyimide precursor is heated to induce a ring-closing reaction (imidation reaction). In this case, there are concerns about warping of the substrate and damage to the semiconductor device due to heating at high temperatures. However, with the above-mentioned photosensitive resin composition, the reactant (A) can be cured at a low temperature (for example, 200°C or below), thus suppressing adverse effects caused by heating at high temperatures, such as warping of the substrate and damage to semiconductor elements. The curing temperature may be 200°C or lower, but it may also be higher than 200°C depending on the type of substrate used.

[0017] Furthermore, the reactant (A) described above can be crosslinked by exposure in the presence of a photoradical polymerization initiator (C) described later. Subsequently, it is cured by heating in the presence of a thermobase generator (B) described later. Before heating, the isocyanate compound (A2) having a (meth)acryloyl group is bonded to the polyimide resin precursor (A1), and it is presumed that heating causes some of the isocyanate compound (A2) to be cleaved from the polyimide resin precursor (A1), and also causes a ring-closing reaction.

[0018] The following describes the essential and optional components that may be included in the photosensitive resin composition.

[0019] <Reactant (A)> The photosensitive resin composition comprises a 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.

[0020] [Polyimide resin precursor (A1)] The polyimide resin precursor (A1) has a constituent unit represented by the above formula (a1). The polyimide resin precursor (A1) may consist only of the constituent units represented by formula (a1), or it may have constituent units other than those represented by formula (a1). In the latter case, the polyimide resin precursor (A1) may be partially imidized. That is, if the polyimide resin precursor (A1) has constituent units other than those represented by formula (a1), the polyimide resin precursor (A1) may have the constituent units represented by formula (a1) and constituent units having an imide structure (imide constituent units).

[0021] When the polyimide resin precursor (A1) has a constituent unit represented by formula (a1) and a constituent unit other than the constituent unit represented by formula (a1), the content of the constituent unit 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 preferably 50 mol% or more and 95 mol% or less. When the polyimide resin precursor (A1) has a constituent unit represented by formula (a1) and a constituent unit having an imide structure (imide constituent unit), the content of the imide constituent unit in the polyimide resin precursor (A1) is not particularly limited, but is preferably 5 mol% or more and 70 mol% or less, and more preferably 5 mol% or more and 50 mol% or less.

[0022] Polyimide resin precursor (A1) is typically a polymer of a diamine compound and a tetracarboxylic dianhydride, a polymer in which a portion of this polymer is imidized, or a polymer in which a portion of the carboxyl groups of these polymers is esterified. Note that "a polymer in which a portion of the carboxyl groups of these polymers is esterified" is represented by the above formula (a1), and R A1 , and R A2 The polymer has constituent units in which some of the components are organic groups 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 ethylenically unsaturated double bonds, and (meth)acryloyl group-containing groups. The polyimide resin precursor (A1) is preferably a polymer of a diamine compound and a tetracarboxylic dianhydride, or a polymer in which a portion of this polymer is imidized. Diamine compounds and tetracarboxylic dianhydrides are selected such that the polyimide resin precursor (A1) satisfies the above-mentioned requirements.

[0023] (Diamine compounds) Diamine compounds are represented by the following formula (a1a). H2N-Y A1 -NH2···(a1a) (In equation (a1a), Y A1 (This represents a divalent organic group with 4 to 40 carbon atoms.)

[0024] Y A1 Y is a divalent organic group with 4 to 40 carbon atoms. A1 In addition to the two amino groups, it may have one or more substituents. Preferred examples of substituents include fluorine atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, fluorinated alkyl groups having 1 to 6 carbon atoms, fluorinated alkoxy groups having 1 to 6 carbon atoms, carboxyl groups, or hydroxyl groups. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferable that it be a perfluoroalkyl group or a perfluoroalkoxy group.

[0025] Y A1 The lower limit of the number of carbon atoms in the organic group is 4, preferably 6, and the upper limit is 40, preferably 30. Y A1 This may be an aliphatic group, but it is preferably an organic group containing one or more aromatic rings.

[0026] Y A1 If the organic group contains one or more aromatic rings, the organic group may be one aromatic group itself, or it may be a group in which two or more aromatic groups are bonded via bonds containing aliphatic hydrocarbon groups and halogenated aliphatic hydrocarbon groups, or heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. A1 Examples of heteroatom-containing bonds, such as oxygen atoms, sulfur atoms, and nitrogen atoms, include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, with -COO-, -O-, -CO-, and -S- being preferred.

[0027] Y that binds to an amino group A1 The aromatic ring inside is preferably a benzene ring. A1 If the ring bonded to the amino group is a condensed ring containing two or more rings, it is preferable that the ring bonded to the amino group in the condensed ring is a benzene ring. Also, Y A1 The aromatic ring contained therein may be an aromatic heterocycle.

[0028] Y A1 If the organic group contains an aromatic ring, it is preferable that the organic group is at least one of the groups represented by the following formulas (21) to (24) in order to improve the electrical and mechanical properties of the polyimide resin formed using the polyimide resin precursor (A1). [ka]

[0029] (21)~(24) Medium, R 111 Q represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a carboxyl group, a sulfonic acid group, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, and a halogenated alkyl group having 1 to 4 carbon atoms. In formula (24), Q 1 This refers to the 9,9'-fluorenylidene group, or the formula: -C6H4-, -C6H4-C6H4-, -O-C6H4-C6H4-O-, -O-C6H4-CO-C6H4-O-, -O-C6H4-C(CH3)2-C6H4-O-, -OCO-C6H4-COO-, -OCO-C6H4-C6H4-COO-, -OCO-, -O-, -CO-, -C(CF3)2-, -C(CH3)2-, -CH2-, -O-C6H4-SO2-C6H4-O-, -C(CH3)2-C6H4-C(CH3)2-, -OC 10 H6-O-, -O-C6H4-O-, -O-CH2-O-, and -O-(CH2) n This indicates one selected from the group consisting of groups represented by -O-.

[0030] Q 1 In the example, -C6H4- is a phenylene group, and m-phenylene groups and p-phenylene groups are preferred, with p-phenylene groups being more preferred. Also, -C 10 H6- is a naphthalenediyl group, preferably a naphthalene-1,2-diyl group, a naphthalene-1,4-diyl group, a naphthalene-2,3-diyl group, a naphthalene-2,6-diyl group, and a naphthalene-2,7-diyl group, and more preferably a naphthalene-1,4-diyl group and a naphthalene-2,6-diyl group. Q 1 In the example, n is an integer greater than or equal to 1, preferably an integer between 1 and 20, more preferably an integer between 1 and 12, and even more preferably an integer between 1 and 6.

[0031] Y A1As a diamine compound containing the group represented by formula (24), the compound represented by the following formula (a2) is preferred. For n in formula (a2), Q in formula (24) 1 As explained above. [ka]

[0032] 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 groups, ethyl groups, or trifluoromethyl groups are more preferred, and hydrogen atoms or trifluoromethyl groups are particularly preferred.

[0033] Q in equation (24) 1 In terms of the electrical and mechanical properties of the formed resin film, -C6H4-C6H4-, -O-C6H4-C6H4-O-, -O-C6H4-CO-C6H4-O-, -O-C6H4-C(CH3)2-C6H4-O-, -OCO-C6H4-COO-, -OCO-C6H4-C6H4-COO-, -OCO-, -O-, -CO-, -C(CF3)2-, -C(CH3)2-, -CH2-, -O-C6H4-SO2-C6H4-O-, -C(CH3)2-C6H4-C(CH3)2-, -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- are preferred. From the viewpoint of improving the electrical and mechanical properties of the polyimide resin formed using the polyimide resin precursor, Q in formula (24) is preferred. 1 As for the group, -O-C6H4-C6H4-O-, -O-C6H4-C(CH3)2-C6H4-O-, and -O- are more preferred, and groups represented as -O-C6H4-C6H4-O- where both -C6H4- are p-phenylene groups, and -O- are particularly preferred.

[0034] When using an aromatic diamine compound as the diamine compound represented by formula (a1a), for example, the aromatic diamine compounds shown below can be suitably used. In other words, 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 (m-tolidine), 3,3'-dimethyl-4,4'-diaminobiphenyl (o-tolidine), 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 9,10-diaminoanthracene, 9,10-bis(4-aminophenyl)anthracene, 4,4'-diamino- 2,2'-Bis(trifluoromethyl)biphenyl, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-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-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'-diaminodi Phenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfo-4,4'-diaminodiphenyl ether, 4,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, bis(3-amino-4-hydroxyphenyl) ether, bis[4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl] ether, 4,4'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(4-aminophenoxy)biphenyl, 3,3 '-Bis(4-aminophenoxy)biphenyl, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[4-(4-aminophenoxy [C)phenyl]ketone, 2,2-bis[4-{4-amino-2-(trifluoromethyl)phenoxy}phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-amino-3-methylphenyl)fluorene, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 9,9-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 9,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 2,7-diamine Nofluorene, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(3-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-6-aminobenzoxazole, 2-(3-aminophenyl)-6-aminobenzoxazole, 1,4-bis(5-amino-2-benzoxazolyl)benzene, 1,4-bis(6-amino-2-benzoxazolyl)benzene, 1,3-bis(5-amino-2-benzoxazolyl)benzene, 1,3-bis(6-amino-2-benzoxazolyl)benzene, 2,6-bis(4-aminophenyl)benzobisoxazole, 2,6-bis(3-aminophenyl)benzobisoxazole, bis[(3-aminophenyl)-5-benzoxazol], bis[(4-aminophenyl)-5-benzoxazol], bis[(3-aminophenyl)-6-benzoxazol], bis[(4-aminophenyl)-6-benzoxazol], 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 Examples include N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'-[1,4-phenylenebis(1-methylethane-1,1-diyl)]dianiline, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 4-aminobenzoic acid 4-aminophenyl ester, 1,3-bis(4-anilino)tetramethyldisiloxane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, and ortho-tolidine sulfone. Among these, 4,4'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(4-aminophenoxy)biphenyl, and 3,3'-bis(4-aminophenoxy)biphenyl are preferred in terms of improving electrical and mechanical properties.

