Photosensitive resin composition

Abstract

The present invention addresses the need to provide a photosensitive resin composition that exhibits good durability and low dielectric tangent in a patterned resin film formed under high-speed accelerated stress testing (HAST), a photosensitive dry film having a photosensitive layer formed from the photosensitive resin composition, a method for manufacturing the aforementioned photosensitive dry film, and a method for manufacturing a patterned resin film using the aforementioned photosensitive resin composition. The solution involves incorporating a polyfunctional thiol compound (D) into a photosensitive resin composition containing at least one resin (A) selected from the group consisting of polyimide resin (AI), polyamide (A-II), and polyamide resin (A-III), and a photosensitizer (C), which, when formed under specific conditions, can form a resin film exhibiting a dielectric tangent below a specific value.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition comprising at least one of a group consisting of a polyimide resin, polyamide, polyamide resin, polybenzoxazole resin, and a polybenzoxazole resin precursor, which includes constituent units derived from diamine compounds of a specific structure, and a photosensitive agent; a photosensitive dry film having a photosensitive layer formed from the photosensitive resin composition; a method for manufacturing the aforementioned photosensitive dry film; and a method for manufacturing a patterned resin film using the aforementioned photosensitive resin composition. Prior Technology

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

[0003] In recent years, the use of higher frequencies in communication devices such as mobile phones has been progressing. Therefore, the insulation components of communication devices that insulate metal wiring also need to be adapted to higher frequencies. Here, the higher the frequency, the greater the transmission loss, and if the transmission loss increases, the electrical signal attenuates. Therefore, for polyimide resins and polyamide resins, in order to further reduce transmission loss in response to higher frequencies, it is required to have a lower dielectric tangent and a lower dielectric constant in the high-frequency band.

[0004] Furthermore, in the fabrication of various components or electronic substrates, there are often situations where it is necessary to form insulating or protective materials only at desired locations. Therefore, photosensitive resin compositions exhibiting low dielectric tangent and low dielectric constant, and capable of forming patterned resin films, are in demand.

[0005] Based on the requirements described above, for example, as a photosensitive resin composition capable of forming a patterned polyimide resin film, a photosensitive resin composition is proposed that contains an aromatic polyimide resin having a specific structure derived from 4,4'-bis(4-aminophenoxy)biphenyl, and a photopolymerization initiator (see Example 1 of Patent Document 1); or a photosensitive resin composition that contains a polyimide precursor having unsaturated double bonds in its side chains, and a photopolymerization initiator having an oxime structure exhibiting a specific amount of free radical generation (see Patent Document 2). [Previous Technical Documents] [Patent Literature]

[0006] [Patent Document 1] International Publication No. 2019 / 044874 [Patent Document 2] International Publication No. 2021 / 020463 Summary of the Invention

[0007] [The problem that the invention aims to solve]

[0008] When using the photosensitive resin composition described in Patent Document 1 or Patent Document 2, a patterned polyimide resin film with a low dielectric tangent can be formed by applying photolithography. However, when using the photosensitive resin composition described in Patent Document 1 or Patent Document 2 to form a patterned resin film, there is a problem that it is not easy to form a resin film that exhibits good durability in the High Accelerated Stress Test (HAST).

[0009] The present invention was made in view of the above-mentioned problems, and its object is to provide a photosensitive resin composition that exhibits good durability in high-speed accelerated stress test (HAST) and can form a patterned resin film with low dielectric tangent, a photosensitive dry film having a photosensitive layer formed from the photosensitive resin composition, a method for manufacturing the aforementioned photosensitive dry film, and a method for manufacturing a patterned resin film using the aforementioned photosensitive resin composition. [Methods used to solve problems]

[0010] The inventors discovered that the above-mentioned problems can be solved by incorporating a polyfunctional thiol compound (D) into a photosensitive resin composition, thus completing the present invention. The photosensitive resin composition contains at least one resin (A) selected from the group consisting of polyimide resins (AI), polyamides (A-II), and polyamide resins (A-III), and a photosensitizer (C), and can form a resin film exhibiting a dielectric tangent below a specific value when film-forming under specific conditions. More specifically, the present invention provides the following.

[0011] The first embodiment of the present invention is a photosensitive resin composition, which is a photosensitive resin composition containing resin (A), photosensitizer (C), and polyfunctional thiol compound (D), wherein... Resin (A), containing selected Polyimide resins (AI) and polyamides (A-II) derived from diamine compounds and tetracarboxylic dianhydrides, and At least one of the group consisting of polyamide resins (A-III) derived from diamine compounds and dicarboxylic acid compounds or amide-forming derivatives of dicarboxylic acid compounds. Resin (A) has free radical polymerizable groups on its molecular chain, and photosensitizer (C) is a photoradical polymerization initiator (C1), or resin (A) has cationic polymerizable groups on its molecular chain, and photosensitizer (C) is a photocationic polymerization initiator (C2). A resin film with a thickness of 10 μm formed using a photosensitive resin composition was used as the sample, and the dielectric tangent value measured by the cavity resonator method under the conditions of room temperature 25°C, humidity 50%, and frequency 36 GHz was less than 0.01.

[0012] The second embodiment of the present invention is a photosensitive dry film having a substrate film and a photosensitive layer formed on the surface of the substrate film, wherein the photosensitive layer is composed of the photosensitive resin composition of the first embodiment.

[0013] The third embodiment of the present invention is a method for manufacturing a photosensitive dry film, which comprises coating a photosensitive resin composition of the first embodiment onto a substrate film to form a photosensitive layer.

[0014] The fourth embodiment of the present invention is a method for manufacturing a patterned resin film, which includes a lamination step of laminating a photosensitive layer formed of the photosensitive resin composition of the first embodiment onto a substrate. The exposure step, which involves selectively irradiating the photosensitive layer with active light or radiation, is similar to... The development step involves developing the exposed photosensitive layer to obtain a patterned resin film. [Effects of the Invention]

[0015] According to the present invention, a photosensitive resin composition capable of forming a patterned resin film with low dielectric tangent by applying photolithography, a photosensitive dry film having a photosensitive layer formed from the photosensitive resin composition, a method for manufacturing the aforementioned photosensitive dry film, and a method for manufacturing a patterned resin film using the aforementioned photosensitive resin composition are provided. Implementation

[0016] Photosensitive resin composition

[0017] The photosensitive resin composition contains resin (A), photosensitizer (C), and polyfunctional thiol compound (D). The resin (A) comprises at least one type selected from the group consisting of polyimide resins (AI) derived from diamine compounds and tetracarboxylic dianhydrides and polyamides (A-II), and polyamide resins (A-III) derived from diamine compounds and dicarboxylic acid compounds or amide-forming derivatives of dicarboxylic acid compounds. In the photosensitive resin composition, the resin (A) has free radical polymerizable groups on its molecular chain, and the photosensitizer (C) is a photoradical polymerization initiator (C1), or the resin (A) has cationic polymerizable groups on its molecular chain, and the photosensitizer (C) is a photocationic polymerization initiator (C2).

[0018] The amount of free radical polymerizable groups or cationic polymerizable groups in resin (A) is not particularly limited to the extent that it does not impede the purpose of the present invention. The amount of free radical polymerizable groups or cationic polymerizable groups in resin (A), for example, in moles of functional groups relative to the weight of resin (A), is preferably 0.0005 mol / g or more and 0.0500 mol / g or less, more preferably 0.001 mol / g or more and 0.0380 mol / g or less, and even more preferably 0.0015 mol / g or more and 0.0028 mol / g or less. The amount of free radical polymerizable groups or cationic polymerizable groups in resin (A) can typically be determined by NMR analysis.

[0019] The photosensitizer (C) is the component that imparts photosensitivity to the photosensitive resin composition. As described above, the resin (A) has free radical polymerizable groups or cationic polymerizable groups. The photosensitizer (C) can be a so-called polymerization initiator that initiates the polymerization reaction between these polymerizable groups. Therefore, the photosensitive resin composition becomes insoluble in the developer by curing through exposure. In other words, a photosensitive resin composition containing a resin (A) having polymerizable groups and a photosensitizer (C) as a polymerization initiator is equivalent to a negative photosensitive resin composition.

[0020] Using a 10 μm thick resin film formed from a photosensitive resin composition as a sample, the dielectric tangent value measured by the cavity resonator method at room temperature 25°C, humidity 50%, and frequency 36 GHz was less than 0.01.

[0021] When using a photosensitive resin composition that can form a resin film with a low dielectric tangent as described above, and forming a patterned resin film by photolithography, it is not easy to form a resin film with good durability as shown in HAST.

[0022] However, when a photosensitive resin composition having the above-described structure is used for forming, a patterned resin film exhibiting good durability can be formed on HAST. The following describes the essential or optional components of photosensitive resin compositions.

[0023] <Resin (A)> As previously stated, resin (A) comprises at least one type selected from the group consisting of polyimide resins (AI) derived from diamine compounds and tetracarboxylic dianhydrides, polyamide resins (A-II), polyamide resins (A-III) derived from diamine compounds and dicarboxylic acid compounds, or amide-forming derivatives of dicarboxylic acid compounds.

[0024] The following describes polyimide resin (AI), polyamide (A-II), and polyamide resin (A-III).

[0025] [Polyimide resin (AI) and polyamide (A-II)] Polyimide resin (AI) and polyamide (A-II) are resins derived from diamine compounds and tetracarboxylic dianhydrides. The types of diamine compounds and tetracarboxylic dianhydrides imparted to polyimide resin (AI) and polyamide (A-II) are not particularly limited, as long as resin (A) has free radical polymerizable groups or cationic polymerizable groups, and a photosensitive resin composition can be used to form a resin film displaying the aforementioned specific dielectric tangent.

[0026] From the viewpoint of low dielectric tangent of the resin film formed using a photosensitive resin composition, the diamine compounds of polyimide resin (AI) and polyamide acid (A-II) preferably each contain one or more of the following formulas (A1): (In formula (A1), X is an organic group with 1 to 100 carbon atoms, Ra1 is a hydroxyl, carboxyl, or halogen atom, Ra2 is an aliphatic, hydroxyl, carboxyl, sulfonic acid, or halogen atom with 1 to 20 carbon atoms, Ar is a phenyl group that can be substituted by Ra2, or a naphthyl group that can be substituted by Ra2, ma1 is an integer from 0 to 10, ma2 is an integer from 0 to 7, and ma3 is an integer from 1 to 10.) The diamine compound (A-1) has the following formula (A2): (In formula (A2), Ra3 and Ra4 are independently alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, or halogen atoms, respectively; and ma4 and ma5 are independently integers with 0 to 4.) The partial structure shown, and not equivalent to diamine compound (A-1), is a diamine compound (A-2) having the following formula (A3): (In formula (A3), Ra5 and Ra6 are independently alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, or halogen atoms, respectively; ma6 and ma7 are independently integers with 0 to 4 carbon atoms, respectively; Ra7 and Ra8 are independently hydrogen atoms, alkyl groups with 1 to 4 carbon atoms, haloalkyl groups with 1 to 4 carbon atoms, or phenyl groups, respectively; Ra7 and Ra8 can also be bonded to each other to form a ring.) The partial structure is represented, and is not equivalent to diamine compound (A-3) and diamine compound (A-2), and is a dimer diamine compound (A4).

[0027] The manufacturing method of polyimide resin (AI) is not particularly limited. Polyimide resin (AI) can usually be obtained by cyclizing and amide-imidizing polyamide acid (A-II) obtained by reacting a diamine compound with a tetracarboxylic acid dianhydride.

[0028] (Diamine compounds) Diamine compounds are represented by the following formula (A2). H₂N-A₁-NH₂･･･(A₂) (In formula (A2), A1 represents a divalent organic group).

[0029] A1 is a divalent organic group. In addition to the two amino groups, A1 may also have one or more substituents. Suitable examples of substituents are preferably 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 or a fluorinated alkoxy group, it is preferred to be a perfluoroalkyl or a perfluoroalkoxy group.

[0030] The lower limit for the number of carbon atoms in the organic group of A1 is preferably 2, more preferably 6; the upper limit is preferably 50, more preferably 30. A1 can also be an aliphatic group, but it is preferred to be an organic group containing one or more aromatic rings.

[0031] When A1 is an organic group containing one or more aromatic rings, the organic group can be a single aromatic group itself, or it can be a group formed by the bonding of two or more aromatic groups through aliphatic hydrocarbon groups and halogenated aliphatic hydrocarbon groups, or heteroatoms containing oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of heteroatoms in A1, including oxygen atoms, sulfur atoms, and nitrogen atoms, include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO 2-, -S-, and -SS-, with -COO-, -O-, -CO-, and -S- being more preferred.

[0032] The aromatic ring in A1 bonded to the amino group is preferably a benzene ring. When the ring in A1 bonded to the amino group is a condensed ring containing two or more rings, the ring bonded to the amino group in the condensed ring is preferably a benzene ring. Furthermore, the aromatic ring contained in A1 can also be an aromatic heterocycle.

[0033] When A1 is an organic group containing an aromatic ring, from the viewpoint of improving the electrical and mechanical properties of the formed resin film, the organic group is preferably at least one of the groups represented by the following formulas (21) to (24).

[0034] In (21)~(24), R 111 represents one of the groups selected from hydrogen atoms, fluorine atoms, carboxyl groups, sulfonic acid groups, hydroxyl groups, alkyl groups with 1 to 4 carbon atoms, and halogenated alkyl groups with 1 to 4 carbon atoms. In equation (24), Q1 represents 9,9'-pyranyl, or can be any of the following free forms: -C6H4-, -C6H4-C6H4-, -OC6H4-C6H4-O-, -OC6H4-CO-C6H4-O-, -OC6H4-C(CH3)2-C6H4-O-, -OCO-C6H4-COO-, -OCO-C6H4-C6H4-COO-, -OCO-, -O-, -CO-, -C(CF3)2-, -C(CH3)2-, -CH2-, -OC6H4-SO2-C6H4-O-, -C(CH3)2-C6H4-C(CH3) One of the groups consisting of the bases represented by 2-, -OC 10H 6-O-, -OC 6H 4-O-, -O-CH 2-O-, -O-(CH 2) 2-O-, -O-(CH 2) 3-O-, -O-(CH 2) 4-O-, -O-(CH 2) 5-O-, and -O-(CH 2) 6-O-.

[0035] In the example of Q1, -C6H4- is an extensiphenyl, preferably m-extensiphenyl and p-extensiphenyl, and more preferably p-extensiphenyl. Also, -C10H6- is a naphthidyl, preferably naphth-1,2-diyl, naphth-1,4-diyl, naphth-2,3-diyl, naphth-2,6-diyl and naphth-2,7-diyl; more preferably naphth-1,4-diyl and naphth-2,6-diyl.

[0036] As for R 111 in formulas (21) to (24), from the viewpoint of improving the electrical properties of the formed resin film, it is more preferably a hydrogen atom, a fluorine atom, a methyl atom, an ethyl atom, or a trifluoromethyl atom; it is especially preferably a hydrogen atom or a trifluoromethyl atom.

