JP7671182B2 - Photosensitive resin composition - Google Patents

Description

The present invention relates to a photosensitive resin composition containing at least one selected from the group consisting of polyimide resins, polyamic acids, polyamide resins, polybenzoxazole resins, and polybenzoxazole resin precursors, each of which contains a structural unit that can be derived from a diamine compound having a specific structure, and a photosensitizer; a photosensitive dry film having a photosensitive layer made of the photosensitive resin composition; a method for producing the photosensitive dry film; and a method for producing a patterned resin film using the photosensitive resin composition.

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

In recent years, communication devices such as mobile phones have become increasingly higher in frequency, which has led to demand for insulating parts that insulate the metal wiring of communication devices to be able to handle higher frequencies.
Here, the higher the frequency, the greater the transmission loss, and the greater the transmission loss, the greater the attenuation of the electrical signal. Therefore, for resins such as polyimide resins, polyamide resins, and polybenzoxazole resins, there is a demand for further lowering the dielectric tangent and the dielectric constant in the high frequency band in order to further reduce the transmission loss in response to the increase in frequency.

In addition, when producing various elements and electronic substrates, it is often necessary to form insulating materials or protective materials only in desired positions. For this reason, there is a demand for photosensitive resin compositions that exhibit low dielectric tangent and low dielectric constant and can form patterned resin films.

In response to the above demands, for example, photosensitive resin compositions capable of forming patterned polyimide resin films have been proposed, such as a photosensitive resin composition containing an aromatic polyamide resin of a specific structure having structural units derived from 4,4'-bis(4-aminophenoxy)biphenyl and a photopolymerization initiator (see Patent Document 1, Examples), and a photosensitive resin composition containing a polyimide precursor having an unsaturated double bond in the side chain and a photopolymerization initiator having an oxime structure that generates a specific amount of radicals (see Patent Document 2).

International Publication No. 2019/044874 International Publication No. 2021/020463

When using the photosensitive resin compositions described in Patent Document 1 and Patent Document 2, a patterned polyimide resin film with a relatively low dielectric tangent can be formed by applying a photolithography method. On the other hand, it is desirable to further reduce the dielectric tangent of the polyimide resin film formed from the photosensitive resin composition described in Patent Document 1.

The present invention has been made in consideration of the above problems, and aims to provide a photosensitive resin composition capable of forming a patterned resin film with a low dielectric tangent by applying a photolithography method, a photosensitive dry film having a photosensitive layer made of the photosensitive resin composition, a method for manufacturing the photosensitive dry film, and a method for manufacturing a patterned resin film using the photosensitive resin composition.

The present inventors have found that the above problems can be solved by using at least one resin selected from the group consisting of polyimide resins, polyamic acids, polyamide resins, polybenzoxazole resins, and polybenzoxazole resin precursors, which contain structural units derived from diamine compounds of a specific structure having an aromatic group, in a photosensitive resin composition containing a resin and a photosensitizer, and have completed the present invention. More specifically, the present invention provides the following.

（式（Ａ１）中、Ｘは、炭素原子数１以上１００以下の有機基であり、Ｒ^ａ１は、ヒドロキシ基、カルボキシ基、又はハロゲン原子であり、Ｒ^ａ２は、炭素原子数１以上２０以下の脂肪族基、ヒドロキシ基、カルボキシ基、スルホン酸基、又はハロゲン原子であり、Ａｒは、Ｒ^ａ２で置換されていてもよいフェニル基、又はＲ^ａ２で置換されていてもよいナフチル基であり、ｍａ１は、０以上１０以下の整数であり、ｍａ２は、０以上７以下の整数であり、ｍａ３は、１以上１０以下の整数である。）
で表される化合物に由来する構成単位を含む、感光性樹脂組成物である。 The first aspect of the present invention includes a resin (A) and a photosensitizer (C),
Resin (A) is
A polyimide resin (AI) derived from a diamine compound and a tetracarboxylic dianhydride, and a polyamic acid (A-II),
A polyamide resin (A-III) derived from a diamine compound and a dicarboxylic acid compound or an amide-forming derivative of a dicarboxylic acid compound, and
the polybenzoxazole resin (A-IV) is derived from a diamine compound, which is an aromatic compound having two amino groups bonded to an aromatic ring and a hydroxyl group bonded to a carbon atom adjacent to the carbon atom to which the amino groups on the aromatic ring are bonded, and a dicarboxylic acid compound or an amide-forming derivative of a dicarboxylic acid compound; and the polybenzoxazole resin precursor (A-V) is at least one selected from the group consisting of polybenzoxazole resin (A-IV) and polybenzoxazole resin precursor (A-V),
The resin (A) is represented by the following formula (A1):