[0035] Also, Y A1 As such, silicon atom-containing groups that may have a chain-like aliphatic group and / or an aromatic ring can be used. Typical silicon atom-containing groups that can be used are those shown below. [ka]

[0036] Specific examples of compounds having amino groups at both ends and silicon atom-containing groups include methylphenyl silicones with amino groups at both ends (for example, X-22-1660B-3 (number average molecular weight approximately 4,400) and X-22-9409 (number average molecular weight approximately 1,300) from Shin-Etsu Chemical Co., Ltd.), and dimethyl silicones with amino groups at both ends (for example, 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) from Shin-Etsu Chemical Co., Ltd.; BY16-835U from Toray Dow Corning (number average molecular weight approximately 900); and Cyraplane FM3311 from JNC Corporation (number average molecular weight approximately 1,000)).

[0037] Furthermore, diamines having an oxyalkylene group can also be preferably used as the diamine compound represented by formula (a1a). Preferred examples of the oxyalkylene group include ethylene oxy group and propylene oxy group (-C(CH3)-CH2-O-, -CH2-C(CH3)-O-, or -CH2CH2CH2-O-). A diamine having an oxyalkylene group may contain a combination of two or more oxyalkylene groups. When a diamine having an oxyalkylene group contains two or more oxyalkylene groups, the two or more oxyalkylene groups may be contained in the diamine in a block-like manner or randomly. Diamines having an oxyalkylene group are preferably free of cyclic groups, and more preferably free of aromatic groups. Specific examples of diamines having an oxyalkylene group include, respectively, Jeffermin® KH-511, Jeffermin® ED-600, Jeffermin® ED-900, Jeffermin® ED-2003, Jeffermin® EDR-148, Jeffermin® EDR-176, Jeffermin® D-200, Jeffermin® D-400, Jeffermin® D-2000, and Jeffermin® D-4000, as well as 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, all manufactured by HUNTSUMAN.

[0038] Based on the solubility of the polyimide resin precursor (A1) in organic solvents, the diamine compound is represented by formula (a1a), and Y A1 However, a diamine compound containing a group represented by formula (24), represented by formula (a1a), and Y A1 However, the diamine compound (A1) is represented by the following formula (A1-1), and is represented by formula (a1a), and Y A1 However, it is preferable to include one or more compounds selected from the group consisting of a diamine compound (A-2) having a substructure represented by formula (A2-1) described later and not corresponding to diamine compound (A-1), a diamine compound (A-3) having a substructure represented by formula (A3) described later and not corresponding to diamine compound (A-1) and diamine compound (A-2), and a dimer amine compound (A-4). Among these, it is preferable to include one represented by formula (a1a) and Y A1 However, diamine compounds containing a group represented by formula (24), diamine compound (A-1), and diamine compound (A-2) are preferred.

[0039] (Diamine compound (A-1)) The diamine compound (A-1) is represented by formula (a1a), and Y A1 However, it is a diamine compound whose group is represented by the following formula (A1-1). [ka] (In formula (A1-1), X is an organic group having 1 or more carbon atoms and 100 or less, R a1 R is a hydroxyl group, a carboxyl group, or a halogen atom. a2 is an aliphatic group, hydroxyl group, carboxyl group, sulfonic acid group, or halogen atom having 1 to 20 carbon atoms, and Ar is R a2 A phenyl group which may be substituted with, or R a2 The naphthyl group may be substituted with ma1, where ma1 is an integer between 0 and 10 (inclusive), ma2 is an integer between 0 and 7 (inclusive), and ma3 is an integer between 1 and 10 (inclusive).

[0040] In equation (A1-1), Ar is R a2 A phenyl group which may be substituted with, or R a2 It is a naphthyl group which may be substituted with . Ar is preferably a phenyl group or a naphthyl group. In other words, in formula (A1-1), ma2 is preferably 0.

[0041] In equation (A1-1), R a2 R is an aliphatic group, hydroxyl group, carboxyl group, sulfonic acid group, or halogen atom having 1 to 20 carbon atoms. a2 The organic group may include heteroatoms such as O, N, S, P, B, Si, and halogen atoms. R a2 The number of carbon atoms in the aliphatic group is preferably 1 to 12, and more preferably 1 to 6.

[0042] R a2Aliphatic 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-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and Chain-like alkyl groups such as n-icosyl group; chain-like alkenyl groups such as vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n-butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group; chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group Halogenated linear alkyl groups such as perfluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and perfluorodecyl group; halogenated cycloalkyl groups such as 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group, and 4-bromocyclohexyl group; hydroxylinear alkyl groups such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, and 4-hydroxy-n-butyl group; hydroxycycloalkyl groups such as 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group, and 4-hydroxycyclohexyl group;Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonyloxy group Chain-like alkoxy groups such as decyloxy groups and n-icosyloxy groups; chain-like alkenyloxy groups such as vinyloxy groups, 1-propenyloxy groups, 2-n-propenyloxy groups (allyloxy groups), 1-n-butenyloxy groups, 2-n-butenyloxy groups, and 3-n-butenyloxy groups; methoxymethyl groups, ethoxymethyl groups, n-propoxymethyl groups, 2-methoxyethyl groups, 2-ethoxyethyl groups, 2-n-propoxyethyl groups, 3-methoxy-n-propyl groups, 3-ethoxy-n-propyl groups, 3-n-propoxy-n-propyl groups, 4-methoxymethyl groups Alkoxyalkyl groups such as xy-n-butyl group, 4-ethoxy-n-butyl group, and 4-n-propoxy-n-butyl group; Alkoxyalkoxy groups such as methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 3-methoxy-n-propoxy group, 3-ethoxy-n-propoxy group, 3-n-propoxy-n-propoxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n-propoxy-n-butyloxy group Aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanol group, octanoyl group, nonanoyl group, and decanoyl group; linear alkyloxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyloxycarbonyl group;These are aliphatic acyloxy groups such as formyloxy, acetyloxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanyloxy, octanoyloxy, nonanoyloxy, and decanoyloxy.

[0043] 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.

[0044] In formula (A1-1), X is an organic group having 1 to 100 carbon atoms. The number of carbon atoms in the organic group as X is preferably 2 to 80, and more preferably 6 to 50. The organic group as X may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms. In the compound represented by formula (A1-1), the two amino groups are each bonded to carbon atoms in the organic group as X.

[0045] The organic group X may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group. The organic group X may be a group bonded via a bond containing heteroatoms such as an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of heteroatom-containing bonds in the organic group X that include an oxygen atom, a sulfur atom, and a nitrogen atom include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, with -O-, -CO-, and -S- being preferred.

[0046] If the organic group X is an aliphatic group, it may be either a saturated or unsaturated aliphatic group. If the organic group X is an aliphatic group, it is preferable that it is an aliphatic hydrocarbon group. If the organic group X is an aliphatic group, it may be linear, cyclic, or a combination of a linear aliphatic group and a cyclic aliphatic group. The linear aliphatic group may be branched.

[0047] When the organic group X is an aliphatic group, the aliphatic group is preferably an alkylene group having 1 to 20 carbon atoms from which (ma1+ma3+2) hydrogen atoms have been removed, more preferably an alkylene group having 1 to 16 carbon atoms from which (ma1+ma3+2) hydrogen atoms have been removed, and even more preferably an alkylene group having 1 to 12 carbon atoms from which (ma1+ma3+2) hydrogen atoms have been removed.

[0048] If the organic group X is a group containing an aromatic group, then X, Ar, and R in formula (A1-1) a1 , and R a2 Examples of groups composed of these are those represented by the following equations (11) to (15). [ka]

[0049] In equations (11) to (15), Ar, R a1 , R a2ma1, ma2, and ma3 are the same as those in equation (A1). In equation (13), ma4 and ma5 are each independent integers between 0 and 4. ma6 and ma7 are each independent integers between 0 and 4, and the sum of ma6 and ma7 is between 1 and 8. In equation (14), ma8, ma9, and ma10 are each independent integers between 0 and 4. The sum of ma8, ma9, and ma10 is between 0 and 10. ma11, ma12, and ma13 are each independent integers between 0 and 4. The sum of ma11, ma12, and ma13 is between 1 and 10. In equation (15), ma14 is an integer between 0 and 3. ma15 is an integer between 0 and 5. The sum of ma14 and ma15 is between 0 and 8. ma16 is an integer between 0 and 3. ma17 is an integer between 0 and 5 (inclusive). The sum of ma16 and ma17 is between 1 and 8 (inclusive).

[0050] In formula (11), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2. In formula (12), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2. In formula (13), ma2 is preferably 0, ma4 and ma5 are each preferably 0, ma6 and ma7 are each preferably 0, 1, or 2, and the sum of ma6 and ma7 is 1 or more, and preferably 4 or less. In formula (14), ma2 is preferably 0, ma8, ma9, and ma10 are each preferably 0, ma11, ma12, and ma13 are each preferably 0, 1, or 2, and the sum of ma11, ma12, and ma13 is 1 or more, and preferably 6 or less. In formula (15), ma2 is preferably 0, ma14 and ma15 are each preferably 0, ma16 and ma17 are each preferably 0, 1, or 2, and the sum of ma16 and ma17 is 1 or more and preferably 4 or less.

[0051] In equations (11) to (15), R a3The 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 having 1 to 20 carbon atoms, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, as well as groups formed by combining 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 a linking group may have one or more unsaturated bonds, may be branched, and may contain a ring structure. Specific examples of aliphatic hydrocarbon groups used as linking groups include methylene group, ethane-1,2-diyl group (ethylene group), ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, and undecane-1,1 Examples include 1-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, octadecane-1,18-diyl group, nonadecane-1,19-diyl group, icosane-1,20-diyl group, ethene-1,2-diyl group (vinylene group), propene-1,3-diyl group, ethyne-1,2-diyl group, and propyne-1,3-diyl group.

[0052] Preferred examples of linking groups include alkylene groups having 1 to 6 carbon atoms, alkenylene groups having 2 to 6 carbon atoms, alkylene groups having 2 to 6 carbon atoms, alkylene oxy groups having 1 to 6 carbon atoms, alkenylene oxy groups having 2 to 6 carbon atoms, alkylene oxy groups having 2 to 6 carbon atoms, alkylentho groups having 1 to 6 carbon atoms, alkenylene oxy groups having 2 to 6 carbon atoms, alkylene amino groups having 1 to 6 carbon atoms, alkenylene amino groups having 2 to 6 carbon atoms, alkylene amino groups having 2 to 6 carbon atoms, -CONH-, -NH-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, -OCONH-, and -OCOO-.