[0037] As for Q1 in formula (24), from the viewpoint of the electrical and mechanical properties of the formed resin film, the preferred options are -C6H4-C6H4-, -OC6H4-C6H4-O-, -OC6H4-CO-C6H4-O-, -OC6H4-C(CH3)2-C6H4-O-, -OCO-C6H4-COO-, -OCO-C6H4-C6H4-COO-, -OCO-, -O-, -CO-, -C(CF3)2-, -C(CH3)2-, -CH2-, -OC6H4-SO2-C6H4-O-, -C(CH3)2-C6H4-C(CH3)2-, -OC10H 6-O-, -OC 6H 4-O-, -O-CH 2-O-, -O-(CH 2) 2-O-, -O-(CH 2) 3-O-, -O-(CH 2) 4-O-, -O-(CH 2) 5-O-, and -O-(CH 2) 6-O-. From the viewpoint of improving the electrical and mechanical properties of resin (A) in the photosensitive resin composition, Q 1 in formula (24) is preferably -OC 6H 4-C 6H 4-O-, -OC 6H 4-C(CH 3) 2-C 6H 4-O-; particularly preferably represented by -OC 6H 4-C 6H 4-O-, and -C 6H 4- are all p-exenylphenyl groups.

[0038] When using an aromatic diamine compound as a diamine compound represented by formula (A2), for example, the aromatic diamine compound shown below may be suitable. That is, as aromatic diamine compounds, examples include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 9,10-diaminoanthracene, 9,10-bis(4-aminophenyl)anthracene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3, 4'-Diaminodiphenylsulfide, 4,4'-Diaminodiphenylsulfide, 3,3'-Diaminodiphenylsulfide, 3,4'-Diaminodiphenylsulfide, 4,4'-Diaminodiphenylmethane, 3,3'-Diaminodiphenylmethane, 3,4'-Diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis[N-(3 [N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfonyl-4,4'-diaminodiphenyl ether, 4,4'-diaminobenzoaniline, 3,3'-diaminobenzoaniline, 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) phenoxide, bis(4-aminophenoxyphenyl) phenoxide, bis(3-aminophenoxyphenyl) phenoxide, bis[4-(4-aminophenoxy)phenyl] phenoxide, bis[4-(3-aminophenoxy)phenyl] phenoxide, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl] phenoxide, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl] phenoxide, bis[4-(4-aminophenoxy)phenyl] ketone, 2,2-bis[4-{4-amino-2-(trifluoromethyl)phenoxy}phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl) phenoxide, 9,9-bis(4-amino-3-methyl) 9,9-bis(3-amino-4-hydroxyphenyl)benzene, 9,9-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]benzene, 9,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]benzene, 2,7-diaminobenzene, 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-benzoxazoleyl)benzene, 1,4-bis(6-amino-2-benzoxazoleyl)benzene, 1,3-bis(5-amino-2-) Benzoxazolyl)benzene, 1,3-bis(6-amino-2-benzoxazolyl)benzene, 2,6-bis(4-aminophenyl)benzobisoxazole, 2,6-bis(3-aminophenyl)benzobisoxazole, bis[(3-aminophenyl)-5-benzoxazolyl], bis[(4-aminophenyl)-5-benzoxazolyl], bis[(3-aminophenyl)-6-benzoxazolyl], bis[(4-aminophenyl)-6-benzoxazolyl], N,N'-bis(3-aminobenzoxazolyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoxazolyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoxazolyl)-4,4' -Diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'-[1,4-epoxyphenylbis(1-methylethane-1,1-diyl)]diphenylamine, 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, o-toluidine, etc. Of these, from the viewpoint of improving electrical and mechanical properties, 4,4'-bis(4-aminophenoxy)biphenyl and 3,4'-bis(4-aminophenoxy)biphenyl and 3,3'-bis(4-aminophenoxy)biphenyl.

[0039] Furthermore, as A1, a silicon-containing base that may have a chain-like aliphatic group and / or aromatic ring can be used. Typically, the following bases can be used as such silicon-containing bases.

[0040] Specific examples of compounds having amino groups at both ends and having silicon-containing groups include amino-modified methylphenyl polysiloxanes at both ends (e.g., X-22-1660B-3 (number average molecular weight around 4,400) and X-22-9409 (number average molecular weight around 1,300) manufactured by Shin-Etsu Chemical Co., Ltd.), amino-modified dimethyl polysiloxanes at both ends (e.g., X-22-161A (number average molecular weight around 1,600), X-22-161B (number average molecular weight around 3,000) and KF8012 (number average molecular weight around 4,400) manufactured by Shin-Etsu Chemical Co., Ltd.; BY16-835U (number average molecular weight around 900) manufactured by Dow Corning Toray Industries Co., Ltd.; and Silaplane FM3311 (number average molecular weight around 1,000) manufactured by JNC Corporation), etc.

[0041] Furthermore, as a diamine compound represented by formula (A2), it is also preferable to use a diamine having an oxoalkyl group. Preferred examples of oxoalkyl groups include oxoethoxy and oxopropoxy (-C(CH3)-CH2-O-, -CH2-C(CH3)-O-, or -CH2CH2CH2-O-). A diamine having an oxoalkyl group may also contain two or more oxoalkyl groups. When a diamine having an oxoalkyl group contains two or more oxoalkyl groups, the two or more oxoalkyl groups may be contained in the diamine in a block form or in a random form. It contains alkyl diamines, preferably free of cyclic groups, and more preferably free of aromatic groups. Specific examples of diamines containing oxoalkyl groups include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) EDR-176, JEFFAMINE (registered trademark) D-200, JEFFAMINE (registered trademark) D-400, JEFFAMINE (registered trademark) D-2000, and JEFFAMINE (registered trademark) D-4000, as well as 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, and 1-(1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, etc.

[0042] As mentioned above, the diamine compound preferably includes one or more of the group consisting of a diamine compound (A-1) represented by the above formula (A1), a diamine compound (A-2) having a partial structure represented by the above formula (2) and not equivalent to diamine compound (A-1), a diamine compound (A-3) having a partial structure represented by the above formula (A3) and not equivalent to diamine compound (A-1) and diamine compound (A-2), and a dimer diamine compound (A4).

[0043] (Diamine compound (A-1)) The diamine compound (A-1) is a compound represented by the following formula (A1). (In formula (A1), X is an organic group with 1 to 100 carbon atoms, Ra1 is a hydroxyl, carboxyl, or halogen atom, Ra2 is an aliphatic, hydroxyl, carboxyl, sulfonic acid, or halogen atom with 1 to 20 carbon atoms, Ar is a phenyl group that can be substituted by Ra2, or a naphthyl group that can be substituted by Ra2, ma1 is an integer from 0 to 10, ma2 is an integer from 0 to 7, and ma3 is an integer from 1 to 10).

[0044] In formula (A1), Ar is a phenyl group that can be substituted with Ra2, or a naphthyl group that can be substituted with Ra2. Ar is preferably phenyl or naphthyl. In other words, in formula (A1), ma2 is preferably 0.

[0045] In formula (A1), Ra2 is an aliphatic group, hydroxyl group, carboxyl group, sulfonic acid group, or halogen atom with 1 to 20 carbon atoms. As an organic group of Ra2, it may also contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms. The number of carbon atoms in the aliphatic group of Ra2 is preferably 1 to 12, and more preferably 1 to 6.

[0046] The aliphatic group of Ra2 is a chain alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, and n-eicosyl; a chain alkenyl group such as vinyl, 1-propenyl, 2-n-propenyl (allyl), 1-n-butenyl, 2-n-butenyl, and 3-n-butenyl; a cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl; chloromethyl, dichloromethyl Halogenated chain alkyl groups such as methyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, and perfluorodecyl; halogenated cycloalkyl groups such as 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2,4-dichlorocyclohexyl, 2-bromocyclohexyl, 3-bromocyclohexyl, and 4-bromocyclohexyl; hydroxy-chain alkyl groups such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxy-n-propyl, and 4-hydroxy-n-butyl; hydroxy-cycloalkyl groups such as 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, and 4-hydroxycyclohexyl; methoxy, ethoxy, n -Propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-hexyloxy, n-heptoxy, n-octoxy, 2-ethylhexyloxy, n-nonoxy, n-decoxy, n-undecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecanyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecanyloxy, and n-eicosyloxy, etc., chain alkoxy groups; vinyloxy, 1-propenoxy, 2-n-propenoxy (allyloxy), 1-n-butenoxy, 2-n-butenoxy, and 3-n-butenoxy, etc., chain alkenyloxy groups; methoxymethyl, ethoxymethyl, n-propoxymethyl Alkoxyalkyl groups such as 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 3-methoxy-n-propyl, 3-ethoxy-n-propyl, 3-n-propoxy-n-propyl, 4-methoxy-n-butyl, 4-ethoxy-n-butyl, and 4-n-propoxy-n-butyl; alkoxyalkyl groups such as methoxymethoxy, ethoxymethoxy, n-propoxymethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-n-propoxyethoxy, 3-methoxy-n-propoxy, 3-ethoxy-n-propoxy, 3-n-propoxy-n-propoxy, 4-methoxy-n-butoxy, 4-ethoxy-n-butoxy, and 4-n-propoxy-n-butoxy.Aliphatic acetylated groups such as methyl, acetylated, propionic, butylated, pentatylated, hexyl, heptatylated, octyl, nonatylated, and decyl; chain-like alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, n-pentoxycarbonyl, n-hexylcarbonyl, n-heptoxycarbonyl, n-octoxycarbonyl, n-nonoxycarbonyl, and n-decylcarbonyl; and aliphatic acetylated groups such as methyloxy, acetylated, propionic, butoxy, pentatylated, hexoxy, heptatylated, octoxy, nonoxy, and decyloxy.

[0047] In formula (A1), 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 is appropriately selected according to the structure of X. The value of ma3 is preferably between 1 and 4, and more preferably 1 or 2.

[0048] In formula (A1), X is an organogroup with 1 to 100 carbon atoms. The number of carbon atoms in the organogroup X is preferably 2 to 80, and more preferably 6 to 50. The organogroup X may also contain heteroatoms such as O, N, S, P, B, Si, or halogen atoms. Furthermore, in the compound represented by formula (A1), two amine groups are each bonded to a carbon atom in the organogroup X.

[0049] The organic group X can be an aliphatic group, an aromatic group, or a combination of aliphatic and aromatic groups. The organic group X can also be a group bonded through heteroatoms such as oxygen, sulfur, and nitrogen atoms. Examples of heteroatoms in the organic group X, including oxygen, sulfur, and nitrogen atoms, include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO₂-, -S-, and -SS-, with -O-, -CO-, and -S- being more preferred.

[0050] When the organic group X is an aliphatic group, it can be either a saturated or unsaturated aliphatic group. Preferably, the aliphatic group is an aliphatic hydrocarbon group. The aliphatic group can be chain-like, cyclic, or a combination of chain-like and cyclic aliphatic groups. Chain-like aliphatic groups can also be branched.

[0051] When the organic group of X is an aliphatic group, the aliphatic group is preferably a group in which (ma1+ma3+2) hydrogen atoms are removed from an alkyl group having 1 to 20 carbon atoms, more preferably a group in which (ma1+ma3+2) hydrogen atoms are removed from an alkyl group having 1 to 16 carbon atoms, and even more preferably a group in which (ma1+ma3+2) hydrogen atoms are removed from an alkyl group having 1 to 12 carbon atoms.

[0052] When the organic group of X is a group containing an aromatic group, the groups formed by X, Ar, Ra1 and Ra2 in formula (A1) can be represented by the following formulas (11) to (15).

[0053] In equations (11) to (15), Ar, Ra1, Ra2, ma1, ma2, and ma3 are the same as those in equation (A1). In equation (13), ma4 and ma5 are each an integer between 0 and 4. ma6 and ma7 are each an integer 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 an integer between 0 and 4. The sum of ma8, ma9, and ma10 is between 0 and 10. ma11, ma12, and ma13 are each an integer 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. The sum of ma16 and ma17 is between 1 and 8.

[0054] In equation (11), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2. In equation (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 preferably 0, ma6 and ma7 are preferably 0, 1 or 2 respectively, and the sum of ma6 and ma7 is 1 or more, preferably 4 or less. In formula (14), ma2 is preferably 0, ma8, ma9 and ma10 are preferably 0 respectively, ma11, ma12 and ma13 are preferably 0, 1 or 2 respectively, and the sum of ma11, ma12 and ma13 is 1 or more, preferably 6 or less. In formula (15), ma2 is preferably 0, ma14 and ma15 are preferably 0 respectively, ma16 and ma17 are preferably 0, 1 or 2 respectively, and the sum of ma16 and ma17 is 1 or more, preferably 4 or less.

[0055] In formulas (11) to (15), Ra3 is a single bond or a divalent linker. However, the divalent linker is not a group containing an aromatic group. Examples of divalent linkers include aliphatic hydrocarbon groups with 1 to 20 carbon atoms, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, as well as combinations of two or more groups selected from these groups. The number of carbon atoms in the linker is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. The aliphatic hydrocarbon group as the linker may also have one or more unsaturated bonds, may be branched, or may contain a ring structure. Specific examples of aliphatic hydrocarbon groups that act as linking groups include methylene, ethane-1,2-diyl (ethyl), ethane-1,1-diyl, propane-1,3-diyl, propane-1,2-diyl, propane-1,1-diyl, propane-2,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane- 1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, octadecane-1,18-diyl, nonadecane-1,19-diyl, eicosane-1,20-diyl, ethylene-1,2-diyl (vinylene), propylene-1,3-diyl, acetylene-1,2-diyl, and propyne-1,3-diyl, etc.

[0056] Suitable examples of linking groups include alkyl groups with 1 to 6 carbon atoms, alkenyl groups with 2 to 6 carbon atoms, alkyne groups with 2 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, alkenyloxy groups with 2 to 6 carbon atoms, alkyneoxy groups with 2 to 6 carbon atoms, alkyneoxy groups with 2 to 6 carbon atoms, alkylthio groups with 1 to 6 carbon atoms, alkenylthio groups with 2 to 6 carbon atoms, alkynethio groups with 2 to 6 carbon atoms, alkyneamine groups with 1 to 6 carbon atoms, alkenylamine groups with 2 to 6 carbon atoms, alkyneamine groups with 2 to 6 carbon atoms, -CONH-, -NH-, -COO-, -O-, -CO-, -SO-, -SO 2-, -S-, -OCONH-, and -OCOO-, etc.

[0057] From the viewpoint that the formed resin film exhibits low dielectric tangent and good mechanical properties, the diamine compound (A-1) represented by formula (A1) is preferably of the following formula (A1-1): (In formula (A1-1), Ra1, Ra2, Ar, ma1, ma2, and ma3 are the same as those in formula (A1), Ya1 is an organogroup or single bond with 1 to 20 carbon atoms, Ya2 is an organogroup with 1 to 20 carbon atoms, na1 is 0 or 1, and na2 is 0 or 1. When na1 is 1, Ya1 is not a single bond). The compound represented.

[0058] In formula (A1-1), the organic group of Ya1 may also include heteroatoms such as O, N, S, P, B, Si, and halogen atoms. The organic group of Ya1 is preferably a hydrocarbon group. The hydrocarbon group of Ya1 may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The hydrocarbon group of Ya1 is preferably an aromatic hydrocarbon group, and more preferably an enantylphenyl and a naphthyldiyl group. Suitable specific examples of the aromatic hydrocarbon group of Ya1 include p-enantylphenyl, m-enantylphenyl, o-enantylphenyl, naphth-1,4-diyl, naphth-1,2-diyl, naphth-1,3-diyl, naphth-1,5-diyl, naphth-1,6-diyl, naphth-1,7-diyl, naphth-1,8-diyl, naphth-2,6-diyl, naphth-2,7-diyl, and naphth-2,3-diyl. Among these aromatic hydrocarbon groups, p-phenyl and m-phenyl are preferred, and p-phenyl is even more preferred.