(In formula (A1), X is an organic group having 1 to 100 carbon atoms, R ^a1 is a hydroxy group, a carboxy group, or a halogen atom, R ^a2 is an aliphatic group having 1 to 20 carbon atoms, a hydroxy group, a carboxy group, a sulfonic acid group, or a halogen atom, Ar is a phenyl group which may be substituted with R ^a2 , or a naphthyl group which may be substituted with R ^a2 , ma1 is an integer of 0 to 10, ma2 is an integer of 0 to 7, and ma3 is an integer of 1 to 10.)
The photosensitive resin composition includes a structural unit derived from a compound represented by the formula:

The second aspect of the present invention is a photosensitive dry film having a base film and a photosensitive layer formed on the surface of the base film, the photosensitive layer being made of the photosensitive resin composition according to the first aspect.

The third aspect of the present invention is a method for producing a photosensitive dry film, which includes applying the photosensitive resin composition according to the first aspect onto a substrate film to form a photosensitive layer.

A fourth aspect of the present invention is a method for producing a photosensitive resin composition comprising the steps of: laminating a photosensitive layer made of the photosensitive resin composition according to the first aspect on a substrate;
an exposure step of exposing the photosensitive layer to actinic rays or radiation in a position-selective manner;
and a developing step of developing the exposed photosensitive layer to obtain a patterned resin film.

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a patterned resin film having a low dielectric tangent by applying a photolithography method, a photosensitive dry film having a photosensitive layer made of the photosensitive resin composition, a method for manufacturing the above-mentioned photosensitive dry film, and a method for manufacturing a patterned resin film using the above-mentioned photosensitive resin composition.

（式（Ａ１）中、Ｘは、炭素原子数１以上１００以下の有機基であり、Ｒ^ａ１は、ヒドロキシ基、カルボキシ基、又はハロゲン原子であり、Ｒ^ａ２は、炭素原子数１以上２０以下の脂肪族基、ヒドロキシ基、カルボキシ基、スルホン酸基、又はハロゲン原子であり、Ａｒは、Ｒ^ａ２で置換されていてもよいフェニル基、又はＲ^ａ２で置換されていてもよいナフチル基であり、ｍａ１は、０以上１０以下の整数であり、ｍａ２は、０以上７以下の整数であり、ｍａ３は、１以上１０以下の整数である。）
で表される化合物に由来する構成単位を含む。
樹脂（Ａ）が、上記式（Ａ１）で表される化合物に由来する構成単位を含むことによって、高周波帯域における誘電正接の低い樹脂膜を形成できる。 ≪Photosensitive resin composition≫
The photosensitive resin composition includes a resin (A) and a photosensitizer (C). The resin (A) includes at least one selected from the group consisting of a polyimide resin (A-I) derived from a diamine compound and a tetracarboxylic dianhydride, a polyamic acid (A-II), a polyamide resin (A-III) derived from a diamine compound and a dicarboxylic acid compound or an amide-forming derivative of a dicarboxylic acid compound, and a polybenzoxazole resin (A-IV) derived from a diamine compound, which is an aromatic compound having two amino groups bonded to an aromatic ring and a hydroxyl group bonded to a carbon atom adjacent to the carbon atom to which the amino group on the aromatic ring is bonded, and a dicarboxylic acid compound or an amide-forming derivative of a dicarboxylic acid compound, and a polybenzoxazole resin precursor (A-V).
The resin (A) has the following formula (A1):