[0053] From the standpoint of exhibiting low dielectric loss tangent and good mechanical properties, the divalent group represented by formula (A1-1) is preferred over the divalent group represented by formula (A1-2) below. [ka] (In formula (A1-2), R a1 , R a2 Ar, ma1, ma2, and ma3 are the same as those in equation (A1-1), and Y a1 This is an organic group having 1 to 20 carbon atoms, or a single bond, Y a2 (This refers to an organic group with 1 to 20 carbon atoms, where na1 is either 0 or 1, and na2 is either 0 or 1. If na1 is 1, Ya1 is not a single bond.)

[0054] In formula (A1-2), Y a1 The organic group may include heteroatoms such as O, N, S, P, B, Si, and halogen atoms. a1 The organic group is preferably a hydrocarbon group. a1 The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. a1As the hydrocarbon group, an aromatic hydrocarbon group is preferred, and a phenylene group and a naphthalene diyl group are more preferred. a1 Suitable examples of aromatic hydrocarbon groups include p-phenylene, m-phenylene, o-phenylene, naphthalene-1,4-diyl, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, and naphthalene-2,3-diyl. Among these aromatic hydrocarbon groups, p-phenylene and m-phenylene are preferred, with p-phenylene being more preferred.

[0055] In formula (A1-2), it is preferable that na2 is 1, and both na1 and na2 are 1, Y a1 It is more preferable that the group is an organic group. In this case, due to the high steric degree of freedom of the ether bond, the structural units derived from the diamine compound (A-1) having a divalent group represented by formula (A1-2) are easily packed, and it is thought that a polyimide resin precursor (A1) that gives a polyimide resin with excellent mechanical properties, thermal properties, electrical properties, etc., can be easily obtained.

[0056] In formula (A1-2), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2.

[0057] The following compounds are specific examples of the diamine compound (A-1) described above. [ka]

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] (Diamine compound (A-2)) Diamine compound (A-2) has a substructure represented by the following formula (A2-1) and is a diamine compound that does not correspond to diamine compound (A-1). [ka] (In formula (A2-1), R a3 and R a4 Each of these is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and ma4 and ma5 are independently integers between 0 and 4.

[0066] In formula (A2-1), R a3 and R a4Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. Among these alkyl groups, methyl and ethyl groups are preferred, with methyl being more preferred. In formula (A2-1), 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 groups. Among these alkoxy groups, methoxy and ethoxy groups are preferred, with methoxy groups being more preferred. In formula (A2-1), R a3 and R a4 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Among these halogen atoms, chlorine and bromine are preferred.

[0067] In formula (A2-1), ma4 and ma5 are each an independent integer between 0 and 4. Because the diamine compound (A-2) is readily available, ma4 and ma5 are preferably integers between 0 and 2, and more preferably 0.

[0068] Suitable divalent groups having a substructure represented by formula (A2-1) include the divalent group represented by the following formula (A2-2). [ka] (In formula (A2-2), X 1 and X 2 Each of these is an aromatic hydrocarbon group that may be independently substituted with 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. a3 , R a4, ma4, and ma5 are the same as these in formula (A2-1). However, the upper limit of the number of carbon atoms of the divalent group represented by formula (A2-2) is 40.)

[0069] X in formula (A2-2) 1 and X 2 are each independently a divalent aromatic hydrocarbon group which may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom.) Examples of the alkyl group having 1 to 4 carbon atoms as a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these alkyl groups, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.) Examples of the alkoxy group having 1 to 4 carbon atoms as a substituent include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.) Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these halogen atoms, a chlorine atom and a bromine atom are preferred.)

[0070] X 1 and X 2 The number of carbon atoms of the aromatic hydrocarbon group as X and X is not particularly limited as long as the number of carbon atoms of the divalent group represented by formula (A2-2) is 40 or less. The number of carbon atoms of the aforementioned aromatic hydrocarbon group does not include the number of carbon atoms of the substituent.) X 1 , and X[[ID= 27]] 2Examples of the aromatic hydrocarbon group as such include phenylene groups such as o-phenylene group, m-phenylene group, and p-phenylene group; naphthalenediyl groups such as naphthalene-1,4-diyl group, naphthalene-1,3-diyl group, naphthalene-2,6-diyl group, and naphthalene-2,7-diyl group; and biphenyldiyl groups such as biphenyl-4,4'-diyl group, biphenyl-3,4'-diyl group, and biphenyl-3,3'-diyl group are preferable.

[0071] X 1 、and X 2 Examples of such include p-phenylene group, m-phenylene group, naphthalene-1,4-diyl group, and biphenyl-4,4'-diyl group are preferable, p-phenylene group and biphenyl-4,4'-diyl group are more preferable, and p-phenylene group is even more preferable.

[0072] Specific examples of the diamine compound (A-2) having a divalent group having the partial structure represented by the formula (A2-1) described above include the following compounds.

Chemical formula

[0073] (Diamine compound (A-3)) The diamine compound (A-3) has a partial structure represented by the following formula (A3) and is a diamine compound that does not correspond to the diamine compound (A-1) and the diamine compound (A-2).

Chemical formula

[0074] In formula (A3), R a5 and R a6 Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. Among these alkyl groups, methyl and ethyl groups are preferred, with methyl being more preferred. In formula (A3), 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 groups. Among these alkoxy groups, methoxy and ethoxy groups are preferred, with methoxy groups being more preferred. In formula (A3), R a5 and R a6 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Among these halogen atoms, chlorine and bromine are preferred.

[0075] In formula (A3), ma6 and ma7 are each independent integers between 0 and 4. Because the diamine compound (A-3) is readily available, ma6 and ma7 are preferably integers between 0 and 2, and more preferably 0.

[0076] In formula (A3), R a7 and R a8 Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. In formula (A3), R a7 and R a8Examples of halogenated alkyl 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. R in formula (A3) a7 and R a8 As such, hydrogen atoms, methyl groups, ethyl groups, trifluoromethyl groups, and phenyl groups are preferred because the polyimide resin precursor (A1) has good solubility in organic solvents and the diamine compound (A-3) is readily available. Also, R a7 and R a8 It is also preferable that these groups bond with each other to form cycloalkylidene groups having 5 to 8 carbon atoms, such as cyclopentylidene groups, cyclohexylidene groups, cycloheptylidene groups, and cyclooctylidene groups.

[0077] The following are some suitable examples of the substructure represented by formula (A3). [ka]

[0078] Suitable compounds for the diamine compound (A-3) include the compound represented by the following formula (A3-1). [ka] (In formula (A3-1), X 3 and X 4 Each of these is an aromatic hydrocarbon group that may be independently substituted with 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. a5 , R a6 , R a7 , R a8 , and ma6 and ma7 are the same as those in formula (A3).

[0079] X in equation (A3-1) 3 and X 4 Each of these is a divalent aromatic hydrocarbon group that may be independently substituted with 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. Examples of alkyl groups having 1 to 4 carbon atoms as substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. Among these alkyl groups, methyl and ethyl groups are preferred, with methyl groups being more preferred. Examples of alkoxy groups having 1 to 4 carbon atoms as substituents include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy groups. Among these alkoxy groups, methoxy and ethoxy groups are preferred, with methoxy groups being more preferred. Examples of halogen atoms used as substituents include fluorine, chlorine, bromine, and iodine. Among these halogen atoms, chlorine and bromine are preferred.

[0080] X 3 and X 4 The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited, but is preferably 6 to 50, and more preferably 6 to 20. Note that the number of carbon atoms in the aromatic hydrocarbon group mentioned above does not include the number of carbon atoms in substituents. X 3 and X 4 Preferred aromatic hydrocarbon groups include phenylene groups such as o-phenylene, m-phenylene, and p-phenylene groups; naphthalenediyl groups such as naphthalene-1,4-diyl, naphthalene-1,3-diyl, naphthalene-2,6-diyl, and naphthalene-2,7-diyl groups; and biphenyldiyl groups such as biphenyl-4,4'-diyl, biphenyl-3,4'-diyl, and biphenyl-3,3'-diyl groups.

[0081] X 3 and X 4 The preferred groups are 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.

[0082] The following compounds are specific examples of the diamine compound (A-3) represented by formula (A3) described above. [ka]

[0083] [ka]

[0084] (Dimer amine compound (A-4)) Dimer amine compounds (A-4) are also preferred as diamine compounds because they easily yield polyimide resin precursors (A1) that provide polyimide resins with low dielectric constant and dielectric loss tangent in the high-frequency band. Dimer amine compounds (A-4) are diamine compounds obtained by substituting the two terminal carboxyl groups of a dimer acid with aminomethyl groups or amino groups. Dimer acids are known dibasic acids obtained by intermolecular polymerization reactions of unsaturated fatty acids. Industrial manufacturing processes for producing dimer acids are almost standardized. Typically, dimer acids are obtained by dimerizing unsaturated fatty acids with 11 to 22 carbon atoms in the presence of a clay catalyst or the like. Industrially obtained dimer acids are mainly composed of dibasic acids with 36 carbon atoms obtained by dimerizing unsaturated fatty acids with 18 carbon atoms, such as oleic acid, linoleic acid, and linolenic acid. Industrially obtained dimer acids may contain arbitrary amounts of monomeric acids with 18 carbon atoms, trimer acids with 54 carbon atoms, and other polymeric fatty acids with 20 to 54 carbon atoms, depending on the degree of purification. As the dimer amine compound (A-4), a diamine compound represented by the following formula (31) is preferred. [ka]

[0085] 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 dashed part represents a carbon-carbon single bond or a carbon-carbon double bond.