[0059] In formula (A1-1), na2 is preferably 1, and more preferably both na1 and na2 are 1, and Ya1 is an organic group. This can be attributed to the high degree of stereochemical freedom of the ether bond; when using photosensitive resin components to form a hardened film, the constituent units represented by formula (A1-1) are easily and well-packed, easily forming a hardened film with excellent mechanical, thermal, and electrical properties.

[0060] In formula (A1-1), ma1 is preferably 0, ma2 is preferably 0, and ma3 is preferably 1 or 2.

[0061] Specific examples of diamine compounds (A-1) represented by formula (A1) described above can be listed below.

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069] (Diamine compound (A-2)) Diamine compound (A-2) is a diamine compound having a partial structure represented by the following formula (A2) and not equivalent to diamine compound (A-1). (In formula (A2), Ra3 and Ra4 are independently alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, or halogen atoms, respectively, and ma4 and ma5 are independently integers with 0 to 4.)

[0070] In formula (A2), alkyl groups having 1 to 4 carbon atoms in Ra3 and Ra4 can be exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among these alkyl groups, methyl and ethyl are preferred, and methyl is even more preferred. In formula (A2), alkoxy groups having 1 to 4 carbon atoms in Ra3 and Ra4 can be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy. Among these alkoxy groups, methoxy and ethoxy are preferred, and methoxy is more preferred. In formula (A2), fluorine, chlorine, bromine, and iodine atoms can be listed as halogen atoms for Ra3 and Ra4. Among these halogen atoms, chlorine and bromine atoms are preferred.

[0071] In formula (A2), ma4 and ma5 are each an integer between 0 and 4. For reasons such as the easy availability of diamine compound (A-2), ma4 and ma5 are preferably integers between 0 and 2, and more preferably 0.

[0072] Suitable compounds as diamine compounds (A2) include those represented by the following formula (A2-1). (In formula (A2-1), X1 and X2 are each independently an aromatic hydrocarbon group that can be substituted by one or more groups selected from the group consisting of alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, and halogen atoms. Ra3, Ra4, ma4, and ma5 are the same as those in formula (A2).)

[0073] In formula (A2-1), X1 and X2 are respectively independently divalent aromatic hydrocarbon groups that can be substituted by one or more groups selected from alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, and halogen atoms. Alkyl groups having 1 to 4 carbon atoms as substituents may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among these alkyl groups, methyl and ethyl are preferred, and methyl is even more preferred. Alkoxy groups having 1 to 4 carbon atoms as substituents include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy. Among these alkoxy groups, methoxy and ethoxy are preferred, and methoxy is even more preferred. Halogen atoms that can be used as substituents include fluorine, chlorine, bromine, and iodine atoms. Among these halogen atoms, chlorine and bromine atoms are preferred.

[0074] The number of carbon atoms in the aromatic hydrocarbon groups X1 and X2 is not particularly limited, but is preferably 6 to 50, and more preferably 6 to 20. Furthermore, the aforementioned number of carbon atoms in the aromatic hydrocarbon groups does not include the number of carbon atoms in the substituents. The aromatic hydrocarbon groups of X1 and X2 are preferably o-extensive phenyl, m-extensive phenyl, and p-extensive phenyl, etc.; naphthyl-1,4-diyl, naphthyl-1,3-diyl, naphthyl-2,6-diyl, and naphthyl-2,7-diyl, etc.; and biphenyl-4,4'-diyl, biphenyl-3,4'-diyl, and biphenyl-3,3'-diyl, etc.

[0075] X1 and X2 are preferably 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.

[0076] Specific examples of diamine compounds (A-2) represented by formula (A2) as described above can be listed below.

[0077] (Diamine compound (A-3)) Diamine compound (A-3) is a diamine compound having a partial structure represented by the following formula (A3) and not equivalent to diamine compounds (A-1) and (A-2). (In formula (A3), Ra5 and Ra6 are independently alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, or halogen atoms, respectively; ma6 and ma7 are independently integers with 0 to 4 carbon atoms, respectively; Ra7 and Ra8 are independently hydrogen atoms, alkyl groups with 1 to 4 carbon atoms, halogenated alkyl groups with 1 to 4 carbon atoms, or phenyl groups, respectively; Ra7 and Ra8 can also be bonded to each other to form a ring).

[0078] In formula (A3), alkyl groups having 1 to 4 carbon atoms in Ra5 and Ra6 can be exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among these alkyl groups, methyl and ethyl are preferred, and methyl is even more preferred. In formula (A3), alkoxy groups having 1 to 4 carbon atoms in Ra5 and Ra6 can be exemplified by methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy. Among these alkoxy groups, methoxy and ethoxy are preferred, and methoxy is even more preferred. In formula (A3), fluorine, chlorine, bromine, and iodine atoms can be listed as halogen atoms for Ra5 and Ra6. Among these halogen atoms, chlorine and bromine atoms are preferred.

[0079] In formula (A3), ma6 and ma7 are each an integer between 0 and 4. For reasons such as the easy availability of diamine compounds (A-3), ma6 and ma7 are preferably integers between 0 and 2, and more preferably 0.

[0080] In formula (A3), alkyl groups having 1 to 4 carbon atoms in Ra7 and Ra8 can be exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. In formula (A3), alkyl halides having 1 to 4 carbon atoms in Ra7 and Ra8 can be listed as chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, and 1,1,2,2,2-pentafluoroethyl. For the reasons that polyimide resin (AI) has good solubility in organic solvents or that diamine compound (A-3) is readily available, Ra7 and Ra8 in formula (A3) are preferably hydrogen atoms, methyl, ethyl, trifluoromethyl, and phenyl. Alternatively, Ra7 and Ra8 may be bonded together to form cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene, etc., with 5 to 8 carbon atoms.

[0081] The following structures are suitable examples of the partial structures represented by equation (A3).

[0082] Suitable compounds as diamine compounds (A3) include those represented by the following formula (A3-1). (In formula (A3-1), X3 and X4 are each independently an aromatic hydrocarbon group that can be substituted by one or more groups selected from the group consisting of alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, and halogen atoms. Ra5, Ra6, Ra7, Ra8, and ma6 and ma7 are the same as those in formula (A3).)

[0083] In formula (A3-1), X3 and X4 are independently divalent aromatic hydrocarbon groups that can be substituted by one or more groups selected from alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, and halogen atoms. Alkyl groups having 1 to 4 carbon atoms as substituents may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among these alkyl groups, methyl and ethyl are preferred, and methyl is even more preferred. Alkoxy groups having 1 to 4 carbon atoms as substituents include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy. Among these alkoxy groups, methoxy and ethoxy are preferred, and methoxy is even more preferred. Halogen atoms that can be used as substituents include fluorine, chlorine, bromine, and iodine atoms. Among these halogen atoms, chlorine and bromine atoms are preferred.

[0084] The number of carbon atoms in the aromatic hydrocarbon groups X3 and X4 is not particularly limited, but is preferably 6 to 50, and more preferably 6 to 20. Furthermore, the aforementioned number of carbon atoms in the aromatic hydrocarbon groups does not include the number of carbon atoms in the substituents. As aromatic hydrocarbon groups of X3 and X4, preferred are o-extensive phenyl, m-extensive phenyl, and p-extensive phenyl; naphthyl-1,4-diyl, naphthyl-1,3-diyl, naphthyl-2,6-diyl, and naphthyl-2,7-diyl; biphenyl-4,4'-diyl, biphenyl-3,4'-diyl, and biphenyl-3,3'-diyl.

[0085] X3 and X4 are preferably 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.

[0086] Specific examples of diamine compounds (A-3) represented by formula (A3) described above can be listed below.

[0087]

[0088] (Dimeric diamine compound (A-4)) For ease of use of photosensitive resin compositions, the formation of hardened compounds with high-frequency dielectric properties and low dielectric tangent, diamine compounds are preferably dimer diamine compounds (A-4). Diamine compounds (A-4) are diamine compounds formed by substituting the two terminal carboxyl groups of dimer acids with aminomethyl or amino groups. Diamine acids are known dicarboxylic acids obtained through intermolecular polymerization of unsaturated fatty acids. The industrial manufacturing process for producing dimer acids is almost standardized. Typically, dimer acids are obtained by dimerizing unsaturated fatty acids with 11 to 22 carbon atoms in the presence of clay catalysts, etc. Industrially obtained dimer acids are mainly composed of 36-carbon dicarboxylic acids obtained by dimerizing 18-carbon unsaturated fatty acids such as oleic acid, linoleic acid, and alpha-linolenic acid. Industrially obtained dimer acids, depending on the degree of purification, may contain any amount of monomeric acids with 18 carbon atoms, trimeric acids with 54 carbon atoms, and other polymeric fatty acids with 20 to 54 carbon atoms. As a dimerized diamine compound (A-4), it is preferred to be a diamine compound represented by the following formula (31).

[0089] In formula (31), e, f, g, and h are 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 formula (31), the wavy line indicates a carbon-carbon single bond or a carbon-carbon double bond. However, at least one of the compounds represented by formula (31) must contain a carbon-carbon double bond.

[0090] The reason why a hardened compound with better elongation can be formed is that the diamine compound represented by formula (31) is preferably the compound represented by formula (32) below.

[0091] Commercially available diamine compounds represented by formula (31) may include Versamine 551 (manufactured by BASF) and Priamine 1074 (manufactured by Croda Japan), which contain compounds represented by formula (33) below, or Versamine 552 (manufactured by BASF), Priamine 1073 (manufactured by Croda Japan), and Priamine 1075 (manufactured by Croda Japan), which contain compounds represented by formula (32) above. Such commercially available dimer diamine compounds (A-4) are generally mixtures containing multiple amine compounds.

[0092] Furthermore, by reacting the diamine compound represented by formula (31) with an acid halide derived from trimellitic anhydride, a tetracarboxylic dianhydride represented by formula (34) can be obtained. It is also preferable to use the tetracarboxylic dianhydride represented by formula (34) as a raw material for manufacturing polyimide resin (AI) and polyamide (A-II). In equation (34), i, j, k, and l are integers greater than or equal to 0. i+j is an integer between 6 and 17, and k+l is an integer between 8 and 19. In equation (34), the wavy line indicates a carbon-carbon single bond or a carbon-carbon double bond.

[0093] When resin (A) is polyimide resin (AI) or polyamide (A-II), the ratio of the number of moles derived from one or more compounds selected from the group consisting of diamine compounds (A-1, A-2, A-3, and A-4) to the total number of moles derived from all constituent units of diamine compounds in polyimide resin (AI) and polyamide (A-II) is preferably 10 mol% to 100 mol%, more preferably 15 mol% to 100 mol%, and even more preferably 20 mol% to 100 mol%.

[0094] As mentioned above, the resin (A) incorporated in the photosensitive resin composition, from the viewpoint of photosensitivity, has free radical polymerizable groups or cationic polymerizable groups on its molecular chain that can be polymerized by the action of the photosensitizer (C).

[0095] The bonding positions of free radical polymerizable groups or cationic polymerizable groups in the molecular chains of polyimide resin (AI) and polyamide (A-II) are not particularly limited. As a free radical polymerizable group, typically, groups containing vinyl unsaturated double bonds can be listed. Groups containing vinyl unsaturated double bonds are preferably alkenyl groups such as vinyl and allyl groups, and more preferably groups containing (meth)acrylic acid groups. Typical examples of cationic polymerizable groups include groups containing epoxy groups, groups containing oxocyclic butyl groups, and groups containing ethyleneoxy groups. Among these, groups containing epoxy groups and groups containing ethyleneoxy groups are preferred. Among groups containing epoxy groups, groups containing alicyclic epoxy groups or glycidyl groups are preferred. Furthermore, an alicyclic epoxy group refers to an aliphatic cyclic group in which two carbon atoms of adjacent ring constituent atoms are bonded through an oxygen atom. In other words, an alicyclic epoxy group is an epoxy group on an aliphatic ring that comprises a three-membered ring consisting of two carbon atoms and one oxygen atom.

[0096] The aforementioned free radical polymerizable groups and cationic polymerizable groups are preferably bonded to the aromatic rings in the molecular chains of polyimide resin (AI) and polyamide (A-II). Therefore, the divalent organic group A1 in formula (A2) can, for example, be a group on the aromatic ring of the aromatic group represented by the aforementioned formulas (21) to (24) with a free radical polymerizable group or a cationic polymerizable group further bonded.

[0097] Suitable examples of free radical polymerizable groups bonded to the aromatic rings in the molecular chains of polyimide resins (AI) and polyamides (A-II) can be listed as groups represented by the following formula (Aa) or the following formula (Ab), which are not equivalent to groups containing ethylene oxide groups.

[0098] In formulas (Aa) and (Ab), R01 is an alkenyl group with 2 to 10 carbon atoms. R02 is an alkyl group with 1 to 10 carbon atoms. A 01 is -O-, -CO-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, or -NH-. A 02 is -O-, -CO-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, or -NH-. na is 0 or 1.

[0099] Suitable examples of free radical polymerizable groups bonded to the aromatic ring in the main chain can be listed. The basis of representation. These. R03 in the radical is allyl or (meth)acrylic.

[0100] Preferably, it is an aromatic ring bonded to the molecular chain of polyimide resin (AI) and polyamide (A-II). Suitable examples of cationic polymerizable groups bonded to the aromatic ring in the molecular chain of polyimide resin (AI) and polyamide (A-II) include ethyleneoxy groups and groups represented by formulas (Ac) to (Ah) below.

[0101] In formulas (Ac) to (Ah), R02 is an alkyl group having 1 to 10 carbon atoms. R04 is an epoxy alkyl group having 2 to 20 carbon atoms, or an alicyclic epoxy group having 3 to 20 carbon atoms. R05 is an alicyclic epoxy group having 3 to 20 carbon atoms. R06 is a vinyl group. R07 is an alkyl group having 1 to 10 carbon atoms. A 01 is -O-, -CO-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, or -NH-. A 03 is either -O- or -NH-. nb is 0 or 1.

[0102] Suitable examples of cationic polymerizable groups bonded to the aromatic ring in the main chain can be listed. The basis of representation. These are the basis. R 07 in the formula is ethyleneoxy, glycidoxy, epoxycyclopentyl, epoxycyclohexyl, or epoxycycloheptyl.

[0103] When A1 in formula (A2) is an aromatic group having free radical polymerizability or cationic polymerizability, specific examples of such aromatic group can be listed below.

[0104]

[0105]

[0106] (Tetracarboxylic acid dianhydride) As a tetracarboxylic dianhydride, the tetracarboxylic dianhydride that has been used in the manufacture of polyamide and polyimide resins since the past can be used without particular restrictions. As tetracarboxylic dianhydrides, compounds represented by the following formula (A3) can be listed. Tetracarboxylic dianhydrides can be used alone or in combination of two or more. (In formula (A3), A2 is a tetravalent organic group with 6 to 50 carbon atoms).

[0107] In formula (A3), A2 is a tetravalent organic group with 6 to 50 carbon atoms. In addition to the two anhydride groups represented by -CO-O-CO- in formula (A3), it may also have one or more substituents. Suitable examples of substituents are preferably 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. Furthermore, the compound represented by formula (a1-1) may contain carboxyl groups and carboxylic acid ester groups in addition to anhydride groups. When the substituent is a fluorinated alkyl or a fluorinated alkoxy group, it is preferred to be a perfluoroalkyl or a perfluoroalkoxy group. Regarding the above substituents, it can be said that they are the same as those for aromatic compounds, which are described later based on the presence of one or more substituents on the aromatic ring.