(In formula (A1), X is an organic group having 1 to 100 carbon atoms, R ^a1 is a hydroxy group, a carboxy group, or a halogen atom, R ^a2 is an aliphatic group having 1 to 20 carbon atoms, a hydroxy group, a carboxy group, a sulfonic acid group, or a halogen atom, Ar is a phenyl group which may be substituted with R ^a2 , or a naphthyl group which may be substituted with R ^a2 , ma1 is an integer of 0 to 10, ma2 is an integer of 0 to 7, and ma3 is an integer of 1 to 10.)
The compound includes a structural unit derived from the compound represented by the formula:
When the resin (A) contains a structural unit derived from the compound represented by the above formula (A1), a resin film having a low dielectric tangent in the high frequency band can be formed.

The photosensitizer (C) is a component that imparts photosensitivity to the photosensitive resin composition. For example, when the resin (A) has a polymerizable group or the photosensitive resin composition contains a compound having a polymerizable group, the photosensitizer (C) may be a so-called polymerization initiator that advances the polymerization reaction between the polymerizable groups. When the photosensitive resin composition contains a combination of a resin (A) having a polymerizable group or a compound other than the resin (A) having a polymerizable group and a polymerization initiator as the photosensitizer (C), the photosensitive resin composition becomes insoluble in the developer by curing due to exposure. In other words, a photosensitive resin composition that contains a combination of a resin (A) having a polymerizable group or a compound other than the resin (A) having a polymerizable group and a polymerization initiator as the photosensitizer (C) corresponds to a negative photosensitive resin composition.

From the viewpoint of good photolithography properties, it is preferable that the resin (A) has a polymerizable group on its molecular chain that can be polymerized by the action of the photosensitizer (C). Typically, the polymerizable group is preferably a radical polymerizable group or a cation polymerizable group, and more preferably a radical polymerizable group.
When the resin (A) has a polymerizable group, typically, the resin (A) has a radically polymerizable group on its molecular chain and the photosensitizer (C) is a photoradical polymerization initiator (C1), or the resin (A) has a cationic polymerizable group on its molecular chain and the photosensitizer (C) is a photocationic polymerization initiator (C2).

The amount of radically polymerizable groups or cationic polymerizable groups in resin (A) is not particularly limited as long as it does not impair the object of the present invention. The amount of radically polymerizable groups or cationic polymerizable groups in resin (A) is, for example, 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, in terms of the number of moles of functional groups relative to the weight of resin (A). The amount of radically polymerizable groups or cationic polymerizable groups in resin (A) can typically be measured by NMR analysis.

The photosensitizer (C) may also be a component that is itself soluble in a developer by the action of light. For example, a compound having a naphthoquinone diazide group is soluble in an alkaline developer by the generation of a carboxyl group by exposure to light. When a photosensitive resin composition contains a photosensitizer (C) that is itself soluble in a developer by the action of light, the photosensitive resin composition corresponds to a positive-type photosensitive resin composition that is soluble in a developer by exposure to light.

The photosensitive resin composition containing the above resin (A) and photosensitizer (C) not only provides a patterned resin film with a low dielectric tangent when photolithography is applied, but also suppresses clouding of the resin film formed using the photosensitive resin composition and provides a resin film with excellent mechanical properties such as tensile elongation.

Below, we will explain the essential and optional components of the photosensitive resin composition.

（式（Ａ１）中、Ｘは、炭素原子数１以上１００以下の有機基であり、Ｒ^ａ１は、ヒドロキシ基、カルボキシ基、又はハロゲン原子であり、Ｒ^ａ２は、炭素原子数１以上２０以下の脂肪族基、ヒドロキシ基、カルボキシ基、スルホン酸基、又はハロゲン原子であり、Ａｒは、Ｒ^ａ２で置換されていてもよいフェニル基、又はＲ^ａ２で置換されていてもよいナフチル基であり、ｍａ１は、０以上１０以下の整数であり、ｍａ２は、０以上７以下の整数であり、ｍａ３は、１以上１０以下の整数である。）
で表される化合物に由来する構成単位を含む。 <Resin (A)>
As described above, the resin (A) includes at least one selected from the group consisting of polyimide resin (A-I) and polyamic acid (A-II) derived from a diamine compound and a tetracarboxylic dianhydride, polyamide resin (A-III) derived from a diamine compound and a dicarboxylic acid compound or an amide-forming derivative of a dicarboxylic acid compound, and polybenzoxazole resin (A-IV) derived from a diamine compound, which is an aromatic compound having two amino groups bonded to an aromatic ring and a hydroxyl group bonded to a carbon atom adjacent to the carbon atom to which the amino group on the aromatic ring is bonded, and a dicarboxylic acid compound or an amide-forming derivative of a dicarboxylic acid compound, and polybenzoxazole resin precursor (A-V).
The resin (A) has the following formula (A1):