[0086] Furthermore, since it is easier to obtain a polyimide resin precursor (A1) that can form a polyimide resin with superior elongation, the compound represented by formula (32) below is preferred as the diamine compound represented by formula (31). [ka]

[0087] Commercially available diamine compounds represented by formula (31) include Versamin 551 (manufactured by BASF) and Priamine 1074 (manufactured by Croda Japan), which contain the compound represented by formula (33) below, and Versamin 552 (manufactured by BASF), Priamine 1073 (manufactured by Croda Japan), and Priamine 1075 (manufactured by Croda Japan), which contain the compound represented by formula (32) above. Such commercially available dimer amine compounds (A-4) are usually mixtures containing multiple amine compounds. [ka]

[0088] Furthermore, by reacting the diamine compound represented by formula (31) with an acid halide derived from trimellitic anhydride, a tetracarboxylic dianhydride represented by the following formula (34) can be obtained. It is also preferable to use the tetracarboxylic dianhydride represented by the following formula (34) as a raw material for producing polyimide resin precursor (A1). 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 dashed part represents a carbon-carbon single bond or a carbon-carbon double bond. [ka]

[0089] The ratio of the number of moles of one or more compounds selected from the group consisting of diamine compound (A-1), diamine compound (A-2), diamine compound (A-3), and dimeramine compound (A-4) to the total number of moles of diamine compounds is preferably 10 mol% or more and 100 mol% or less, more preferably 15 mol% or more and 100 mol% or less, and even more preferably 20 mol% or more and 100 mol% or less.

[0090] (Tetracarboxylic acid dianhydride) The tetracarboxylic dianhydride is not particularly limited as long as the desired effect is not impaired. Typically, tetracarboxylic dianhydrides that have been conventionally used in the production of polyamic acids and polyimide resins can be used. Examples of tetracarboxylic dianhydrides include compounds represented by the following formula (A3). [ka] (In formula (A3), X A1 (This refers to a tetravalent organic group with 4 to 40 carbon atoms.)

[0091] In formula (A3), X A1 This is a tetravalent organic group having 4 to 40 carbon atoms, and may have one or more substituents in addition to the two -CO-O-CO- acid anhydride groups represented by formula (A3). Preferred examples of substituents include fluorine atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, fluorinated alkyl groups having 1 to 6 carbon atoms, and fluorinated alkoxy groups having 1 to 6 carbon atoms. In addition, the compound represented by formula (A3) may contain a carboxyl group or a carboxylic acid ester group in addition to the acid anhydride group. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferable that it be a perfluoroalkyl group or a perfluoroalkoxy group. The same applies to the substituents described above, as well as to the one or more substituents that the aromatic group may have on its aromatic ring, as described later.

[0092] X A1 The number of carbon atoms constituting the compound is preferably 8 or more, and more preferably 12 or more. Also, X A1 The number of carbon atoms constituting it is preferably 30 or less. A1 This can be an aliphatic group, an aromatic group, or a group that combines these structures. A1 In addition to carbon atoms and hydrogen atoms, it may also contain halogen atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. A1 If it contains an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, nitrogen atom, or sulfur atom is a group selected from a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, X A1 It may be included as a group selected from -O-, -CO-, -S-, and X A1 It is preferable to give birth to them.

[0093] The tetracarboxylic dianhydride represented by formula (A3) may be an aliphatic tetracarboxylic dianhydride having two dicarboxylic anhydride groups bonded to an aliphatic group, or an aromatic tetracarboxylic dianhydride having at least one dicarboxylic anhydride group bonded to an aromatic group. Furthermore, it is preferable that the aromatic tetracarboxylic dianhydride has two dicarboxylic anhydride groups bonded to the aromatic group. That is, X A1 The tetravalent organic group is preferably a residue obtained by removing two dicarboxylic acid anhydride groups from an aromatic tetracarboxylic dianhydride.

[0094] Aliphatic tetracarboxylic dianhydrides may contain an alicyclic structure. This alicyclic structure may be polycyclic. An example of an aliphatic tetracarboxylic dianhydride that does not have an alicyclic structure is 1,2,3,4-tetracarboxylic dianhydride (e.g., Ricacid BT-100, manufactured by Shin Nippon Rika Co., Ltd.). Aliphatic tetracarboxylic dianhydrides having an alicyclic structure include cyclobutanetetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride (e.g., Enehyde® CpODA, manufactured by ENEOS Corporation), 2,2-bis(2, Examples include 3-dicarboxyphenoxy)hexafluoropropane dianhydride [5,5'-(1,4-phenylene)bisnorbornane]-2,2',3,3'-tetracarboxylic dianhydride (e.g., Enehyde® BzDA, manufactured by ENEOS Corporation) and 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione (e.g., Ricacid TDA-100, manufactured by Shin Nippon Rika Co., Ltd.).

[0095] Examples of aromatic tetracarboxylic dianhydrides represented by formula (A3) and having two dicarboxylic acid anhydride groups bonded to an aromatic group include pyromellitic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 4,4'-oxydiphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, and 3,3',4,4'-benzophenone tetracarboxylate. Dianhydride of benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic acid dianhydride, trimellitic acid (3,4-dicarboxyphenyl) dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 2,3,5,6-pyridine tetracarboxylic acid Acidic dianhydrides, 3,4,9,10-perylenetetracarboxylic acid dianhydride, bis(2,3-dicarboxyphenoxy)methane dianhydride, 1,1-bis(2,3-dicarboxyphenoxy)ethane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride (bis(1,3-dioxo-1,3-dihydroisobenzofuran) Examples include (-5-carboxylic acid)=1,1'-biphenyl-4,4'-diyl), 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride, 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (e.g., Ricacid TMEG100, manufactured by Shin Nippon Rika Co., Ltd.), and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane Kasei Co., Ltd.). Among these aromatic tetracarboxylic dianhydrides, 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride, 4,4'-bis(3,4-dicarboxyphenyloxy)biphenyl dianhydride, 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride, and α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride are preferred because they readily form cured products with excellent electrical properties. α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride is a compound represented by the following formula (a1). [ka]

[0096] In formula (a1), n ​​is an integer of 1 or more, preferably between 1 and 20, and more preferably between 2 and 12. Suitable specific examples of α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkane dianhydride include 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (e.g., Ricacid TMEG100, manufactured by Shin Nippon Rika Co., Ltd.) and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane Kasei Co., Ltd.).

[0097] Furthermore, it is preferable that the aromatic tetracarboxylic dianhydride is biphenyltetracarboxylic dianhydride, as this suppresses warping of the formed polyimide resin film and improves the photolithography properties of the photosensitive resin composition. Examples of biphenyltetracarboxylic dianhydrides include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyltetracarboxylic dianhydride, with 3,3',4,4'-biphenyltetracarboxylic dianhydride being preferred.

[0098] The aromatic tetracarboxylic dianhydride may also be, for example, a compound represented by the following general formulas (a3-2) to (a3-4). [ka]

[0099] In the above equations (a3-2) and (a3-3), R a01 , R a02 and R a03 Each of these represents a divalent group consisting of an aliphatic group which may be substituted with a halogen, an oxygen atom, a sulfur atom, an aromatic group via one or more divalent elements, or a combination thereof. a02 and R a03 They may be the same or different. That is, R a01 , R a02 and R a03 This may include a carbon-carbon single bond, a carbon-oxygen-carbon ether bond, or a halogen element (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)benzene dianhydride.

[0100] Furthermore, in the above formula (a3-4), R a04 , R a05R represents a monovalent substituent consisting of an aliphatic group which may be substituted with a halogen, an aromatic group via one or more divalent elements, a halogen, or a combination thereof. a04 , and R a05 These may be the same or different. As the compound represented by formula (a3-4), difluoropyromellitic dianhydride and dichloropyromellitic dianhydride can also be used.

[0101] The polyimide resin precursor (A1) is also preferably characterized by having radical polymerizable group-containing groups on its molecular chain. Therefore, the tetravalent organic group X in formula (A3) A1 The base may be represented by the following formulas (a3-5) to (a3-7). [ka] In equations (a3-5) to (a3-7), R a01 , R a02 , and R a03 In the aforementioned equations (a3-2), (a3-3), and (a3-4), R a01 , R a02 , and R a03 It is similar to that. In equations (a3-5), (a3-6), and (a3-7), R a06 This is a radical polymerizable group-containing group.

[0102] (Method for producing polyimide resin precursor (A1)) The polyimide resin precursor (A1) can be produced by reacting the aforementioned diamine compound with a tetracarboxylic dianhydride.

[0103] The reaction between a diamine compound and a tetracarboxylic dianhydride is usually carried out in a solvent. The solvent used in the reaction between the diamine compound and the tetracarboxylic dianhydride is not particularly limited as long as it can dissolve the diamine compound and the tetracarboxylic dianhydride and does not react with the diamine compound and the tetracarboxylic dianhydride. One solvent may be used alone, or two or more solvents may be used in combination.

[0104] Examples of solvents used in the reaction between diamine compounds and 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 cellulose acetate, and ethyl cellulose acetate; and phenolic solvents such as cresols and xylene-based mixed solvents.

[0105] The reaction temperature is generally 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, but is usually between 3 and 24 hours.

[0106] The amounts of diamine compound and tetracarboxylic dianhydride used in the production of polyimide resin precursor (A1) are not particularly limited, but it is preferable to use 0.8 moles to 1.2 moles of diamine compound per mole of tetracarboxylic dianhydride, more preferably 0.9 moles to 1.1 moles, and particularly preferably 0.95 moles to 1.05 moles.

[0107] A partially imidized polyimide resin precursor (A1) can be produced, for example, by reacting a diamine compound with a tetracarboxylic dianhydride, then imidizing it by heating or other means to produce a polymer having imide units, and then reacting this polymer with a diamine compound and a tetracarboxylic dianhydride. Alternatively, a partially imidized polyimide resin precursor (A1) can also be produced by reacting a diamine compound with a tetracarboxylic dianhydride, and then imidizing it by heating or other means.

[0108] The polyimide resin precursor (A1) is represented by formula (a1), R A1 , and R A2 If at least one of the constituent units is an organic group, a polyimide resin precursor (A1) can be produced by reacting one of the dicarboxylic acid anhydride groups in the tetracarboxylic dianhydride represented by formula (A3) with an alcohol to open the ring, and then condensing the resulting compound with a diamine compound according to a conventional method. In this case, the tetracarboxylic dianhydride represented by formula (A3) may be condensed with a diamine compound, along with a compound obtained by reacting one of the dicarboxylic anhydride groups in the tetracarboxylic dianhydride represented by formula (A3) with an alcohol to open its ring.