[0108] The number of carbon atoms constituting A2 is preferably 8 or more, and even more preferably 12 or more. Furthermore, the number of carbon atoms constituting A2 is preferably 40 or less, and even more preferably 30 or less. A2 can be an aliphatic group, an aromatic group, or a group combining these structures. In addition to carbon and hydrogen atoms, A2 may also contain halogen atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. When A2 contains oxygen, nitrogen, or sulfur atoms, the oxygen, nitrogen, or sulfur atoms may be selected from nitrogen-containing heterocyclic groups, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -SS-, and included in A1; more preferably, they may be selected from -O-, -CO-, -S-, and included in A1.

[0109] The tetracarboxylic dianhydride represented by formula (A3) can 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, the aromatic tetracarboxylic acid dianhydride preferably has two diancarboxylic acid anhydride groups bonded to the aromatic group.

[0110] Aliphatic tetracarboxylic dianhydrides can also contain an alicyclic structure. This alicyclic structure can also be polycyclic. Examples of aliphatic tetracarboxylic dianhydrides that do not have an alicyclic structure include 1,2,3,4-tetracarboxylic dianhydrides (e.g., Rikacid BT-100, manufactured by Shin Nippon Rika Co., Ltd.). Aliphatic tetracarboxylic dianhydrides with an alicyclic structure include cyclobutanetetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norcamphene-2-spiro-α-cyclopentanone-α'-spiro-2”-norcamphene-5,5”,6,6”-tetracarboxylic dianhydride (e.g., Enehyde CpODA, ENEOS), and 2,2-bis(2,3) -Dicarboxyphenoxy)hexafluoropropane dianhydride [5,5'-(1,4-epoxyphenyl)bisnorbornene]-2,2',3,3'-tetracarboxylic dianhydride (e.g., Enehyde (registered trademark) BzDA, manufactured by ENEOS), 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-disideoxy-3-furanyl)naphtho[1,2-C]furan-1,3-dione (e.g., Rikacid TDA-100, manufactured by Shin Nippon Rikka Co., Ltd.).

[0111] Aromatic tetracarboxylic dianhydrides, represented by formula (A3) and having two dicarboxylic anhydride groups bonded to an aromatic group, include, for example, benzopyrene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phenyl dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, and trimellitic acid (3,4-dicarboxyphenyl) Dihydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis(2,3-dicarboxyphenoxy)methane dianhydride, 1,1-bis(2,3-dicarboxyphenoxy)ethane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride, 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride, 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (e.g., Rikacid) TMEG100 (manufactured by Shin Nippon Rika Co., Ltd.), and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane Kasei Co., Ltd.), etc. From the viewpoint that these aromatic tetracarboxylic acid dianhydrides readily form hardened compounds with excellent electrical properties, 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)alkyl dianhydride are preferred. The number of carbon atoms in the straight-chain extended alkyl group of the α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkyl dianhydride is preferably 1 to 20, more preferably 2 to 12. Suitable specific examples of α,ω-bis(3,4-dicarboxyphenylcarbonyloxy)alkyl dianhydrides include 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (e.g., Rikacid TMEG100, manufactured by Shin Nippon Rikka Co., Ltd.) and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane Kasei Co., Ltd.).

[0112] Furthermore, from the viewpoint of suppressing warping of the hardened film of the photosensitive resin composition or having good photolithography properties of the photosensitive resin composition, the aromatic tetracarboxylic dianhydride is also preferred to be biphenyl tetracarboxylic dianhydride. Examples of biphenyl tetracarboxylic acid dianhydrides include 3,3',4,4'-biphenyl tetracarboxylic acid dianhydrides, 2,3,3',4'-biphenyl tetracarboxylic acid dianhydrides, and 2,2',3,3'-biphenyl tetracarboxylic acid dianhydrides, with 3,3',4,4'-biphenyl tetracarboxylic acid dianhydrides being preferred.

[0113] Furthermore, as an aromatic tetracarboxylic acid dianhydride, it can also be a compound represented by the following general formulas (a3-2)~(a3-4).

[0114] In the above formulas (a3-2) and (a3-3), Ra01, Ra02, and Ra03 represent any of the following: an aliphatic group that can be substituted with a halogen, an oxygen atom, a sulfur atom, or an aromatic group separated by one or more divalent elements, or represent a divalent group formed by such combinations. Ra02 and Ra03 may be the same or different. That is, Ra01, Ra02, and Ra03 may contain carbon-carbon single bonds, carbon-oxygen-carbon ether bonds, or halogen elements (fluorine, chlorine, bromine, iodine). Examples of compounds represented by formula (a3-2) include 2,2-bis(3,4-dicarboxyphenoxy)propane dianhydride, bis(3,4-dicarboxyphenoxy)methane dianhydride, 1,1-bis(3,4-dicarboxyphenoxy)ethane dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene, 2,2-bis(3,4-dicarboxyphenoxy)hexafluoropropane dianhydride, and 1,4-bis(3,4-dicarboxyphenoxy)phenyl dianhydride.

[0115] Furthermore, in the above formula (a3-4), Ra04 and Ra05 are any of the following: an aliphatic group that can be substituted by a halogen, an aromatic group separated by one or more divalent elements, or a halogen; or they represent a monovalent substituent formed by a combination of these. Ra04 and Ra05 may be the same or different. As compounds represented by formula (a3-4), difluorophenyltetracarboxylic dianhydride and dichlorophenyltetracarboxylic dianhydride may also be used.

[0116] As mentioned above, polyimide resin (AI) and polyamide (A-II) preferably have free radical polymerizable groups or cationic polymerizable groups on their molecular chains. Therefore, the tetravalent organic group A2 in formula (A3) can also be represented by the following formulas (a3-5) to (a3-7). In equations (a3-5) to (a3-7), Ra01, Ra02 and Ra03 are the same as Ra01, Ra02 and Ra03 in the aforementioned equations (a3-2), (a3-3) and (a3-4). In formulas (a3-5), (a3-6), and (a3-7), Ra06 is a free radical polymerizable group or a cationic polymerizable group. The aforementioned groups can be listed as free radical polymerizable groups or cationic polymerizable groups, respectively. Tetracarboxylic dianhydrides are inherently reactive. For example, epoxy groups readily react with carboxylic anhydride groups. Therefore, when introducing a building block equivalent to a tetracarboxylic dianhydride unit derived from a group represented by formulas (a3-5) to (a3-7) into polyimide resin (AI) or polyamide (A-II), it is preferable to introduce a free radical polymerizable group or a cationic polymerizable group onto the molecular chain of the polyimide resin (AI) or polyamide (A-II) after the synthesis of the polyimide resin (AI) or polyamide (A-II).

[0117] Reactions used to introduce free radical polymerizable groups or cationic polymerizable groups, for example, can be listed as follows. 1) The etherification reaction of halogen atoms bonded to the aromatic rings in the molecular chains of polyimide resins (AI) or polyamides (A-II) with alcohol compounds possessing free radical polymerizability or cationic polymerizability. 2) The esterification reaction of hydroxyl groups bonded to the aromatic rings of polyimide resins (AI) or polyamides (A-II) with carboxylic acid halides possessing free radical polymerizability or cationic polymerizability. 3) The esterification reaction of carboxyl groups bonded to the aromatic rings of polyimide resins (AI) or polyamides (A-II) with organohalides possessing free radical polymerizability or cationic polymerizability, and 4) The amine group bonded to the aromatic ring in the molecular chain of polyimide resin (AI) or polyamide (A-II) undergoes N-substitution reaction with organohalides having free radical polymerizable groups or cationic polymerizable groups. Reactions used to introduce free radical polymerizable groups or cationic polymerizable groups are not limited to these reactions.

[0118] Furthermore, for example, after synthesizing a polyimide resin (AI) or polyamide (A-II) with a hydroxyl group protected by a protecting group such as acetyl, or a carboxylic acid ester group such as methoxycarbonyl, or an amine group protected by a protecting group such as tert-butoxycarbonyl, the protection can be removed by a known method to obtain a polyimide resin (AI) or polyamide (A-II) with a hydroxyl group, carboxyl group, or amine group on the aromatic ring.

[0119] (Manufacturing method of polyimide resin (AI) and polyamide (A-II)) The manufacturing methods for polyimide resin (AI) and polyamide (A-II) are not particularly limited. Typically, the polyimide resin (AI) described above can be manufactured by reacting the above-mentioned diamine compound with tetracarboxylic dianhydride to obtain polyamide (A-II), and then by amide-imidizing the polyamide (A-II). In the manufacture of polyamide (A-II), tetracarboxylic acid dianhydride and diamine can be used individually or in combination of two or more. Polyimide resins (AI) and polyamides (A-II), as mentioned above, may also have free radical polymerizable groups or cationic polymerizable groups. These free radical polymerizable groups or cationic polymerizable groups may also be introduced onto the molecular chain after the synthesis of polyamides (A-II) or polyimide resins (AI). When free radical polymerizable groups or cationic polymerizable groups are introduced onto the molecular chain of polyacrylic acid (A-II) or polyimide resin (AI) after the synthesis of polyacrylic acid (A-II) or polyimide resin (AI), the method of introduction is not particularly limited. Typical examples of methods for introducing free radical polymerizable groups or cationic polymerizable groups onto a molecular chain include the reaction of polyamide (A-II) or polyimide resin (AI) having functional groups such as hydroxyl, amine, and carboxyl groups with carboxylic acids, carboxylic acid halides, alcohols, phenols, amines, halogenated compounds, carboxylic acids, carboxylic acid halides, alcohols, phenols, amines, or halogenated compounds, using known methods such as condensation reactions with well-known condensing agents or Williamson etherification reactions.

[0120] From the viewpoint of facilitating the reaction or obtaining compounds with free radical polymerizable groups or cationic polymerizable groups, it is preferable to condense one or all of the carboxyl groups of polyamide (A-II) with alcohols with free radical polymerizable groups or cationic polymerizable groups. Furthermore, even if the carboxyl group of polyacrylic acid (A-II) is modified by an alcohol with a free radical polymerizable group or an alcohol with a cationic polymerizable group, the modified polyacrylic acid (A-II) is amide-iminated by methods such as heating. In this case, amide-imination occurs by ring closure while simultaneously removing the alcohol with a free radical polymerizable group or an alcohol with a cationic polymerizable group. The method of condensation reaction is not particularly limited. For example, the carboxyl group of polyamide (A-II) can be condensed with an alcohol having a free radical polymerizable group or an alcohol having a cationic polymerizable group in the presence of a condensing agent such as a carbodiimide compound. Alternatively, after reacting the carboxyl group of polyacrylic acid (A-II) with a halogenating agent such as thionyl chloride to form a halocarbonyl group (carboxylic acid halide group), the halocarbonyl group can be reacted with an alcohol having a free radical polymerizable group or an alcohol having a cationic polymerizable group.

[0121] Examples of alcohols possessing free radical polymerizable groups include mono(meth)propyl groups such as 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, 3-hydroxypropane-2-yl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, 2-(2-hydroxyethoxy)ethyl methacrylate, and 1-(2-(meth)acryloxyethyl)2-(2-hydroxypropyl) phthalate. Acrylates; hydroxyl-containing polyols such as glycerol-1,3-di(meth)acrylate, glycerol-1,2-di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate; hydroxyalkyl-substituted (meth)acrylamides such as N-(2-hydroxyethyl)(meth)acrylamide; (hydroxymethyl)vinyl ketones, and (2- Ketones containing hydroxyl groups, such as hydroxyethyl vinyl ketone; alkenyl alcohols such as allyl alcohol, 5-hexen-1-ol, 3-hexen-1-ol, 6-hepten-1-ol, 5-octen-1-ol, 3-octen-1-ol, 3-nonen-1-ol, 6-nonen-1-ol, 9-decen-1-ol, 4-decen-1-ol, 10-undecen-1-ol, 11-dodecen-1-ol, 9,12-octadecadien-1-ol, oleyl alcohol, linolenic acid alcohol, linolenic acid alcohol, and 13-eicosyl alcohol. Furthermore, in the description of this application, (meth)acrylate means both acrylate and methacrylate. Examples of alcohols having cationic polymerizable groups include ethylene glycol monoglycidyl ether, 1,3-propanediol monoglycidyl ether, propylene glycol monoglycidyl ether, 1,4-butanediol monoglycidyl ether, 1,5-pentanediol monoglycidyl ether, 1,6-hexanediol monoglycidyl ether, diethylene glycol monoglycidyl ether, and dipropylene glycol monoglycidyl ether, as well as hydroxyl-substituted epoxyalkanes such as 3,4-epoxy-1-butanol.

[0122] The amount of tetracarboxylic dianhydride and diamine compound used in the synthesis of polyacrylic acid (A-II) is not particularly limited. However, relative to 1 mol of tetracarboxylic dianhydride, it is preferable to use 0.8 mol or more and 1.2 mol or less of diamine compound, more preferably 0.9 mol or more and 1.1 mol or less, and especially preferably 0.95 mol or more and 1.05 mol or less. Furthermore, the weight-average molecular weight of the obtained polyacrylic acid (A-II) can be appropriately set according to its intended use. The weight-average molecular weight of the resin can be determined by GPC (gel permeation chromatography) as the weight-average molecular weight converted to polystyrene. For example, from the viewpoint of obtaining a hardened film with good mechanical properties, the weight-average molecular weight of polyacrylic acid (A-II), converted to polystyrene as described above, is 5000 or more, preferably 15000 or more, and more preferably 250,000,000 or more. On the other hand, from the viewpoint of improving reproducibility, the weight-average molecular weight of the obtained polyacrylic acid (A-II), for example, is 100,000 or less, preferably 80,000 or less, and more preferably 50,000 or less, converted to polystyrene as described above. The weight-average molecular weight can be obtained by adjusting the amount of tetracarboxylic dianhydride and diamine compound, or by adjusting reaction conditions such as solvent or reaction temperature, to achieve the aforementioned value.

[0123] The reaction of tetracarboxylic dianhydride with diamine compounds is usually carried out in an organic solvent. The organic solvent used in this reaction is not particularly limited, as long as it can dissolve both the tetracarboxylic dianhydride and the diamine compound without reacting with them. Two or more organic solvents can be used alone or in combination.

[0124] Examples of organic solvents used in the reaction of tetracarboxylic dianhydrides with diamine compounds include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, N,N-dimethylacetamide, N,N-dimethylpropionic acid, N,N-dimethylisobutylamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylisobutylamide, methoxy-N,N-dimethylpropionic acid, butoxy-N,N-dimethylpropionic acid, N-methylcaprolactam, N,N'-dimethylacrylurea, N,N,N',N'-tetramethylurea, and pyridine. Dimethyl sulfoxide; cyclobutane; lactones such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ-caprolactone; esters such as methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate; carbonates such as ethyl carbonate and propylene carbonate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetonitrile; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, and tetrahydrofuran; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, and o-dichlorobenzene; hexane, heptane, benzene, toluene, and xylene. These organic solvents can be used alone or in combination of two or more.

[0125] Among these organic solvents, in terms of the solubility of the resulting polyamide acid (A-II) and polyimide resin (AI), nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, and N,N,N',N'-tetramethylurea are preferred.

[0126] The temperature at which tetracarboxylic dianhydride reacts with the diamine compound is not particularly limited, as long as the reaction proceeds well. Typically, the reaction temperature of tetracarboxylic dianhydride with the diamine compound is preferably between -5°C and 120°C, more preferably between 0°C and 80°C, and particularly preferably between 0°C and 50°C. The reaction time of tetracarboxylic dianhydride with the diamine compound also varies depending on the reaction temperature, but typically it is preferably between 30 minutes and 20 hours, more preferably between 1 hour and 8 hours, and particularly preferably between 2 hours and 6 hours.

[0127] Furthermore, when polyamide (A-II) is manufactured using the above method, a partial ring closure occurs in a portion of the polyamide, resulting in partial amide imidization. For convenience, resins with an amide imidization rate of less than 50% are referred to as polyamide (A-II), and resins with an amide imidization rate exceeding 50% are referred to as polyimide resins (AI).

[0128] Furthermore, when the tetracarboxylic dianhydride and / or diamine compound has a radical-containing polymerizable group containing an ethylene unsaturated double bond, a small amount of polymerization inhibitor may be used to prevent cross-linking between the ethylene unsaturated double bonds during the reaction. Examples of polymerization inhibitors include hydroquinone, 4-methoxyphenol, tert-butylcatechol, and phenols such as bis-tert-butylhydroxytoluene, or phenothiazines. The amount of polymerization inhibitor used, for example, is preferably 0.01 mol% to 5 mol% relative to the mole number of the ethylene unsaturated double bonds.

[0129] Using the methods described above, a solution containing polyacrylic acid (A-II) can be obtained. By cyclocloning the obtained polyamide (A-II) and then amide-imidizing it, polyamide resin (AI) is generated. The method of amide imidization is not particularly limited. Amylation can be carried out by heating or by using an amide imidizing agent.

[0130] When acetilimation is carried out by heating, the heating can be carried out on a solution or suspension of polyacrylic acid (A-II) or on solid polyacrylic acid (A-II). When heating a solution of polyamide (A-II) to perform amide imidization, it is preferable to remove the water that is generated as a byproduct during amide imidization while heating. The heating conditions used for aceimination are not particularly limited as long as the polyamide (A-II) or polyamide resin (AI) does not decompose and aceimination is carried out well. When heating a solution of polyacrylic acid (A-II), the preferred heating temperature is typically 80°C to 220°C, more preferably 100°C to 200°C, and particularly preferably 120°C to 180°C. When heating solid polyacrylic acid (A-II), the preferred heating temperature is typically 180°C to 400°C, and more preferably 200°C to 350°C. Although the heating time varies depending on the heating temperature, it is generally preferred to be more than 1 hour and less than 24 hours, and even more preferred to be more than 2 hours and less than 12 hours.

[0131] When amide-imidizing polyamide (A-II) using an amide-imidizing agent, the amide-imidizing agent is typically added to a solution or suspension of polyamide (A-II) to carry out the amide-imidizing process. The organic solvent that can be used for amide-imidization with an amide-imidizing agent is, for example, the same organic solvent that can be used to prepare polyamide (A-II). When amide is amided using an amide-iminizing agent, the concentration of polyamide (A-II) in the solution or suspension of polyamide (A-II) is not particularly limited. Typically, the concentration of polyamide (A-II) in the solution or suspension of polyamide (A-II) is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less. The amount of amide used is not particularly limited. The amount of amide used depends on the type of amide chosen to amide polyamide (A-II) to the desired degree. The reaction temperature for amide imidization using an amide imidizing agent is not particularly limited. The reaction temperature is preferably between 0°C and 100°C, and more preferably between 5°C and 50°C. The duration of the amide reaction when using an amide is not particularly limited. Depending on the type of amide, the amide reaction may preferably be carried out for 30 minutes to about 24 hours, more preferably for 1 hour to 12 hours, and even more preferably for 2 hours to 6 hours.

[0132] Examples of acetic anhydride agents include acetic anhydride, propionic anhydride, benzoic anhydride, trifluoroacetic anhydride, acetochlor, toluenesulfonyl chloride, methanesulfonyl chloride, ethyl chloroformate, triphenylphosphine and dibenzimidazolyl disulfide, dicyclohexylcarbodiimide, carbodiimidazole, 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline, and N,N'-disuccinimidyl oxalate, as well as basic compounds such as pyridine, methylpyridine, 2,6-dimethylpyridine, colinine, triethylamine, N-methylmorpholine, 4-N,N'-dimethylaminopyridine, isoquinoline, triethylamine, 1,4-diazabicyclo[2.2.2]octane, and 1,8-diazabicyclo[5.4.0]-7-undecene.

[0133] [Polyamide resin (A-III)] Polyamide resin (A-III) is a resin derived from diamine compounds, dicarboxylic acid compounds, or amide-forming derivatives of dicarboxylic acid compounds.

[0134] (Diamine compounds) As a diamine compound, the same compound as that described for polyimide resin (AI) and polyamide (A-II) can be used. As mentioned above, the resin (A) incorporated into the photosensitive resin composition has free radical polymerizable groups or cationic polymerizable groups on its molecular chain that can be polymerized by the action of the photosensitizer (C).

[0135] The bonding positions of the free radical polymerizable groups or cationic polymerizable groups in the molecular chain of polyamide resin (A-III) are not particularly limited. This is as described above for free radical polymerizable groups and cationic polymerizable groups, as well as for polyamide resin (AI) and polyamide acid (A-II). The amount of free radical polymerizable groups or cationic polymerizable groups in polyamide resin (A-III) is the same as that in polyimide resin (AI) and polyamide (A-II).

[0136] (Dicarboxylic acid compounds, and amide-forming derivatives of dicarboxylic acid compounds) As a dicarboxylic acid compound, various dicarboxylic acid compounds that have been used as raw materials for polyamide resins since the past can be used without particular restrictions. As a dicarboxylic acid compound, it is preferred to be an aliphatic dicarboxylic acid with 2 to 50 carbon atoms or an aromatic dicarboxylic acid with 8 to 50 carbon atoms.

[0137] Examples of amide-forming derivatives of dicarboxylic acid compounds include dicarboxylic acid halides and activated dicarboxylic acid compounds. Preferred dicarboxylic acid halides are dicarboxylic acid chlorides and bromides, with dicarboxylic acid chlorides being more preferred. Among activated dicarboxylic acid compounds, active groups derived from the carboxyl group include phenoxycarbonyl, (2-thiono-2,3-dihydrobenzoxazol-3-yl)carbonyl, 1H-1,2,3-triazol-1-ylcarbonyl, 1H-benzotriazol-1-oxycarbonyl, 1H-imidazol-1-ylcarbonyl, succinimidoxycarbonyl, and 3H-1,2,3-triazol[4,5-b]pyridin-3-oxycarbonyl. When the active group derived from the carboxyl group contains an aromatic ring, the aromatic ring may also be substituted by one or more substituents selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, trifluoromethyl, chlorine atom, bromine atom, iodine atom, phenoxy, and nitro.

[0138] Suitable examples of dicarboxylic acid compounds include adipic acid, sebacic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 4,4'-dicarboxybiphenyl, as well as alkyl, alkoxy, or halogenated derivatives of these compounds. The alkyl group, as a substituent, is preferably an alkyl group having 1 to 4 carbon atoms. The alkoxy group, as a substituent, is preferably an alkoxy group having 1 to 4 carbon atoms. When the aforementioned dicarboxylic acid compound is substituted with an alkyl, alkoxy, or halogen, the number of substitutions is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0139] Alternatively, a dicarboxylic acid compound having two carboxyl groups and two carboxylic ester groups or two carboxylic acid amine groups can be suitably used as a dicarboxylic acid compound by reacting the anhydride group of the carboxylic dianhydride described for polyimide resin (AI) and polyamide (A-II) with a monohydroxy compound or a monoamine compound.

[0140] Suitable examples of aromatic tetracarboxylic dianhydrides include benzopyrene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, and trimellitic acid (3,4-dicarboxyphenyl) dianhydride. 1,2,5,6-Naphthalenetetracarboxylic dianhydride, 2,3,6,7-Naphthalenetetracarboxylic dianhydride, 2,3,5,6-Pyridinetetracarboxylic dianhydride, 3,4,9,10-Perylenetetracarboxylic dianhydride, [5,5'-(1,4-epenylphenyl)bisnorbornene]-2,2',3,3'-tetracarboxylic dianhydride (e.g., Enehyde (registered trademark) BzDA, ENEOS), 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-disideoxy-3-furanyl)naphtho[1,2-C]furan-1,3-dione (e.g., Rikacid) The dicarboxylic acid compounds corresponding to TDA-100 (manufactured by Shin Nippon Rikka Co., Ltd.), 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride, 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride, 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (e.g., Rikacid TMEG100, manufactured by Shin Nippon Rikka Co., Ltd.), and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane Kasei Co., Ltd.), are preferably dicarboxylic acid compounds obtained by reacting these aromatic tetracarboxylic acid dianhydrides with an alcohol represented by Ra21-OH or an amine represented by Ra21-NH2. Ra21 is a monovalent organic group. Such a dicarboxylic acid compound has two pairs of carboxyl groups on adjacent carbon atoms and groups represented by -CO-X aR a21. X a is -O- or -NH.

[0141] The number of carbon atoms in the monovalent organogroup of Ra21 is preferably 1 to 20, more preferably 1 to 16, even more preferably 1 to 12, and most preferably 1 to 8. Examples of monovalent organic groups of Ra21 include alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, alkoxyalkyl groups with 2 to 20 carbon atoms, alkoxyalkylalkyl groups with 3 to 20 carbon atoms, (meth)propenyloxyalkyl groups with 4 to 20 carbon atoms, (meth)propenyloxyalkoxyalkyl groups with 5 to 20 carbon atoms, glycidyloxyalkyl groups with 4 to 20 carbon atoms, and glycidyloxyalkoxyalkyl groups with 5 to 20 carbon atoms.

[0142] Among the aforementioned dicarboxylic acid compounds having two pairs of carboxyl groups and a group represented by -CO-X aRa21, there are isomers in which the position of the carboxyl group differs from the position of the group represented by -CO-X aRa21. As the aforementioned dicarboxylic acid compound, one of such isomers may be used alone, or two or more may be used in combination. As an example, regarding dicarboxylic acid compounds corresponding to benzopyrenic acid dianhydride, isomers include compounds represented by formulas (a4-a1) and (a4-a2). Furthermore, regarding dicarboxylic acid compounds corresponding to 1,4-bis(3,4-dicarboxyphenoxy)benzodianhydride, isomers include compounds represented by formulas (a4-b1), (a4-b2), and (a4-b3). In the following formulas (a4-a1), (a4-a2), and (a4-b1) to (a4-b3), X a and Ra21 are respectively as described above.

[0143]

[0144] The dicarboxylic acid compounds corresponding to the tetracarboxylic acid dianhydrides represented by formulas (a3-2) to (a3-4) can be listed below as compounds represented by formulas (a4-2a) to (a4-2c), (a4-3a) to (a4-3c), and (a4-4a) to (a4-4c). In formulas (a4-2a) to (a4-2c), (a4-3a) to (a4-3c), and (a4-4a) to (a4-4c), Ra01 to Ra05 are the same as those in formulas (a3-2) to (a3-4). In formulas (a4-2a) to (a4-2c), (a4-3a) to (a4-3c), and (a4-4a) to (a4-4c), Xa and Ra21 are as described above.

[0145] The dicarboxylic acid compounds corresponding to the tetracarboxylic acid dianhydrides represented by formulas (a3-5) to (a3-7) can be listed below as compounds represented by formulas (a4-5a) to (a4-5c), (a4-6a) to (a4-6c), (a4-7a), and (a4-7b). In formulas (a4-5a) to (a4-5c), (a4-6a) to (a4-6c), (a4-7a), and (a4-7b), Ra01 to Ra03, Ra06, m1, and m2 are the same as those in formulas (a3-5) to (a3-7). In equations (a4-5a) to (a4-5c), (a4-6a) to (a4-6c), (a4-7a) and (a4-7b), Xa and Ra21 are as described above.

[0146]

[0147] Monohydroxy compounds of dicarboxylic acids obtained by reacting with tetracarboxylic acid dianhydrides include, for example, alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol; phenols or naphthols such as phenol, p-cresol, m-cresol, o-cresol, α-naphthol, and β-naphthol; monoethers of diols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, 1,3-propanediol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; alcohols with free radical polymerizable groups as described above; and alcohols with cationic polymerizable groups as described above.

[0148] The reaction of tetracarboxylic dianhydride with the aforementioned monohydroxy or monoamine compounds can be carried out by the same method as the reaction of tetracarboxylic dianhydride with diamine compounds described above, which is used in the production of polyacrylic acid (II). The reaction of tetracarboxylic dianhydride with the aforementioned monohydroxy or monoamine compounds can also be carried out in the presence of organic bases such as pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, and 1,4-azabicyclo[2,2,2]octane. These bases can be used alone or in combination of two or more. The amount of monohydroxy or monoamine compounds used is preferably 1.8 mol to 2.2 mol, and more preferably 2 mol to 2.1 mol, relative to 1 mol of tetracarboxylic dianhydride. Dicarboxylic acid compounds can be obtained by reacting tetracarboxylic dianhydride with the aforementioned monohydroxy or monoamine compounds. In the manufacture of dicarboxylic acid compounds, depending on the manufacturing conditions, there may be cases where only one dicarboxylic acid anhydride group reacts with a monohydroxy or monoamine compound to generate a monocarboxylic acid compound containing a dicarboxylic acid anhydride group, or where a portion of the tetracarboxylic acid dianhydride reacts with water in the reaction system to generate a tetracarboxylic acid compound or a tricarboxylic acid compound. Provided the resin is available, a dicarboxylic acid compound comprising at least one of the above-mentioned monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds may be used in the manufacture of polyamide resin (A-III). When the dicarboxylic acid compound contains at least one of the above-mentioned monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds as an impurity, the content of the at least one of the above-mentioned monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds as an impurity in the dicarboxylic acid compound is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 1% by mass or less, relative to the mass of the dicarboxylic acid compound containing the impurity.

[0149] (Manufacturing method of polyamide resin (A-III)) The manufacturing method of polyamide resin (A-III) is not particularly limited. Preferred methods for manufacturing polyamide resins (A-III) include, for example, condensing a diamine compound with a dicarboxylic acid compound using a condensing agent. Examples of condensing agents include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate.

[0150] Other preferred methods include the condensation of a dicarboxylic acid compound or its acid halide with a diamine compound in the presence of a base. In this method, a base and a condensing agent may also be used together, if necessary. As acid halides, acid chlorides and acid bromides are preferred, and acid chlorides are even more preferred. Examples of bases include pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, and 1,4-azabicyclo[2,2,2]octane. Examples of condensing agents include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylureon tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylureon hexafluorophosphate, (2,3-dihydro-2-thiono-3-benzoxazolyl)phosphonate diphenyl ester, and 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)4-methoxymorpholinium chloride hydrate, etc.

[0151] Specifically, a dicarboxylic acid compound or its acid halide, and a diamine compound are reacted in an organic solvent in the presence of the aforementioned base, for example at a temperature between -20°C and 150°C, preferably between 0°C and 50°C, for a period of 30 minutes to 24 hours, preferably between 1 hour and 4 hours. The amount of alkali used should be such that it is easily removed and that high molecular weight molecules are easily obtained. Ideally, it should be more than 2 moles and less than 4 moles relative to the mole number of the dicarboxylic acid compound or its acid halide.