[0109] The alcohols reacted with the tetracarboxylic dianhydride represented by formula (A3) may be unsaturated alcohols having an ethylenically unsaturated double bond, or saturated alcohols.

[0110] Specific examples of unsaturated alcohols include allyl alcohol; butenols such as buta-3-en-1-yl alcohol and buta-2-en-1-yl alcohol; pentenols such as penta-4-en-1-yl alcohol, penta-3-en-1-yl alcohol and penta-2-en-1-yl alcohol; hexenols such as hexa-5-en-1-yl alcohol, hexa-4-en-1-yl alcohol, hexa-3-en-1-yl alcohol and hexa-2-en-1-yl alcohol; and hepta-6-en-1-yl alcohol. Heptenols such as hepta-5-en-1-yl alcohol, hepta-4-en-1-yl alcohol, hepta-3-en-1-yl alcohol, and hepta-2-en-1-yl alcohol; octenols such as octa-7-en-1-yl alcohol, octa-6-en-1-yl alcohol, octa-5-en-1-yl alcohol, octa-4-en-1-yl alcohol, octa-3-en-1-yl alcohol, and octa-2-en-1-yl alcohol; nona-8-en-1-yl alcohol, nona-7-en Nonenols such as nona-1-yl alcohol, nona-6-en-1-yl alcohol, nona-5-en-1-yl alcohol, nona-4-en-1-yl alcohol, nona-3-en-1-yl alcohol, and nona-2-en-1-yl alcohol; deca-9-en-1-yl alcohol, deca-8-en-1-yl alcohol, deca-7-en-1-yl alcohol, deca-6-en-1-yl alcohol, deca-5-en-1-yl alcohol, deca-4-en-1-yl alcohol, deca-3-en-1-yl alcohol, and4-en-1-yl alcohol, deca-3-en-1-yl alcohol, and deca-2-en-1-yl alcohol; Decenols such as car-2-en-1-yl alcohol; undecenols such as undeca-10-en-1-yl alcohol; dodecenols such as dodeca-11-en-1-yl alcohol; tridecenols such as trideca-12-en-1-yl alcohol; tetradecenols such as tetradeca-13-en-1-yl alcohol; pentadecenols such as pentadeca-14-en-1-yl alcohol; hexadecenols such as hexadeca-15-en-1-yl alcohol; heptadecenols such as heptadeca-16-en-1-yl alcohol;Examples include octadecenols such as octadeca-17-en-1-yl alcohol and octadeca-9-en-1-yl alcohol (oleyl alcohol); nonadecenols such as nonadeca-18-en-1-yl alcohol; eicosenols such as eicosan-19-en-1-yl alcohol; and octadienols such as octadeca-9,12-dien-1-yl alcohol (linoleyl alcohol).

[0111] Other specific examples of unsaturated alcohols include mono(meth)acrylates of diols such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxypropan-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 group-substituted (meth)acrylamides such as N-(2-hydroxyethyl)(meth)acrylamide; and hydroxyl group-containing ketones such as (hydroxymethyl) vinyl ketone and (2-hydroxyethyl) vinyl ketone.

[0112] Furthermore, the following compounds are also preferred as unsaturated alcohols. [ka]

[0113] 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 glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, 1,3-propanediol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.

[0114] The weight-average molecular weight of the polyimide resin precursor (A1) may be set appropriately according to the application of the photosensitive resin composition. In this specification, the weight-average molecular weight can be measured as the weight-average molecular weight in polystyrene terms by GPC (gel permeation chromatography). The weight-average molecular weight of the polyimide resin precursor (A1) is preferably 5000 or more, more preferably 15000 or more, and more preferably 250,000,000 or more, in terms of polystyrene terms, from the viewpoint of obtaining a resin film with better mechanical properties. On the other hand, the weight-average molecular weight of the obtained polyimide resin precursor (A1) is preferably 100,000 or less, more preferably 80,000 or less, and more preferably 50,000 or less, in terms of polystyrene terms, from the viewpoint of solubility in organic solvents, etc. This weight-average molecular weight allows for adjustment of the proportions of the aforementioned tetracarboxylic dianhydride and diamine compound, as well as reaction conditions such as the solvent and reaction temperature.

[0115] The main chain ends of the polyimide resin precursor (A1) may be encapsulated with an end-capturing agent. Examples of end-capturing agents include monoamines, acid anhydrides, monocarboxylic acids, monoacid halides, and monoactive ester compounds. Known compounds can be used as monoamines for end-capping. Examples of monoamines include aromatic monoamines such as aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 3-hydroxyaniline, 4-hydroxyaniline, 3-aminothiophenol, and 4-aminothiophenol; aliphatic monoamines that may have a branched structure with 3 to 20 carbon atoms, such as hexylamine and octylamine; monoamines having an alicyclic structure, such as cyclohexylamine; and aminosilanes such as trimethoxyaminopropylsilane and triethoxyaminopropylsilane. Among acid anhydrides, monoacid halides, and monoactive ester compounds used as end-cap sealing 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, xo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, succicic anhydride, maleic anhydride, nadic anhydride, and their derivatives. Regarding the introduction rate of the end encapsulant in the polyimide resin precursor (A1), from the viewpoint of having excellent mechanical properties of the formed polyimide resin film, it is preferable to have a rate of 40 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less, relative to the total number of moles of monomers.

[0116] [Isocyanate compound (A2)] 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.

[0117] The number of (meth)acryloyl groups in the isocyanate compound (A2) is not particularly limited and may be one or two or more. It is preferable that the isocyanate compound (A2) has one or two (meth)acryloyl groups.

[0118] The number of isocyanate groups in isocyanate compound (A2) is not particularly limited and may be one or two or more. It is preferable that isocyanate compound (A2) includes isocyanate compound (A2a) having one isocyanate group.

[0119] A suitable example of the isocyanate compound (A2) is the compound represented by the following formula (a2). H2C=CR 01 -C(=O)-OR 02 -Z 01 -R 03 -NCO···(a2) (In the formula, R 01 is a hydrogen atom or a methyl group, R 02 This is an alkylene group which may have substituents, Z 01 This is a single bond or an oxygen atom, R 03 (This is an alkylene group that may have a single bond or substituents.)

[0120] In formula (a2), R 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. Examples of branched alkylene groups include methylethylene group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 1,1-dimethylethylene group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group, 1,2-dimethylpropane-1,3-diyl group, 1,1-dimethylpropane-1,3-diyl group, and 2,2-dimethylpropane-1,3-diyl group. R 02 A possible substituent that the alkylene group may have is a (meth)acryloyloxy group.

[0121] In formula (a2), R 03Alkylene group and R 03 The substituents that the alkylene group may have include R 02 Alkylene group and R 02 This is similar to the substituents that the alkylene group may have.

[0122] Specific examples of isocyanate compounds (A2) include the following compounds. [ka]

[0123] [Method for producing reactant (A)] 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.

[0124] The reaction between the polyimide resin precursor (A1) and the isocyanate compound (A2) is usually carried out in a solvent. The solvent used in the reaction between the polyimide resin precursor (A1) and the isocyanate compound (A2) is not particularly limited as long as it can dissolve the polyimide resin precursor (A1) and the isocyanate compound (A2) and does not react with the polyimide resin precursor (A1) and the isocyanate compound (A2). One solvent may be used alone, or two or more solvents may be used in combination.

[0125] Examples of solvents used in the reaction between the polyimide resin precursor (A1) and the 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 cellulose acetate, and ethyl cellulose acetate; and phenolic solvents such as cresols and xylene-based mixed solvents.

[0126] 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.

[0127] The amounts of polyimide resin precursor (A1) and isocyanate compound (A2) used in the production of reaction product (A) are not particularly limited. Preferably, the amount of isocyanate groups in the isocyanate compound (A2) is 0.4 moles or more and 1.5 moles or less, and more preferably 0.5 moles or more and 1.3 moles or less, per mole of carboxyl groups in the polyimide resin precursor (A1).

[0128] Here, as described above, reactant (A) is 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. In reactant (A), it is presumed that 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 such as NMR, and the bonding state remains unknown. Therefore, it is impossible to identify the structure of reactant (A), or the work required to identify it would incur excessively high economic expenditure and time. For this reason, reactant (A) cannot be identified by its structure or physical properties, and reactant (A) is identified by the definition "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."

[0129] In this specification and in the claims, reactant (A) may be the reactant itself obtained by reacting a polyimide resin precursor (A1) having a constituent unit represented by formula (a1) with an isocyanate compound (A2) having a (meth)acryloyl group, or it may be obtained by further reacting a diamine compound and a tetracarboxylic dianhydride to add constituent units of the polyimide resin precursor such as polyamic acid. The constituent units of the polyimide resin precursor to be added may be the constituent units represented by formula (a1) above, or constituent units other than those represented by formula (a1) above.

[0130] <Thermobase generator (B)> The photosensitive resin composition contains a thermobase generator (B) that generates imidazole upon heating. The thermal base generator (B) is preferably a compound that generates one imidazole molecule upon heating. The imidazole generated by heating the thermal base generator (B) may have substituents. Examples of substituents include alkyl groups, halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, silyl groups, silanol groups, nitro groups, nitroso groups, phosphino groups, sulfonate groups, phosphinyl groups, and phosphonato groups. Examples of alkyl groups include alkyl groups having 1 to 8 carbon atoms, with specific examples including methyl groups, ethyl groups, and isopropyl groups.

[0131] As the thermal base generator (B), a thermal base generator (B1) having the structure represented by the following formula (b1) is preferred. -R B1 -C(=O)-Imd (b1) (In formula (b1), R B1 (wherein is a single bond or oxygen atom, and Imd is an imidazole-1-yl group which may have substituents.)

[0132] In formula (b1), the substituents that the imidazole-1-yl group may have include alkyl groups, halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, silyl groups, silanol groups, nitro groups, nitroso groups, phosphino groups, sulfonate groups, phosphinyl groups, and phosphonato groups. Examples of alkyl groups include alkyl groups having 1 to 8 carbon atoms, and specific examples include methyl groups, ethyl groups, and isopropyl groups.

[0133] In formula (b1), R B1 It is preferable that it is an oxygen atom.

[0134] The thermal base generator (B1) is R in formula (b1). B1 Preferably, the atom is an oxygen atom and is a tertiary or secondary ester.