[0152] Alternatively, a preferred method is to convert the carboxyl group of a dicarboxylic acid compound into an active group, and then condense the compound having the active group derived from the dicarboxylic acid compound with a diamine compound. Among the activated dicarboxylic acid compounds, the active group derived from the carboxyl group can be phenoxycarbonyl, (2-thiono-2,3-dihydrobenzoxazol-3-yl)carbonyl, 1H-1,2,3-triazol-1-ylcarbonyl, 1H-benzotriazol-1-oxycarbonyl, 1H-imidazol-1-ylcarbonyl, succinimidoxycarbonyl, and 3H-1,2,3-triazol[4,5-b]pyridine-3-oxycarbonyl. When the active group derived from the carboxyl group contains an aromatic ring, the aromatic ring may also be substituted by one or more substituents selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, trifluoromethyl, chlorine atom, bromine atom, iodine atom, phenoxy, and nitro.

[0153] To improve the storage stability of photosensitive resin compositions, or to further enhance the mechanical properties of films formed using photosensitive resin compositions, or to improve the reproducibility of polymerization during the manufacture of resin (A), the main chain ends of resin (A) can also be capped with end-capping agents. Examples of end-capping agents include monoamines, acid anhydrides, monocarboxylic acids, monobasic acid halides, and monoactive ester compounds. The monoamine used for end capping can be a known compound. 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 with 3 to 20 carbon atoms such as hexylamine and octylamine that may have a branched structure; monoamines with an alicyclic structure such as cyclohexylamine; or aminosilanes such as trimethoxyaminopropylsilane and triethoxyaminopropylsilane. Among acid anhydrides, monobasic acid halides, and monoactive ester compounds used as end-capping agents, acid anhydrides are preferred. Known acid anhydrides and their derivatives can be used. Examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, XO-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and their derivatives. [] The rate of introduction of the end-capping agent in resin (A) is preferably 40 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less, relative to the total number of moles of the photosensitive resin composition, from the viewpoint of the excellent mechanical properties of the film formed by using the photosensitive resin composition or the excellent developability of the photosensitive resin composition.

[0154] <Monomer Compound (B)> When resin (A) has a free radical polymerizable group, the photosensitive resin composition may also include, in addition to polyimide resin (A), a monomer compound having an ethylene unsaturated double bond as a monomer compound (B). This monomer compound (B) may be a monofunctional monomer compound or a polyfunctional monomer compound, preferably a polyfunctional monomer compound.

[0155] Examples of monofunctional monomeric compounds include (meth)acrylamide, hydroxymethyl (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, edacic acid, edacic anhydride, citracic acid, citracic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. Butyl acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloxy-2-hydroxypropyl phthalate, glyceryl mono(meth)acrylate, tetrahydrofuran methyl (meth)acrylate, dimethylamine (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, hemi(meth)acrylates of phthalic acid derivatives, etc. These monofunctional photopolymerizable monomers can be used alone or in combination of two or more.

[0156] Examples of multifunctional monomeric compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, and trimethylolpropanediol di(meth)acrylate. Di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(3-(meth)acryloxypropyl) ether, glycerol di(meth)acrylate, tri(meth)acrylate of glycerol ethylene oxide (EO) adduct, tri(meth)acrylate of glycerol propylene oxide (PO) adduct, tri(meth)acrylate of glycerol EO / PO co-adduct, tri(meth)acrylate of trimethylolpropane ethylene EO adduct, tri(meth)acrylate of trimethylolpropane PO adduct, tri(meth)acrylate of trimethylolpropane EO / PO co-adduct, tri(meth)acrylate of trimethylolpropane EO adduct (Meth)acrylate, tri(meth)acrylate of trimethylolethane PO adduct, tri(meth)acrylate of trimethylolethane EO / PO co-adduct, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentapentaerythritol undeca(meth)acrylate, pentapentaerythritol dodeca(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate 1,3-Adamantanediol di(meth)acrylate, 1,3,5-Adamantanetriol di(meth)acrylate, 1,3,5-Adamantanetriol tri(meth)acrylate, 1,4-Cyclohexanediethanol di(meth)acrylate, 2,2-bis(4-(meth)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)propenyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)propenyloxypropyl(meth)acrylate, 9,9-bis[4-(2-(meth)propenyloxyethoxy)phenyl], 9,9-bis[4-(2-(meth)propenyloxypropoxy)-3-methylphenyl], 9,9-Bis[4-(2-(meth)propenyloxyethoxy)-3,5-dimethylphenyl] ester, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, glyceryl triacrylate, glyceryl polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., toluene diisocyanate), the reaction product of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate with 2-hydroxyethyl (meth)acrylate, tri((meth)propenyloxyethyl)isotricyanate, methylene bis(meth)propenylamine, (meth)propenylamine methylene ether, condensates of polyols and N-hydroxymethyl (meth)propenylamine, etc., or triacryl formal, etc. These multifunctional monomeric compounds can be used alone or in combination of two or more.

[0157] Furthermore, it is preferred to use the urethane (meth)acrylates described in Japanese Patent Publication Nos. 48-41708, 50-6034, and 51-37193; the polyester (meth)acrylates described in Japanese Patent Publication Nos. 48-64183, 49-43191, and 52-30490; the epoxy (meth)acrylates formed by the reaction of epoxy resin and (meth)acrylic acid; the compounds described in paragraphs

[0254] to

[0257] of Japanese Patent Publication No. 2008-292970; and compounds containing epoxy groups and ethylene groups, such as polyfunctional carboxylic acids and glycidyl (meth)acrylates. Polyfunctional (meth)acrylates obtained by reacting compounds with ethylene unsaturated groups; compounds or Cardo resins having a cyclopentadienyl ring and having two or more ethylene unsaturated groups as described in Japanese Patent Application Publications No. 2010-160418, 2010-129825, and 4364216; unsaturated compounds described in Japanese Patent Application Publications Nos. 46-43946, 1-40337, and 1-40336; vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 2-25493; compounds containing perfluoroalkyl groups as described in Japanese Patent Application Publication No. 61-22048; and photopolymerizable monomers and oligomers described in the Journal of the Japan Adhesion Association, vol.20, No.7, pp. 300-308 (1984).

[0158] Among these monomeric compounds with ethylene-like unsaturated double bonds, there is a tendency to improve the adhesion of the cured material to the substrate and the strength of the cured material. It is particularly preferred to have polyfunctional monomeric compounds with 3 or more functions, more preferably polyfunctional monomeric compounds with 4 or more functions, and even more preferably polyfunctional monomeric compounds with 5 or more functions.

[0159] When resin (A) has an ethylene oxide group as a cationic polymerizable group, the photosensitive resin composition may also include resin (A) and a vinyl ether compound as a monomer compound (B). This vinyl ether compound may be a monofunctional compound having one ethylene oxide group or a polyfunctional compound having two or more ethylene oxide groups.

[0160] When resin (A) contains epoxy groups as cationic polymerizable groups, the photosensitive resin composition may also contain various epoxy compounds as monomer compounds (B).

[0161] The content of monomer compound (B) in the photosensitive resin composition is not particularly limited to the extent that it does not impede the purpose of the present invention. When the mass of the photosensitive resin composition after removing the solvent (S) described later is 100 parts by mass, the content of monomer compound (B) in the photosensitive resin composition is preferably 0.1 parts by mass to 50 parts by mass, more preferably 0.5 parts by mass to 40 parts by mass, and particularly preferably 1 part by mass to 25 parts by mass.

[0162] <Photosensitive Agent (C)> The photosensitive resin composition contains a photosensitizer (C) of a type corresponding to the type of resin (A). When the resin (A) has free radical polymerizable groups on its molecular chain, a photoradical polymerization initiator (C1) is used as the photosensitizer (C). When the resin (A) has cationic polymerizable groups on its molecular chain, a photocationic polymerization initiator (C2) is used as the photosensitizer (C). The photoradical polymerization initiator (C1) and the photocationic polymerization initiator (C2) are not particularly limited, and conventionally known photopolymerization initiators can be used.

[0163] Specifically, as photoradical polymerization initiators (C1), examples include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropenyl)benzyl]phenyl}-2-methyl-propane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(4-dimethylaminophenyl)one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinylphenyl)-butane-1-one, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-2-(benzoyloximeimino)-1-propanone, 1-phenyl-1,2-butanedione -2-(o-methoxycarbonyl)oxime, 1,3-diphenyltriketone-2-(o-ethoxycarbonyl)oxime, acetone, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1-phenyl-3-ethoxytriketone-2-(O-benzoyl)oxime, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazole-3-yl]acetone oxime (Irgacure) OXE02 (manufactured by BASF JAPAN), (9-ethyl-6-nitro-9H-carbazole-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl] methyl ketone O-acetyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (Irgacure OXE01, manufactured by BASF JAPAN), NCI-831 (manufactured by ADEKA), NCI-930 (manufactured by ADEKA), OXE-03 (manufactured by BASF JAPAN), OXE-04 (manufactured by BASF JAPAN) (Manufactured by JAPAN Corporation), 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-Trimethylpentylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isopentyl 4-dimethylaminobenzoate, ethyl 4-diethylbenzoate, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, methyl benzoylformate, ethyl benzoylformate, 2,4-diethylthioxanone, 2-chlorothioxanone, 2,4-dimethylthioxanone, 1-chloro-4-propoxythioxanone, thioxanone, 2-Chlorothioxanthroline, 2,4-Diethylthioxanthroline, 2-Methylthioxanthroline, 2-Isopropylthioxanthroline, Anthraquinone, 2-Ethylanthraquinone, 2-tert-Butylanthraquinone, Octamethylanthraquinone, 2-Aminoanthraquinone, β-Chlorothioxanthroline, 1,2-Benzanthraquinone, 2,3-Diphenylanthraquinone, Anthraquinone, Benzoanthraquinone, Dibenzocycloheptanone, Methyleneanthraquinone, Azobisisobutyronitrile, Benzoylperoxide, Cumyl hydroperoxide, 2-Mercaptobenzimidazole, 2-Mercaptobenzimidazole, 2-Mercaptobenzimidazole, 2-Mercaptobenzimidazole, 2-(o-chlorophenyl)-4,5-Di(m-methoxyphenyl)-imidazolyl dimer, Benzophenone, 2-Chlorobenzophenone, p,p'-bis(dimethylaminobenzophenone), 4,4'-bis(diethylaminobenzophenone), 4,4'- Dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, 4-hydroxybenzophenone, 4-phenylbenzophenone, benzophenone, diphenyl ethylene glycol, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methylpropionylbenzene, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, 2-phenylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanone, 2-methylthioxanone Ketones, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-sideoxy-9H-thioxanth-2-oxy)-N,N,N-trimethyl-1-propanediamine chloride, 4-azidophenylmethylene acetophenone, 2,6-bis(p-azidobenzylidene)cyclohexane, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone, dibenzocycloheptanone, pentyl-4-dimethylaminobenzoate, 9-phenylacridinium, 1,7-bis-(9-acridyl)heptane, 1,5-bis-(9-acridyl)pentane, 1,3-bis-(9-acridyl)propane, p-methoxytriazine, 2,4,6-Trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3, [4-Dimethoxyphenyl)vinyl]-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 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'-methyldiphenyl ketone, dibenzyl ketone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl) Examples of photoradical polymerization initiators (C1) include benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-propenyloxy)ethyl]benzamide bromide, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propenamine onium chloride monohydrate, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzothiazole disulfide, triphenylphosphine, carbon tetrabromide, and tribromophenyl sulfonium. These photoradical polymerization initiators can be used alone or in combination of two or more. From the perspective of good sensitivity, oxime ester-based photopolymerization initiators (C1) are preferred as photoradical polymerization initiators.

[0164] Among photoradical polymerization initiators (C1), from the viewpoint of sensitivity of photosensitive resin components, oxime ester compounds are preferred. As an oxime ester compound, it is preferred to be a compound having a partial structure represented by the following formula (c1).

[0165] (in formula (c1),) n1 is either 0 or 1. Rc2 is a monovalent organic group. Rc3 is a hydrogen atom, and may contain 1 to 20 carbon atoms of an aliphatic hydrocarbon group or an aryl group that may contain substituents. * indicates the bonding location.

[0166] Onium salts are typically used as photocationic polymerization initiators (C2). Examples of onium salts, ammonium salts, phosphonium salts, strontium salts, and monium salts are also available, with strontium salts and monium salts being more preferred.

[0167] The content of the photoradical polymerization initiator (C1) or the photocationic polymerization initiator (C2) in the photosensitive resin composition is not particularly limited as long as the photosensitive resin composition has the desired photolithography properties. Typically, the content of the photoradical polymerization initiator (C1) or the photocationic polymerization initiator (C2) in the photosensitive resin composition is, relatively speaking, 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total mass of the resin (A) and the monomer compound (B).

[0168] <Polyfunctional Thiol Compounds (D)> The photosensitive resin composition contains a polyfunctional thiol compound (D). By containing the polyfunctional thiol compound (D), the photosensitive resin composition can be used to form a patterned resin film that exhibits good durability and low dielectric tangent in the High Accelerated Stress Test (HAST). A polyfunctional thiol compound (D) is a compound having two or more thiol groups in one molecule, and is not particularly limited as long as it does not impair the desired effect.

[0169] As a polyfunctional thiol compound (D), it is preferred to be a compound represented by the following formula (d1). (In formula (d1), R d1 is a divalent chain aliphatic hydrocarbon group that may have substituents, and R d2 is an n-valent aliphatic group that may contain heteroatoms, where n is an integer between 2 and 4).

[0170] In formula (d1), the divalent chain aliphatic hydrocarbon group of R d1 may contain a carbon-carbon unsaturated double bond, preferably an alkyl group. The number of carbon atoms in the divalent chain aliphatic hydrocarbon group of R d1 is preferably 1 to 20, more preferably 1 to 8.

[0171] Suitable specific examples of divalent chain aliphatic hydrocarbon groups of R d1 include methylene, ethyl(ethane-1,2-diyl), propane-1,3-diyl, propane-1,2-diyl, propane-1,1-diyl, propane-2,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-1,2-diyl, butane-1,1-diyl, butane-2,3-diyl, butane-2,2-diyl, pentane-1,5-diyl, pentane-1,4-diyl, pentane-1,3-diyl, pentane-1,2-diyl, pentane-1,1-diyl, and hexane-1,6-diyl. Hexane-1,5-diyl, hexane-1,4-diyl, hexane-1,3-diyl, hexane-1,2-diyl, hexane-1,1-diyl, heptane-1,7-diyl, heptane-1,6-diyl, heptane-1,5-diyl, heptane-1,4-diyl, heptane-1,3-diyl, heptane-1,2-diyl, heptane-1,1-diyl, octane-1,8-diyl, octane-1,7-diyl, octane-1,6-diyl, octane-1,5-diyl, octane-1,4-diyl, octane-1,3-diyl, octane-1,2-diyl, and octane-1,1-diyl, etc.

[0172] In formula (d1), the n-valent aliphatic group that can contain heteroatoms as R d2 can be linear, branched, or cyclic. Examples of heteroatoms that can be contained in the aliphatic group include nitrogen, oxygen, and sulfur atoms. The number of carbon atoms in the aliphatic group of Rd2 is preferably 1 to 10, and more preferably 3 to 8. Preferred examples of the aliphatic group of Rd2 include groups obtained by removing one, two, or three hydrogen atoms from methyl, ethyl, propyl, butyl, pentyl, hexyl, or heptyl. Furthermore, 2,4,6-trisideroxy-1,3,5-triazinane-1,3,5-triyl, is also preferred as an aliphatic group on the ring.