[0135] The thermobase generator (B1) preferably has one structure represented by formula (b1). Specific examples of thermal base generators (B1) include the following compounds. [ka]

[0136] The content of the thermal base generating agent (B) in the photosensitive resin composition is not particularly limited. Typically, the content of the thermal base 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, per 100 parts by mass of the reactant (A).

[0137] <Photoradical polymerization initiator (C)> The photosensitive resin composition contains a photoradical polymerization initiator (C). The photoradical polymerization initiator (C) is not particularly limited, and conventionally known photopolymerization initiators can be used.

[0138] Specifically, the photoradical polymerization initiator (C) includes 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl [-propionyl)-benzyl]phenyl]-2-methyl-propan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) (Nyl)-butan-1-one, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butan-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-butadione-2-(o -Methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl) oxime, etanone, 1-phenyl-1,2-propanedione-2-(O-benzoyl) oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl) oxime, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazole-3-yl]etanone oxime (Irgacure OXE02, manufactured by BASF Japan), (9-ethyl-6-nitro-9H-carbazole-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(0-acetyloxime),2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (Irgacure OXE01, BASF Japan), NCI-831 (ADEKA), NCI-930 (ADEKA), OXE-03 (BASF Japan), OXE-04 (BASF Japan), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethyl Minobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, ethyl 4-diethylbenzoate, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, methyl benzoylformate, ethyl benzoylformate, 2,4-diethyl Thioxanthones, 2-chlorothioxanthones, 2,4-dimethylthioxanthones, 1-chloro-4-propoxythioxanthones, thioxanthenes, 2-chlorothioxanthenes, 2,4-diethylthioxanthenes, 2-methylthioxanthenes, 2-isopropylthioxanthenes, anthraquinones, 2-ethylanthraquinones, 2-tert-butylanthraquinones, octamethylanthraquinones, 2-aminoanthraquinones, β-chloranthraquinones, 1,2-benzanthraquinones, 2,3-diphenylanthraquinones N, anthron, benzantron, dibenzsuberone, methyleneantron, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-Dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, 4-hydroxybenzophenone, 4-phenylbenzophenone, fluorenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, 2-hydroxy-2-methylpropiophenone, dichloroacetophenone , trichloroacetophenone, p-tert-butylacetophenone, 2-phenylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3-(3,4-di Methyl-9-oxo-9H-thioxanthene-2-yloxy)-N,N,N-trimethyl-1-propanaminonium chloride, 4-azidobenzalacetophenone, 2,6-bis(p-azidobenzylidene)cyclohexane, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone, dibenzosverone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxy Citriaidine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 4-benzoyl-4'- Examples include methyl diphenyl ketone, dibenzyl ketone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethaminonium bromide, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propenaminonium chloride monohydrate, naphthalene sulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone, benzthiazole disulfide, triphenylphosphine, carbon tetrabrominated, and tribromophenylsulfone. These photoradical polymerization initiators (C) can be used alone or in combination of two or more. From the standpoint of good sensitivity, oxime ester-based photopolymerization initiators are preferred as the photoradical polymerization initiator (C).

[0139] Among photoradical polymerization initiators (C), oxime ester compounds are preferred in terms of the sensitivity of the photosensitive resin composition. As the oxime ester compound, a compound having a substructure represented by the following formula (c1) is preferred.

[0140] [ka] (In formula (c1), n1 is 0 or 1, R c2 is a monovalent organic group, R c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, * represents a bond.)

[0141] In the photosensitive resin composition, the content of the photo radical polymerization initiator (C) is not particularly limited as long as the photosensitive resin composition has the desired photolithography characteristics. The content of the photo radical polymerization initiator (C) in the photosensitive resin composition is typically preferably 0.01 part by mass or more and 20 parts by mass or less, more preferably 0.1 part 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 with respect to 100 parts by mass of the reactant (A).

[0142] <Solvent (S)> The photosensitive resin composition usually contains a solvent (S) for the purpose of adjusting coating properties and the like. The type of the solvent (S) is not particularly limited as long as the reactant (A) and other components are well dissolved. Usually, an organic solvent is used as the solvent (S).

[0143] Given the good solubility of reactant (A), specific examples of solvent (S) include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylisobutyrate, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, and N,N-dimethyl Nitrogen-containing polar solvents such as propionamide, N,N-dimethylisobutylamide, N,N-dimethylethylene urea, N,N-dimethylpropylene urea, N,N,N',N'-tetramethylurea, N,N,N',N'-tetraethylurea, and N,N,N',N'-tetrabutylurea; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, diisobutyl ketone, cyclopentanone, cyclohexanone, and isophorone;γ-Butyrolactone, γ-Valerolactone, δ-Valerolactone, γ-Caprolactone, ε-Caprolactone, α-Methyl-γ-Butyrolactone, Methyl Lactate, Ethyl Lactate, Methyl Acetate, Ethyl Acetate, N-Propyl Acetate, N-Butyl Acetate, Isobutyl Acetate, Isopentyl Acetate, N-Pentyl Formate, N-Butyl Propionate, Isopropyl Butyrate, Ethyl Butyrate, N-Butyl Butyrate, Methyl Methoxyacetate, Ethyl Methoxyacetate, N-Butyl Methoxyacetate, Methyl Ethoxyacetate, Ethoxyacetate, Methyl 3-Methoxypropionate 3-ethyl methoxypropionate, 3-methyl ethoxypropionate, 3-ethyl ethoxypropionate, 2-methyl methoxypropionate, 2-ethyl methoxypropionate, 2-methyl ethoxypropionate, 2-ethyl ethoxypropionate, 2-methyl methoxy-2-methylpropionate, 2-methyl ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, propylene glycol Examples include esters such as methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate; alcohols such as diacetone alcohol and 3-methyl-3-methoxybutanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, and diethylene glycol dimethyl ether; aromatic ethers such as anisole; cyclic ethers such as dioxane and tetrahydrofuran; cyclic esters such as ethylene carbonate and propylene carbonate; aromatic solvents such as anisole, toluene, and xylene; aliphatic hydrocarbons such as limonene; and sulfoxides such as dimethyl sulfoxide.

[0144] The amount of solvent (S) used is not particularly limited as long as a uniform liquid photosensitive resin composition can be prepared. The photosensitive resin composition may be a suspension or a solution, but a solution is preferred. Typically, the solvent (S) is used such that the solid content concentration of the photosensitive resin composition is preferably 15% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 45% by mass or less.

[0145] <Other ingredients> The photosensitive resin composition may optionally contain various additives other than those described above. Examples of additives include colorants, dispersants, sensitizers, adhesion promoters, polymerization inhibitors, antioxidants, ultraviolet absorbers, anti-flocculants, defoamers, surfactants, imidation promoters, nitrogen-containing heterocyclic compounds as adhesion improvers, and silane coupling agents. The photosensitive resin composition may also optionally contain various fillers or reinforcing materials.

[0146] 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 derivatives thereof.

[0147] 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-oxyl compounds, and phenothiazine compounds. More specifically, preferred polymerization inhibitors are Irganox1010, Irganox1035, Irganox1098, Irganox1135, Irganox245, Irganox259, Irganox3114 (all manufactured by BASF Japan), 2,6-di-tert-butyl-p-cresol, and 4-methoxyphenol, with Irganox1010, 2,6-di-tert-butyl-p-cresol, and 4-methoxyphenol being more preferred.

[0148] In order to achieve both excellent developability and good antioxidant effect of the photosensitive resin composition, the amount of polymerization inhibitor used is preferably 0.005% to 1% by mass, more preferably 0.01% to 0.5% by mass, and even more preferably 0.03% to 0.3% by mass, relative to the mass of reactant (A).

[0149] Nitrogen-containing heterocyclic compounds improve the adhesion of resin films formed using photosensitive resin compositions to metal surfaces by coordinating and stabilizing them on the metal surface. Known compounds can be used as nitrogen-containing heterocyclic compounds. Examples of nitrogen-containing heterocyclic compounds include pyrazole, indazole, carbazole, triazole, pyrazoline, pyrazolidine, tetrazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid, and their derivatives. Specific examples of nitrogen-containing heterocyclic compounds preferred from the viewpoint of metal coordination 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.

[0150] From the viewpoint of achieving both excellent developability of the photosensitive resin composition and improved adhesion of the polyimide resin film formed using the photosensitive resin composition to a substrate, the amount of nitrogen-containing heterocyclic compound used is preferably 0.01% to 5% by mass, and more preferably 0.05% to 3% by mass, relative to the mass of reactant (A).

[0151] By incorporating a silane coupling agent into a photosensitive resin composition, the adhesion of the resin film formed using the photosensitive resin composition to a substrate can be improved. Known compounds can be used as the silane coupling agent. Examples of silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(epoxycyclohexyl)ethyltrimethoxysilane, 2-(epoxycyclohexyl)triethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, tris(3-triethoxysilylpropyl)isocyanurate, reaction products of 3-aminopropyltrimethoxysilane and acid anhydrides, and reaction products of 3-aminopropyltriethoxysilane and acid anhydrides. Examples of acid anhydrides to be reacted with 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane include succinic anhydride, maleic anhydride, nadic anhydride, 3-hydroxyphthalic anhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, and 4,4'-oxydiphthalic dianhydride.

[0152] 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).

[0153] By incorporating a surfactant into a photosensitive resin composition, the coatability of the photosensitive resin composition is improved, as is the wettability of the photosensitive resin composition with the substrate. Known compounds can be used as the surfactant. Examples of surfactants include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants.

[0154] 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).

[0155] The amounts of various additives used are not particularly limited as long as they do not hinder the objective of the present invention. For additives whose amounts are not specified above, the amount used can be appropriately adjusted within a range of, for example, 0.001% by mass or more and 60% by mass or less, relative to the mass of the solid content of the photosensitive resin composition, and preferably 0.01% by mass or more and 5% by mass or less.

[0156] <Method for preparing a photosensitive resin composition> A photosensitive resin composition can be prepared by uniformly mixing the essential components described above, along with optional components as needed, in desired amounts. The mixing method is not particularly limited. It is preferable to filter the photosensitive resin composition using a filter in order to remove foreign matter from the composition.