[0173] Specific examples of polyfunctional thiol compounds (D) represented by formula (d1) include pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane benzoate (3-mercaptobutyrate), trimethylolpropane benzoate (3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), 1,3-propanediol bis(3-mercaptobutyrate), and 1,4-butanediol (3-mercaptobutyrate). Ethylene glycol bis(3-mercaptopropionate), 1,3-propanediol bis(3-mercaptopropionate), 1,4-butanediol (3-mercaptopropionate), 1,3,5-triazine-2,4,6-trione (2-(3-mercaptobutyryloxy)ethyl)-1,3,5-triazine-2,4,6-trione, and 1,3,5-triazine-2-(3-mercaptopropyloxy)ethyl)-1,3,5-triazine-2,4,6-trione.

[0174] From the viewpoint that the desired effect can be easily obtained by using polyfunctional thiol compounds (D), the amount of polyfunctional thiol compounds (D) used in the photosensitive resin composition is preferably 0.01% to 30% by mass, more preferably 0.05% to 20% by mass, and even more preferably 1% to 10% by mass, relative to polyamide resin.

[0175] <Organic Solvents (S)> Photosensitive resin compositions may also contain organic solvents (S) for purposes such as adjusting coatability. The type of organic solvent (S) is not particularly limited as long as it can dissolve the resin (A) or other components well.

[0176] From the viewpoint of the good solubility of resin (A), specific examples of organic solvents (S) include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and hexamethylphosphatidylamine. Nitrogen-containing polar solvents such as phosphoramide, 1,3-dimethyl-2-imidazolinone, N,N-dimethylisobutylamine, 3-methoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-dimethylpropionic acid, N,N-dimethylpropionic acid, N,N-dimethylisobutylamine, and N,N-dimethylacrylamide; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, diisobutyl ketone, cyclopentanone, cyclohexanone, and isoflavone; and γ-butyrolactone, γ-valerolactone, δ-valerolactone, and γ-caprolactone. Ester, ε-caprolactone, α-methyl-γ-butyrolactone, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, isoamyl acetate, n-pentyl formate, n-butyl propionate, isopropyl butyrate, ethyl butyrate, n-butyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-methoxy Esters of methyl propionate, ethyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, methyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-butyrate, ethyl 2-butyrate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl ceroxythionate, ethyl ceroxythionate, etc. 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 ethyl carbonate and propylene carbonate; aromatic solvents such as anisole, toluene, and xylene; aliphatic hydrocarbons such as limonene; and urethanes such as dimethyl urethane.

[0177] The amount of organic solvent (S) used is not particularly limited as long as it can produce a homogeneous liquid photosensitive resin composition. The photosensitive resin composition can be a suspension or a solution, but is preferably a solution. Typically, the organic solvent (S) is used to make the solid content concentration of the photosensitive resin composition preferably 15% by mass or more and 50% by mass or less, and more preferably 20% by mass or more and 45% by mass or less.

[0178] <Other Ingredients> The photosensitive resin composition may also contain various additives other than those listed above, as needed. Examples of additives include colorants, dispersants, sensitizers, adhesion promoters, polymerization inhibitors, antioxidants, UV absorbers, agglomeration inhibitors, defoamers, surfactants, amide accelerators, nitrogen-containing heterocyclic compounds as adhesion enhancers, and silane coupling agents. Furthermore, the photosensitive resin composition may also contain various fillers or reinforcing materials, as needed.

[0179] As a sensitizer, known compounds can be used. 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.

[0180] Known compounds can be used as polymerization inhibitors. Examples of polymerization inhibitors include compounds with phenolic hydroxyl groups, nitroso compounds, N-oxide compounds, quinone compounds, N-oxygen compounds, and phenothiazine compounds. More specifically, preferred polymerization inhibitors are Irganox 1010, Irganox 1035, Irganox 1098, Irganox 1135, Irganox 245, Irganox 259, Irganox 3114 (all manufactured by BASF JAPAN), 2,6-di-tert-butyl-p-cresol, and 4-methoxyphenol; more preferably, Irganox 1010, 2,6-di-tert-butyl-p-cresol, and 4-methoxyphenol.

[0181] From the viewpoint of balancing the excellent developability and good antioxidant effect of the photosensitive resin composition, the amount of polymerization inhibitor used, relative to the mass of resin (A), is preferably 0.005% by mass or more and 1% by mass, more preferably 0.01% by mass or more and 0.5% by mass, and even more preferably 0.03% by mass or more and 0.3% by mass.

[0182] Nitrogen-containing heterocyclic compounds are stabilized by coordination onto metal surfaces, thereby improving the adhesion of films formed using photosensitive resin compositions to metal surfaces. Known compounds can be used as nitrogen-containing heterocyclic compounds. Examples of nitrogen-containing heterocyclic compounds include imidazole, pyrazole, indazole, carbazole, triazole, pyrazoline, pyrazolidine, tetraazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid, and their derivatives. From the perspective of coordination with metals, specific examples of preferred nitrogen-containing heterocyclic compounds include triazoles such as 1H-benzotriazole, 4-methyl-1H-methylbenzotriazole, 5-methyl-1H-methylbenzotriazole, 4-carboxy-1H-methylbenzotriazole, and 5-carboxy-1H-methylbenzotriazole, or triazoles such as 1H-tetrazole, 5-methyl-1H-tetrazole, and 5-phenyl-1H-tetrazole.

[0183] From the viewpoint of balancing the excellent developability of the photosensitive resin composition with improving the adhesion of the film formed using the photosensitive resin composition to the 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 resin (A).

[0184] By incorporating a silane coupling agent into a photosensitive resin composition, the adhesion of the film formed using the photosensitive resin composition to a substrate or similar material can be improved. The silane coupling agent can be a known compound. Examples of silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, 2-(epoxycyclohexyl)ethyltrimethoxysilane, 2-(epoxycyclohexyl)triethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, tris(3-triethoxysilylpropyl)isocyanurate, the reaction product of 3-aminopropyltrimethoxysilane with acid anhydride, and the reaction product of 3-aminopropyltriethoxysilane with acid anhydride. Examples of acid anhydrides that react with 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane include succinic anhydride, maleic anhydride, norcamphenic anhydride, 3-hydroxyphthalic anhydride, benzopyrene dianhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 2,2',3,3'-benzophenone tetracarboxylic anhydride, and 4,4'-oxydiphthalic anhydride.

[0185] The amount of silane coupling agent used is preferably 0.01% by mass to 10% by mass relative to the mass of resin (A).

[0186] By incorporating surfactants into photosensitive resin compositions, the coatability of the photosensitive resin composition and the wettability between the photosensitive resin composition and the substrate are improved. Known compounds can be used as surfactants. Examples of surfactants include fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and polysiloxane surfactants.

[0187] The amount of surfactant used is preferably 0.001% by mass or less than 1% by mass relative to the mass of resin (A).

[0188] When resin (A) is a resin that can be converted into polyimide resin by heating, the photosensitive resin composition may also contain a cyclization accelerator. The cyclization accelerator is a polyimide resin formed by promoting the cyclization of polyamide (A-II) or polyamide resin (A-III) containing units derived from dicarboxylic acid compounds synthesized by the reaction of tetracarboxylic dianhydrides and monohydroxy compounds. When a photosensitive resin composition contains a cyclization accelerator, the mechanical properties or weather resistance of the film formed by cyclizing the photosensitive resin composition with polyimide resin or benzoxazole resin are improved. Known cyclization accelerators, such as alkali-generating agents or acid-generating agents, can be used.

[0189] The amount of various additives used is not particularly limited without hindering the purpose of the present invention. The amount of additives used, other than those described above, can be appropriately adjusted relative to the mass of the solid components of the photosensitive resin composition, for example, within the range of 0.001% by mass to 60% by mass, preferably 0.01% by mass to 5% by mass.

[0190] <Preparation Method of Photosensitive Resin Composition> A photosensitive resin composition can be prepared by uniformly mixing the necessary components described above with any other required components in the desired amounts. The mixing method is not particularly limited. Preferably, the photosensitive resin composition is filtered through a filter to remove foreign matter.

[0191] Photosensitive dry film A photosensitive dry film comprises a substrate film and a photosensitive layer formed on the surface of the substrate film, wherein the photosensitive layer is composed of the aforementioned photosensitive resin composition.

[0192] As a substrate film, it is preferable to have light transmittance. Specifically, polyethylene terephthalate (PET) film, polypropylene (PP) film, and polyethylene (PE) film can be listed. From the viewpoint of having a good balance between light transmittance and tensile strength, polyethylene terephthalate (PET) film is preferred.

[0193] A photosensitive dry film is manufactured by forming a photosensitive layer by coating the aforementioned photosensitive resin composition onto a substrate film. When forming a photosensitive layer on a substrate film, an applicator, bar coater, wire bar coater, roller coater, or curtain coater is used to coat the photosensitive resin composition on the substrate film and then dry it, so that the film thickness after drying is preferably 0.5 μm to 300 μm, more preferably 1 μm to 300 μm, and especially preferably 3 μm to 100 μm.

[0194] A protective film may be further formed on top of the photosensitive layer in a photosensitive dry film. Examples of such protective films include polyethylene terephthalate (PET) film, polypropylene (PP) film, and polyethylene (PE) film.

[0195] <Method for Manufacturing Patterned Resin Films> This can be achieved by a lamination step including: laminating a photosensitive layer made of the aforementioned photosensitive resin composition onto a substrate. The exposure step, which involves selectively irradiating the photosensitive layer with active light or radiation, is similar to... The method of developing a patterned resin film by developing an exposed photosensitive layer to obtain a patterned resin film is used to manufacture the patterned resin film.

[0196] The substrate used for laminating the photosensitive layer is not particularly limited, and conventionally known substrates can be used, such as substrates for electronic components, or substrates on which specific wiring patterns are formed. Silicon substrates or glass substrates can also be used as substrates.

[0197] The photosensitive layer is laminated onto the substrate, for example, as follows: A liquid photosensitive resin composition is applied to the substrate, and the solvent is removed by heating to form a photosensitive layer of the desired thickness. The thickness of the photosensitive layer is not particularly limited, as long as it allows for the formation of a photoresist pattern as a template. The thickness of the photosensitive layer 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. Alternatively, the aforementioned photosensitive dry film can be applied to a substrate, and a photosensitive layer can be laminated onto the substrate.

[0198] The photosensitive resin composition can be coated onto the substrate using methods such as spin coating, slot coating, roller coating, screen printing, and applicator coating. Pre-baking the photosensitive layer is preferable. Pre-baking conditions vary depending on the type and blending ratio of the components in the photosensitive resin composition and the coating thickness, but are generally between 70°C and 200°C, preferably between 80°C and 150°C for approximately 2 minutes to 120 minutes. For the photosensitive layer formed as described above, active light or radiation, such as ultraviolet or visible light with wavelengths above 300nm and below 500nm, can be selectively irradiated (exposed) through a mask with a specific pattern.

[0199] As sources of radiation, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon lasers can be used. Furthermore, radiation includes microwaves, infrared rays, visible light, ultraviolet rays, X-rays, gamma rays, electron beams, proton beams, neutron beams, and ion beams. While the radiation dose varies depending on the composition of the photosensitive resin or the thickness of the photosensitive layer, for example, when using an ultra-high-pressure mercury lamp, it is generally between 100 mJ / cm² and 10,000 mJ / cm².

[0200] Next, the exposed photosensitive layer is developed using conventional methods to dissolve and remove unwanted portions, thereby forming a resin film patterned into a specific shape. At this time, a developer solution is used that corresponds to the components contained in the photosensitive resin composition. When the photosensitive resin composition contains a resin (A) with alkali-soluble groups, such as polyacrylic acid (A-II), an alkaline aqueous solution is used as the developer solution. When the photosensitive resin composition contains a resin (A) with free radical polymerizable groups or cationic polymerizable groups, and contains little or no components soluble in alkaline aqueous solutions, or components that become soluble in alkaline aqueous solutions through exposure, the aforementioned organic solvent (S) can be used as the developer solution.

[0201] As an alkaline developer, aqueous solutions of bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, 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 also be used as a developer. Alternatively, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or surfactant such as methanol or ethanol to the above-mentioned alkaline aqueous solutions can also be used as a developer.

[0202] The development time varies depending on the composition of the photosensitive resin or the thickness of the photosensitive layer, but it is usually between 1 minute and 30 minutes. The development method can be any of the following: liquid-filled method, immersion method, puddle method, spray development method, etc.

[0203] After development, a wash for 30 to 90 seconds is performed as needed, followed by drying the patterned resin film using an air gun or oven. This forms a resin film of the desired shape on the substrate surface. The washing solvent is not particularly limited. For example, in cases of alkaline development, water or alcohols can be used as the washing solvent. In cases of development with organic solvents, (S) organic solvents can be used within a range that does not cause solvent shock.

[0204] When the resin film contains polyamide (A-II) or polyamide resin (A-III) which comprises units derived from dicarboxylic acid compounds synthesized by the reaction of tetracarboxylic dianhydride and monohydroxy compounds, the polyamide resin (A-III) or polyamide (A-II) can be converted into polyimide resin (A) by baking the developed coated film as needed after development. The baking temperature is the same as that described above for resin (A). Furthermore, from the viewpoint of preventing oxidation of the hardened film and obtaining a hardened film with good mechanical properties, baking is preferably carried out in an inert gas environment such as nitrogen or argon.

[0205] The patterned resin film formed as described above is suitable for use as an insulating film in semiconductor devices, an interlayer insulating film for rewiring layers, or an insulating film or protective film in touch panel displays or organic electroluminescent display panels. Because the aforementioned photosensitive resin composition has good resolution, the patterned resin film formed as described above is preferably used as an interlayer insulating film for rewiring layers, particularly in three-dimensional packaging devices. Furthermore, the patterned resin film formed as described above can also be used as a photoresist, galvanic resist, etching resist, and top solder resist for electronic devices. Furthermore, the patterned resin film formed as described above can also be used in the manufacture of planar or screen printing plates, the formation of etching masks during the etching of shaped parts, the application of protective coatings in electronic components, especially microelectronic components, and the manufacture of dielectric layers. [Example]

[0206] The present invention will be described in detail below by way of examples, but the scope of the present invention is not limited to these examples.

[0207] In Examples 1 to 12 and Comparative Examples 1 to 10, DA1 to DA4 were used as diamine compounds. DA1, DA2 and DA4 are the compounds described below. DA3 is the compound represented by the aforementioned formula (32).

[0208] [Example 1] 31.02 g (0.10 moles) of 4,4'-oxyphthalic dianhydride was dissolved in 69 g of N-methyl-2-pyrrolidone (NMP). 26.03 g (0.20 moles) of 2-hydroxyethyl methacrylate (HEMA), 15.82 g (0.20 moles) of pyridine, and 24.43 g (0.20 moles) of dimethylaminopyridine were added to the resulting solution, and the solution was stirred at room temperature for 16 hours to obtain di-2-methylpropenyloxyethyl 4,4'-oxyphthalic acid.