[0157] Photosensitive dry film The photosensitive dry film comprises a base film and a photosensitive layer formed on the surface of the base film, wherein the photosensitive layer is made of the aforementioned photosensitive resin composition.

[0158] As the base film, one that has light transmittance is preferred. Specifically, examples include polyethylene terephthalate (PET) film, polypropylene (PP) film, and polyethylene (PE) film, but polyethylene terephthalate (PET) film is preferred because it has an excellent balance between light transmittance and tensile strength.

[0159] A photosensitive dry film is manufactured by applying the aforementioned photosensitive resin composition onto a base film to form a photosensitive layer. When forming a photosensitive layer on a substrate film, an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, etc. are used to apply a photosensitive resin composition onto the substrate film so that the film thickness after drying is preferably 0.5 μm or more and 300 μm or less, more preferably 1 μm or more and 300 μm or less, and particularly preferably 3 μm or more and 100 μm or less, and then dried.

[0160] The photosensitive dry film may further have a protective film on the photosensitive layer. Examples of this protective film include a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, etc.

[0161] ≪Method for manufacturing a patterned polyimide resin film≫ Applying the aforementioned photosensitive resin composition onto a substrate to form a coating film, Selectively exposing the coating film in a position-dependent manner, Developing the exposed coating film to obtain a patterned resin film, Heating the patterned resin film to generate a polyimide resin derived from the reactant (A), whereby a patterned polyimide resin film is formed by the method.

[0162] The substrate is not particularly limited, and conventionally known substrates can be used. For example, substrates for electronic components and those with a predetermined wiring pattern formed thereon can be exemplified. As the substrate, a silicon substrate, a glass substrate, etc. can also be used.

[0163] The thickness of the coating film is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, particularly preferably 1 μm or more and 150 μm or less, and most preferably 3 μm or more and 100 μm or less.

[0164] Methods for applying the photosensitive resin composition to the substrate include spin coating, slit coating, roll coating, screen printing, and applicator coating.

[0165] A photosensitive resin composition applied to a substrate is usually dried to form a coating film. The method for drying the photosensitive resin composition applied to the substrate is not particularly limited. Preferably, drying is performed by heating. The heating conditions during drying vary depending on the type and proportion of each component in the photosensitive resin composition, the coating film thickness, etc., but are usually 70°C to 200°C, preferably 80°C to 150°C, for about 2 minutes to 120 minutes.

[0166] The coated film formed as described above is exposed by positionally irradiating it with active light or radiation. Positionally selective exposure is usually performed by positionally irradiating it with active light or radiation, such as ultraviolet or visible light with a wavelength of 300 nm to 500 nm, through a mask of a predetermined pattern.

[0167] As radiation sources, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, etc., can be used. Radiation includes microwaves, infrared rays, visible light, ultraviolet rays, X-rays, gamma rays, electron beams, proton beams, neutron beams, and ion beams. The radiation dose varies depending on the composition of the photosensitive resin composition and the thickness of the coating film, but for example, when using an ultra-high-pressure mercury lamp, it is 100 mJ / cm². 2 More than 10000mJ / cm 2 The following applies:

[0168] Next, the exposed coating film is developed according to a conventionally known method, and unwanted portions are dissolved and removed to form 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 solvent (S) mentioned above can be used as the developer solution. If the reactant (A) mentioned above is a resin having an alkali-soluble group such as a carboxyl group, an alkaline aqueous solution can be used as the developer solution.

[0169] As alkaline developers, aqueous solutions of alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (tetramethylammonium hydroxide), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonane can be used. Alternatively, aqueous solutions of the above alkalis to which appropriate amounts of water-soluble organic solvents such as methanol and ethanol or surfactants can be added can also be used as developers.

[0170] The development time varies depending on the composition of the photosensitive resin and the thickness of the coating film, but is usually between 1 minute and 30 minutes. Any development method is acceptable, such as the liquid-filling method, dipping method, paddle method, or spray development method.

[0171] Next, the patterned resin film is heated to generate polyimide resin derived from reactant (A). This produces a patterned polyimide resin film.

[0172] The heating conditions are not particularly limited, as long as the reactant (A) does not decompose and hardening proceeds well. The heating temperature is preferably 80°C to 220°C, more preferably 100°C to 200°C, and particularly preferably 120°C to 180°C. Here, there are concerns that heating at high temperatures may cause the substrate to warp or damage the semiconductor elements. However, with the above-mentioned photosensitive resin composition, the reactant (A) can be cured at a low temperature (for example, 200°C or below), thus suppressing adverse effects caused by heating at high temperatures, such as warping of the substrate and damage to semiconductor elements. The curing temperature may be 200°C or lower, but it may also be higher than 200°C depending on the substrate used. The heating time depends on the heating temperature, but is typically preferably between 10 minutes and 24 hours, and more preferably between 30 minutes and 2 hours. Heating is preferably carried out under an inert gas atmosphere such as nitrogen or argon, from the viewpoint of preventing oxidation of the resin film and obtaining a resin film with better mechanical properties.

[0173] After heating, wash for 30 to 90 seconds as needed, and dry the patterned polyimide resin film using an air gun or oven. The washing solvent is not particularly limited. For example, when alkaline development is performed, water or alcohols can be used as the washing solvent. When development is performed with solvent (S), solvent (S) can be used as long as solvent shock does not occur.

[0174] The patterned polyimide resin film formed as described above is suitably used, for example, as an insulating film in semiconductor devices, an interlayer insulating film for redistribution layers, and an insulating film or protective film in touch panel displays and organic electroluminescent display panels. Since 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 packaging devices. Furthermore, the patterned polyimide resin film formed as described above can be suitably used as a photoresist, galvanic (electrolytic) resist, etching resist, solder top resist, and the like for electronics. Furthermore, the patterned polyimide resin film formed as described above can also be used for manufacturing printing plates such as offset plates or screen printing plates, forming etching masks when etching molded parts, and manufacturing protective lacquers and dielectric layers in electronic components, particularly microelectronic components.

[0175] As described above, the present inventors provide the following [1] to [6]. [1] A photosensitive resin composition comprising a reaction product (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 thermobase generator (B) that generates imidazole upon heating, and a photoradical polymerization initiator (C). [ka] (In formula (a1), X A1 This is a tetravalent organic group having 4 to 40 carbon atoms. Y A1 This is an organic group having 4 to 40 carbon atoms. R A1 , and R A2 Each is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R A1 , and R A2 At least one of them is a hydrogen atom, R A1 , and R A2 The aforementioned organic group is bonded to the oxygen atom in the ester bond via a CO bond. [2] The photosensitive resin composition according to [1] above, wherein the thermal base generating agent (B) comprises a thermal base generating agent (B1) having a structure represented by the following formula (b1). -R B1 -C(=O)-Imd (b1) (In formula (b1), R B1 (wherein is a single bond or oxygen atom, and Imd is an imidazole-1-yl group which may have substituents.) [3] The aforementioned R B1 The photosensitive resin composition described in [2] above, wherein is an oxygen atom. [4] The photosensitive resin composition according to any one of [1] to [3] above, wherein the isocyanate compound (A2) comprises an isocyanate compound (A2a) having one isocyanate group. [5] X A1 The photosensitive resin composition according to any one of [1] to [4] above, wherein the tetravalent organic group is a residue obtained by removing two dicarboxylic acid anhydride groups from an aromatic tetracarboxylic dianhydride. [6] Applying a photosensitive resin composition described in any one of [1] to [5] above onto a substrate to form a coating film, The coated film is exposed to light in a positionally selective manner, By developing the exposed coating film, a patterned resin film is obtained. A method for producing a patterned polyimide resin film, comprising heating the patterned resin film to generate a polyimide resin derived from the reactant (A). [Examples]

[0176] The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to these examples.

[0177] [Examples 1-21 and Comparative Examples 1-28] In the examples and comparative examples, the following DA-1 to DA-8 were used as diamine compounds.

[0178] [ka]

[0179] DA-5: Dimer amine (product name "PRIAMINE1075", manufactured by Croda Japan Co., Ltd.) DA-6:m-Toridine DA-7: 4,4'-Isopropylidenebis[(4-aminophenoxy)benzene] DA-8: 1,4-Bis(4-aminophenoxy)benzene

[0180] In the examples and comparative examples, the following TC-1 to TC-5 were used as tetracarboxylic dianhydrides. [ka]

[0181] TC-5: Bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)=1,1'-biphenyl-4,4'-diyl

[0182] In the examples and comparative examples, the following IS-1 to IS-4 were used as isocyanate compounds having a (meth)acryloyl group.

[0183] [ka]

[0184] In the examples and comparative examples, the following IM-1 to IM-3 (thermobase generators that generate imidazole upon heating (B)) and B1 to B6 were used as thermobase generators. Note that B1 to B6 are thermobase generators that do not generate imidazole upon heating. [ka] [ka]

[0185] In the examples and comparative examples, the following C1 was used as the photoradical polymerization initiator (C). C1:1,2-Octanedione, 1-[4-(phenylthio) phenyl]-, 2-(o-benzoyloxime)

[0186] (Preparation of 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, as used in Examples 1-14 and Comparative Examples 1-17)

[0187] 0.0322 moles of the tetracarboxylic dianhydride of the type listed in Table 1 were dispersed in 23.33 g of N-methyl-2-pyrrolidone (NMP), and the mixture was cooled to 0°C. To the cooled solution, a solution of 0.0322 moles of the diamine compound of the type listed in Table 1 dissolved in 17.53 g of NMP was added dropwise. After the dropwise addition was complete, the resulting reaction solution was heated to room temperature and stirred for 12 hours to obtain a solution containing a polyimide resin precursor (polyimide resin precursor (A1) having constituent units represented by formula (a1)). The obtained polyimide resin precursor-containing solution was heated to 80°C, and 0.0700 moles of isocyanate compound (A2) of the type listed in Table 1 were added dropwise and stirred for 6 hours. The solution was then added to isopropyl alcohol to obtain a powder precipitate, which was then filtered to obtain a powder. The obtained powder was washed three times with isopropyl alcohol and dried under reduced pressure to obtain a reaction product (A) of polyimide resin precursor (A1) having a structural unit represented by formula (a1) and isocyanate compound (A2) having a (meth)acryloyl group, which is used in the preparation of the photosensitive resin composition in each example and comparative example.

[0188] (Production of polyimide resin precursors used in Comparative Examples 18-26) 0.0645 moles of tetracarboxylic dianhydride of the type listed in Table 1 were dissolved in 40.0 g of N-methyl-2-pyrrolidone (NMP). To the resulting solution, 0.135 moles of hydroxyethyl methacrylate and 0.135 moles of pyridine were added. The resulting solution was stirred at room temperature for 12 hours to obtain dicarboxylic acid, which is the reaction product of tetracarboxylic dianhydride and alcohol (hydroxyethyl methacrylate).

[0189] The resulting solution containing the dicarboxylic acid was cooled to 0°C. To the cooled solution, a condensing agent solution containing 0.142 moles of dicyclohexylcarbodiimide dissolved in 8.5 g of NMP and a solution containing 0.0645 moles of a diamine compound of the type listed in Table 1 dissolved in 35.0 g of NMP were added dropwise.

[0190] After the dropwise addition was complete, the resulting reaction solution was stirred at 30°C for 6 hours to condense the dicarboxylic acid and the diamine compound.

[0191] After the reaction was complete, 15.0 g of methanol was added to the reaction solution. After removing the precipitated by-products by filtration, the filtrate containing the polyimide resin precursor was added dropwise to a large amount of aqueous isopropyl alcohol. After addition, the polyimide resin precursor precipitated in the aqueous solution in isopropyl alcohol was recovered by filtration. The recovered precipitate was washed three times with isopropyl alcohol. The precipitate after washing was dried under reduced pressure to obtain the polyimide resin precursor used in the preparation of the photosensitive resin composition in each comparative example.

[0192] (Preparation of 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, as used in Example 15) The reaction product (A) of a polyimide resin precursor (A1) having a structural unit represented by formula (a1), which was used in Example 15, and an isocyanate compound (A2) having a (meth)acryloyl group was produced by the following steps 1 to 4.

[0193] <Step 1> Synthesis of Imide Constituent Units In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube, 130.0 g (0.25 mol) of TC-4, 751.3 g of diethylene glycol dimethyl ether as solvent, and 132.6 g of methylcyclohexane were charged, and the reaction vessel was heated to 80-85°C. After reaching 80-85°C and the acid anhydride had dissolved, 101.1 g (0.187 mol) of DA-5 was charged. A Dean-Stark tube / condenser was installed and filled with methylcyclohexane. The temperature was then gradually increased, and the water generated by imidization was collected in the Dean-Stark tube. Dehydration was carried out until a predetermined amount of water was generated 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 substances, and then maintained at that temperature for 1 hour.

[0194] <Process 2> The mixture was cooled to 60°C, and 220.4g (0.749mol) of TC-2 was mixed with 300g of dimethylacetamide to form a slurry, which was then added to the mixture. 156.6g (0.738mol) of DA-6, which had been mixed with 261.2g of dimethylacetamide to form a slurry, was added over 30 minutes at 55-60°C. The mixture was then cooled to 50°C and kept warm for 1 hour. Next, it was cooled to room temperature and stirred for 12 hours.

[0195] <Step 3> Reaction of isocyanate compound (A2) having a (meth)acryloyl group The reaction vessel was heated to 80°C, and 229.6 g (1.480 mol) of IS-1 was charged and reacted for 7 hours. After the reaction, the solution was purified twice by reprecipitation with 4 times its weight of isopropyl alcohol, and then dissolved in dimethylacetamide to obtain a solution of (meth)acryloyl group-containing polyimide precursor with a solid content of 30%. The acid anhydride concentration, determined from the amount of aniline that reacted with the (meth)acryloyl group-containing polyimide precursor, was 0.036 mmol / g.

[0196] <Step 4> Addition of polyamic acid constituent units 100.0 g of (meth)acryloyl group-containing polyimide precursor and 4.5 g (0.0153 mol) of TC-2 were charged, and the reaction vessel was heated to 40°C. 3.46 g (0.0163 mol) of DA-6, which had been coated with 43.9 g of dimethylacetamide to form a slurry, was charged over 30 minutes at 40-45°C. The mixture was then cooled to 40°C and kept warm for 1 hour. Next, it was cooled to room temperature and stirred for 12 hours to obtain a polyfunctional amine-extended (meth)acryloyl group-containing polyimide precursor (reactant (A)).

[0197] (Preparation of 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, as used in Examples 16-21 and Comparative Examples 27-28) Except for the changes shown in Table 2 below, the procedure was the same as in "Production of 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, as used in Example 15."

[0198] (Manufacturing of photosensitive resin composition) In Examples 1-21 and Comparative Examples 1-17 and 27-28, 100 parts by mass of the reaction product (A) obtained was dissolved in 300 parts by mass of γ-butyrolactone as solvent (S). This mixture was used to obtain the photosensitive resin compositions for each example and comparative example.

[0199] <Storage Stability Evaluation> The obtained photosensitive resin composition was left standing at room temperature for one week, and its storage stability was evaluated according to the following criteria. ○: Did not gel. ×: It gelled.

[0200] <Photolithography Characteristics (Resolution) Evaluation> A photosensitive resin composition was applied to a silicon wafer on which a copper sputtered film had been formed using a spin coater. The film made of the photosensitive resin composition was then baked at 120°C for 300 seconds to obtain a coating film with a thickness of 10 μm. The coating film was then subjected to i-line exposure using a GHI-line exposure machine (manufactured by Ultratech) through a negative-type mask capable of forming via holes. Negative-type masks capable of forming via holes with aperture diameters of 5 μm and 10 μm were used for exposure. The exposure was 2000 J / m². 2 ~10000 J / m 2 Within the range, the exposure amount is set to 2000 J / m 2The exposure was gradually increased, and the process was repeated multiple times with different exposure levels. In other words, the unexposed coated film was exposed a number of times calculated by (number of exposure conditions) × (number of different mask aperture diameters (2)). The coated films exposed under each exposure condition were paddle-developed with cyclopentanone (CP) for 180 seconds. Then, they were heated at 200°C for 1 hour under a nitrogen atmosphere. The resulting patterned resin film was observed, and its resolution was evaluated according to the following criteria based on the diameter of the via holes that could be resolved according to the mask size. ◎: Via holes with opening diameters of 5 μm and 10 μm were successfully formed. ○: A via hole with an opening diameter of 10 μm was formed, but a via hole with an opening diameter of 5 μm could not be formed. ×: Via holes with opening diameters of 5 μm and 10 μm could not be formed.

[0201] <Chemical Resistance Evaluation> A photosensitive resin composition was coated onto a silicon wafer using a spin coater. The film made of the photosensitive resin composition was baked at 120°C for 300 seconds to obtain a coated film with a thickness of 10 μm. The coated film was subjected to an integrated light intensity of 2000 mJ / cm using a high-pressure mercury lamp. 2 The wafer was exposed to light. After exposure, the film was heated in an inert oven under a nitrogen atmosphere at a heating rate of 5°C / min to 200°C, and the coated film was heated at the same temperature for 1 hour. When the temperature dropped to 100°C, the wafer was removed. Test pieces cut from this wafer into 5cm squares were immersed in 60°C N-methyl-2-pyrrolidone (NMP) for 2 hours. The appearance of the test pieces after immersion was checked for any change from the appearance of the test pieces before immersion. If there was no change in appearance after 2 hours, it was judged as ◎; if there was no change in appearance after 1 hour but there was a change in appearance after 2 hours, it was judged as ○; and if there was a change in appearance after 1 hour, it was judged as ×.

[0202] <Evaluation of mechanical properties (tensile elongation)> A strip-shaped test piece measuring 1 cm wide and 5 cm long was cut from a wafer obtained in the same manner as in the <chemical resistance evaluation>. Tensile tests were performed on the obtained test piece using a tensile testing machine (EZ-test, manufactured by Shimadzu Corporation) under the conditions of a chuck distance 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. Tensile elongation (%) = (Distance between chucks at break (cm) / 2 (cm) - 1) × 100 For tensile elongation, values ​​of 50% or more were judged as "○" and values ​​less than 50% were judged as "×".

[0203] [Table 1]

[0204] [Table 2]

[0205] [Table 3]

[0206] The examples show that a photosensitive resin composition comprising a 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, a thermobase generator (B) that generates imidazole upon heating, and a photoradical polymerization initiator (C) can form a polyimide resin film that is excellent in photolithography properties and storage stability, as well as in mechanical properties and chemical resistance. On the other hand, it can be seen that a photosensitive resin composition that does not contain the reactant (A) or the thermobase generator (B) that generates imidazole upon heating is inferior to the examples in any of the following aspects: photolithography properties, storage stability, mechanical properties, and chemical resistance.

Claims

1. A photosensitive resin composition comprising a reaction product (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 thermobase generator (B) that generates imidazole upon heating, and a photoradical polymerization initiator (C). 【Chemistry 1】 (In formula (a1), X Ａ１ This is a tetravalent organic group having 4 to 40 carbon atoms. Y Ａ１ This is an organic group having 4 or more carbon atoms and 40 or fewer carbon atoms. R Ａ１ , and R Ａ２ Each is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, R Ａ１ , and R Ａ２ At least one of them is a hydrogen atom, R Ａ１ , and R Ａ２ The aforementioned organic group 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 generating agent (B) comprises a thermal base generating agent (B1) having a structure represented by the following formula (b1). -R Ｂ１ -C(=O)-Imd (b1) (In formula (b1), R Ｂ１ (wherein is a single bond or an oxygen atom, and Imd is an imidazole-1-yl group which may have substituents.)

3. The aforementioned R Ｂ１ The photosensitive resin composition according to claim 2, wherein 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 aforementioned X Ａ１ The photosensitive resin composition according to claim 1, wherein the tetravalent organic group is a residue obtained by removing two dicarboxylic acid anhydride groups from an aromatic tetracarboxylic dianhydride.

6. A photosensitive resin composition according to any one of claims 1 to 5 is applied to a substrate to form a coating film, The coated film is exposed to light in a positionally selective manner, By developing the exposed coating film, a patterned resin film is obtained. A method for producing a patterned polyimide resin film, comprising heating the patterned resin film to generate a polyimide resin derived from the reactant (A).

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