[0209] A dicarboxylic acid solution containing 0.1 mole of di-2-methylpropenoxyethyl ester of the obtained 4,4'-oxydiphthalic acid was cooled to 0°C. A solution of 42.30 g (0.21 mole) of dicyclohexylcarbodiimide and 42 g of NMP, and a diamine solution of 36.84 g (0.10 mole) of the above-mentioned DA1 and 3 g of NMP were added dropwise to the dicarboxylic acid solution. After the addition was complete, the resulting reaction solution was stirred at room temperature for 4 hours to carry out a condensation reaction. After the reaction was complete, 19.7 g of methanol was added to the reaction solution, and the precipitate was removed by filtration to obtain the reaction solution. The obtained reaction solution was added dropwise to an aqueous isopropanol solution, causing a brown polyamide resin powder to precipitate. The precipitated powder was recovered by filtration and washed three times with isopropanol. The washed powder was dried under reduced pressure to obtain a polyamide resin of the polycondensate of 4,4'-oxydiphthalic acid di-2-methylpropenoxyethyl ester and the above-mentioned DA1. The obtained polyamide resin has a 2-(methacryloxy)ethoxycarbonyl group as a free radical polymerizable group.

[0210] The obtained polyamide resin was dissolved in γ-butyrolactone at a concentration of 30% by mass. Then, 5% by mass of an oxime ester initiator (Irgacure OXE02 (BASF JAPAN)) relative to the polyamide resin, 1% by mass of a polyfunctional thiol compound (D) relative to the polyamide resin, 0.05% by mass of a polymerization inhibitor (Irganox 1010 (BASF JAPAN)) relative to the polyamide resin, 0.02% by mass of a surfactant (Polyflow NO.77 (Kyoeisha Chemical Co., Ltd.)) relative to the polyamide resin, and 3% by mass of N-[3-(triethoxysilyl)propyl]phthalamide relative to the polyamide resin were added to the resulting solution to obtain a photosensitive resin composition. As a polyfunctional thiol compound (D), pentaerythritol tetra(3-mercaptobutyrate) (Karenz MT PE1 (manufactured by Showa Denko Co., Ltd.)) is used.

[0211] [Example 2] The photosensitive resin composition was obtained in the same manner as in Example 1, except that a polyfunctional thiol compound (D) of 5% by mass relative to the polyamide resin was used.

[0212] [Example 3] The photosensitive resin composition was obtained in the same manner as in Example 1, except that a polyfunctional thiol compound (D) of 10% by mass relative to the polyamide resin was used.

[0213] [Example 4] The photosensitive resin composition was otherwise obtained in the same manner as in Example 1, except that the tetracarboxylic dianhydride was replaced with 0.10 moles of 3,3',4,4'-biphenyltetracarboxylic dianhydride and a polyfunctional thiol compound (D) of 3% by mass relative to the polyamide resin.

[0214] [Example 5] The photosensitive resin composition was obtained in the same manner as in Example 1, except that the diamine compound was replaced with 0.10 moles of the aforementioned DA2, and a polyfunctional thiol compound (D) of 3% by mass relative to the polyamide resin was used.

[0215] [Example 6] The photosensitive resin composition was obtained in the same manner as in Example 1 by replacing 0.10 moles of 4,4'-oxyphthalic dianhydride with a mixture of 0.08 moles of 4,4'-oxyphthalic dianhydride and 0.02 moles of 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (10BTA, manufactured by Black Gold Chemical Co., Ltd.), replacing the diamine compound with 0.10 moles of the above-mentioned DA2, and using a polyfunctional thiol compound (D) at 3% by mass relative to the polyamide resin.

[0216] [Example 7] The photosensitive resin composition was obtained in the same manner as in Example 1, except that the tetracarboxylic dianhydride was replaced with 0.10 moles of 3,3',4,4'-biphenyltetracarboxylic dianhydride, the diamine compound was replaced with 0.08 moles of the above-mentioned DA2 and 0.02 moles of DA3 (the compound represented by the aforementioned formula (32)), and a polyfunctional thiol compound (D) of 3% by mass relative to the polyamide resin was used.

[0217] [Example 8] The photosensitive resin composition was otherwise obtained in the same manner as in Example 1, except that the tetracarboxylic acid dianhydride was replaced with 0.10 moles of 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride and a polyfunctional thiol compound (D) of 3% by mass relative to the polyamide resin was used.

[0218] [Example 9] The polyfunctional thiol compound (D) was replaced with pentaerythritol tetra(3-mercaptobutyrate) (Karenz MT NR1 (manufactured by Showa Denko Co., Ltd.)), and the amount of polyfunctional thiol compound (D) used was changed to 5% by mass relative to the mass of polyamide resin. Otherwise, the photosensitive resin composition was obtained in the same manner as in Example 1.

[0219] [Example 10] The diamine compound was changed to a mixture of 0.08 mol of the above-mentioned DA2 and 0.02 mol of DA3 (the compound represented by the aforementioned formula (32)), the polyfunctional thiol compound (D) was changed to pentaerythritol tetrakis(3-mercaptobutyrate) (Karenz MT NR1 (manufactured by Showa Denko Co., Ltd.)), and the amount of polyfunctional thiol compound (D) was changed to 5% by mass relative to the mass of the polyamide resin. Otherwise, the photosensitive resin composition was obtained in the same manner as in Example 1.

[0220] [Example 11] The diamine compound was changed to a mixture of 0.08 mol of the above-mentioned DA2 and 0.02 mol of the above-mentioned DA4, and the amount of the polyfunctional thiol compound (D) was changed to 5% by mass relative to the mass of the polyamide resin. Otherwise, the photosensitive resin composition was obtained in the same manner as in Example 1.

[0221] [Example 12] The photosensitive resin composition was otherwise obtained in the same manner as in Example 1 by replacing the tetracarboxylic acid dianhydride with 0.10 moles of 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (10BTA, manufactured by Black Gold Chemical Co., Ltd.).

[0222] [Comparative Example 1] The photosensitive resin composition was obtained in the same manner as in Example 1, except that polyfunctional thiol compounds (D) were not used.

[0223] [Comparative Example 2] The photosensitive resin composition was obtained in the same manner as in Example 4, except that polyfunctional thiol compounds (D) were not used.

[0224] [Comparative Example 3] The photosensitive resin composition was obtained in the same manner as in Example 5, except that polyfunctional thiol compounds (D) were not used.

[0225] [Comparative Example 4] The photosensitive resin composition was obtained in the same manner as in Example 6, except that polyfunctional thiol compounds (D) were not used.

[0226] [Comparative Example 5] The photosensitive resin composition was obtained in the same manner as in Example 7, except that polyfunctional thiol compounds (D) were not used.

[0227] [Comparative Example 6] The photosensitive resin composition was obtained in the same manner as in Example 8, except that polyfunctional thiol compounds (D) were not used.

[0228] [Comparative Example 7] The photosensitive resin composition was obtained in the same manner as in Example 9, except that polyfunctional thiol compounds (D) were not used.

[0229] [Comparative Example 8] The photosensitive resin composition was obtained in the same manner as in Example 10, except that polyfunctional thiol compounds (D) were not used.

[0230] [Comparative Example 9] The photosensitive resin composition was obtained in the same manner as in Example 11, except that polyfunctional thiol compounds (D) were not used.

[0231] [Comparative Example 10] The photosensitive resin composition was obtained in the same manner as in Example 12, except that polyfunctional thiol compounds (D) were not used.

[0232] Using the photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 10, the dielectric tangent of the resin film and the high-speed accelerated life test (HAST) of the resin film were evaluated in accordance with the following methods.

[0233] <Dielectric Tangent Evaluation> After the photosensitive resin composition was coated onto a silicon wafer using a spin coater, the thin film of the photosensitive resin composition was baked at 90°C for 240 seconds. The baked coated film was then exposed to a high-pressure mercury lamp with a cumulative light intensity of 2000 mJ / cm². The exposed film was then placed in an oxidation-free oven under a nitrogen atmosphere, and the temperature was increased to 230°C at a rate of 5°C / min, and heated at the same temperature for 1 hour. When the temperature was lowered to 100°C, the wafer was removed and immersed in a 2wt% hydrofluoric acid aqueous solution for 5 to 30 minutes. The resin film was then peeled off from the wafer to obtain the resin film of polyimide resin obtained in the various examples and comparative examples, which was formed by cycloimidization of the resin through ring closure. The thickness of the resin film after peeling was 10 μm.

[0234] The dielectric tangent (tanδ) of the obtained thin films was determined using the method described in the paper "A Study on the Evaluation of Millimeter-Wave Complex Dielectric Coefficient of Photosensitive Insulating Thin Films by Cylinder Resonator Method" (Kohei Takahagi (Utsunomiya University), Kazuaki Ebizawa (Tokyo Ohka Kogyo Co., Ltd.), Yoshinori Furukami (Utsunomiya University), Takashi Shimizu (Utsunomiya University)). Measurements were performed using a network analyzer HP8510C (Keysight Corporation) with the cavity resonator method at room temperature (25°C), humidity (50%), frequency (36 GHz), and sample thickness (10 μm). Based on the measured dielectric tangent values, the dielectric tangent was evaluated according to the following criteria. 〇: Dielectric tangent value below 0.01. × : Dielectric tangent exceeds 0.01.

[0235] <High-Speed ​​Accelerated Life Testing (HAST)> After the photosensitive resin composition was coated onto a copper sputtered wafer using a spin coater, the photosensitive resin film was baked at 90°C for 240 seconds. The baked coating film was then exposed to light using a high-pressure mercury lamp at a cumulative intensity of 2000 mJ / cm². The exposed film was then placed in an oxidation-free oven under nitrogen conditions, with the temperature increased to 230°C at a rate of 5°C / min, and heated at the same temperature for 1 hour. When the temperature was lowered to 100°C, the wafer was removed. The wafer was then exposed to a constant temperature bath (ESPEC STH-120) at 120°C and 85% relative humidity for 100 hours. The wafer was observed using an optical microscope; wafers without floating or peeling were marked 0, and those with such defects were marked ×.

[0236] The results of the above tests, in Examples 1 to 12, were all zero in the dielectric tangent evaluation and high-speed accelerated lifetime test (HAST). On the other hand, for Comparative Examples 1 to 10, all were judged as ○ in the dielectric tangent evaluation, and as × in the high-speed accelerated life test. Based on the comparison of Examples 1-12 and Comparative Examples 1-10, it can be seen that if a resin film with a thickness of 10 μm is used as a sample, and the dielectric tangent value measured by the cavity resonator method at room temperature of 25°C, humidity of 50%, and frequency of 36 GHz is 0.01 or less, and the resin film contains polyamide resin and photosensitizer, then a resin film with excellent HAST resistance can be formed.

[0237] Furthermore, using the photosensitive resin composition of Examples 1 to 12 to form a patterned resin film according to the following method, the resin film with via holes of the desired size can be formed regardless of which example of photosensitive resin composition is used. In other words, the photosensitive resin compositions of Examples 1 to 12 all have good photolithography properties. <Formation of Resin Film Through Graphicalization> The photosensitive resin compositions of each embodiment were coated onto a copper sputtered wafer using a spin coater. The resulting film of the photosensitive resin composition was baked at 80°C for 300 seconds to obtain a coated film with a thickness of 12 μm. The coated film was exposed using a GHI line exposure machine (Ultratech) at 2000 mJ / cm² and a focus of 0 μm through a negative mask capable of forming through-holes with an aperture diameter of 50 μm. The exposed coated film was then immersed in cyclopentanone for 120 seconds for development to form a patterned resin film with through-holes of 50 μm.

Claims

1. A photosensitive resin composition comprising a resin (A), a photosensitizer (C), and a polyfunctional thiol compound (D), wherein the resin (A) comprises a polyamide resin (A-III) derived from a diamine compound and a dicarboxylic acid compound or a amide-forming derivative of a dicarboxylic acid compound, the resin (A) having free radical polymerizable groups on its molecular chain, and the photosensitizer (C) being a photoradical polymerization initiator (C1), wherein a resin film with a thickness of 10 μm formed using the aforementioned photosensitive resin composition is used as a sample, and the dielectric tangent value measured by the cavity resonator method at room temperature 25°C, humidity 50%, and frequency 36 GHz is 0.01 or less.

2. The photosensitive resin composition of claim 1, wherein the aforementioned diamine compound comprises one or more selected from the group consisting of: the following formula (A1): (in formula (A1), X is an organic group having 1 to 100 carbon atoms, Ra1 is a hydroxyl, carboxyl, or halogen atom, Ra2 is an aliphatic, hydroxyl, carboxyl, sulfonic acid, or halogen atom having 1 to 20 carbon atoms, Ar is a phenyl group that can be substituted by Ra2, or a naphthyl group that can be substituted by Ra2, ma1 is an integer of 0 to 10, ma2 is an integer of 0 to 7, and ma3 is an integer of 1 to 10) the diamine compound (A-1) having the following formula (A2): (in formula (A2), Ra3 and Ra4 are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and ma4 and ma5 are each independently an integer of 0 to 4) The partial structure shown, and not equivalent to the aforementioned diamine compound (A-1), is a diamine compound (A-2) having the following formula (A3): (In formula (A3), Ra5 and Ra6 are independently alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, or halogen atoms, respectively; ma6 and ma7 are independently integers with 0 to 4 carbon atoms, respectively; Ra7 and Ra8 are independently hydrogen atoms, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms, or phenyl, respectively; Ra7 and Ra8 may also be bonded to each other to form a ring) The partial structure shown, and not equivalent to the aforementioned diamine compound (A-1) and the aforementioned diamine compound (A-2), is a diamine compound (A-3), and a dimer diamine compound (A4).

3. The photosensitive resin composition of claim 1 or 2, wherein the aforementioned polyfunctional thiol compound (D) comprises the polyfunctional thiol compound represented by the following formula (d1): (in formula (d1), Rd1 is a divalent chain aliphatic hydrocarbon group that may have substituents, Rd2 is an n-valent aliphatic hydrocarbon group that may contain heteroatoms, and n is an integer of 2 to 4) 4. The photosensitive resin composition of claim 1 or 2, wherein the aforementioned resin (A) comprises the aforementioned polyamide resin (A-III), and the aforementioned polyamide resin (A-III) has a constituent unit derived from the reaction product of a tetracarboxylic dianhydride and an alcohol having a free radical polymerizable group, or a constituent unit with the same structure as the constituent unit derived from the aforementioned reaction product.

5. The photosensitive resin composition of claim 1 or 2, wherein the aforementioned resin (A) has free radical polymerizable groups on its molecular chain, and the aforementioned photoradical polymerization initiator (C1) is an oxime ester photopolymerization initiator.

6. A photosensitive dry film having a substrate film and a photosensitive layer formed on the surface of the substrate film, wherein the photosensitive layer is composed of a photosensitive resin composition as claimed in any one of claims 1 to 5.

7. A method for manufacturing a photosensitive dry film, comprising coating a photosensitive resin composition as described in any one of claims 1 to 5 onto a substrate film to form a photosensitive layer.

8. A method for manufacturing a patterned resin film, comprising a lamination step of laminating a photosensitive layer made of a photosensitive resin composition as claimed in any one of claims 1 to 5 on a substrate, an exposure step of selectively irradiating the aforementioned photosensitive layer with active light or radiation to expose it, and a development step of developing the exposed photosensitive layer to obtain a patterned resin film.

9. The method for manufacturing a patterned resin film as claimed in claim 8, wherein the aforementioned resin (A) comprises the aforementioned polyamide resin (A-III) derived from the constituent units of a dicarboxylic acid compound synthesized by reacting a tetracarboxylic acid dianhydride with a monohydroxy compound, and the manufacturing method comprises: after obtaining the patterned aforementioned resin film, baking the aforementioned resin film to convert the aforementioned polyamide resin (A-III), which comprises the constituent units of a dicarboxylic acid compound synthesized by reacting a tetracarboxylic acid dianhydride with a monohydroxy compound, into a polyimide resin (AI).

10. A resin film comprising a photosensitive resin composition as claimed in claim 1 or 2.