(In formula (A1), X is an organic group having 1 to 100 carbon atoms, R ^a1 is a hydroxy group, a carboxy group, or a halogen atom, R ^a2 is an aliphatic group having 1 to 20 carbon atoms, a hydroxy group, a carboxy group, a sulfonic acid group, or a halogen atom, Ar is a phenyl group which may be substituted with R ^a2 , or a naphthyl group which may be substituted with R ^a2 , ma1 is an integer of 0 to 10, ma2 is an integer of 0 to 7, and ma3 is an integer of 1 to 10.)
The compound includes a structural unit derived from the compound represented by the formula:

The following describes polyimide resin (A-I), polyamic acid (A-II), polyamide resin (A-III), polybenzoxazole resin (A-IV), and polybenzoxazole resin precursor (A-V).

[Polyimide resin (AI) and polyamic acid (A-II)]
The polyimide resin (AI) and the polyamic acid (A-II) are resins derived from a diamine compound and a tetracarboxylic dianhydride. The polyimide resin (AI) and the polyamic acid (A-II) each contain a structural unit derived from the compound represented by the above formula (A1).

The method for producing the polyimide resin (A-I) is not particularly limited. The polyimide resin (A-I) is usually obtained by ring-closing and imidizing the polyamic acid (A-II) obtained by reacting a diamine compound containing the compound represented by the above formula (A1) with a tetracarboxylic dianhydride.

(Diamine Compound)
The diamine compound includes a compound represented by the above formula (A1). The diamine compound may include a diamine compound other than the compound represented by the above formula (A1).

In formula (A1), Ar is a phenyl group which may be substituted with R ^a2 , or a naphthyl group which may be substituted with R ^a2 . Ar is preferably a phenyl group or a naphthyl group. That is, in formula (A1), ma2 is preferably 0.

In formula (A1), R ^a2 is an aliphatic group having from 1 to 20 carbon atoms, a hydroxyl group, a carboxyl group, a sulfonic acid group, or a halogen atom. The organic group represented by R ^a2 may contain a heteroatom such as O, N, S, P, B, Si, or a halogen atom.
The aliphatic group represented by R ^a2 preferably has 1 or more and 12 or less, and more preferably has 1 or more and 6 or less, carbon atoms.

Examples of the aliphatic group represented by R ^a2 include chain alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group; a vinyl group, a 1-propenyl group, Chain alkenyl groups such as 2-n-propenyl group (allyl group), 1-n-butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group; chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, pafluoromethyl group, phenyl ... halogenated linear alkyl groups such as perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and perfluorodecyl group; halogenated cycloalkyl groups such as 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group, and 4-bromocyclohexyl group; hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxyethyl group, hydroxycycloalkyl groups such as 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group, and 4-hydroxycyclohexyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-butyloxy group, chain alkoxy groups such as nyloxy group, n-decyloxy group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, and n-icosyloxy group; chain alkenyloxy groups such as vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group, and 3-n-butenyloxy group; methoxy Alkoxyalkyl groups such as a methyl group, an ethoxymethyl group, an n-propoxymethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2-n-propoxyethyl group, a 3-methoxy-n-propyl group, a 3-ethoxy-n-propyl group, a 3-n-propoxy-n-propyl group, a 4-methoxy-n-butyl group, a 4-ethoxy-n-butyl group, and a 4-n-propoxy-n-butyl group; a methoxymethoxy group, an ethoxymethoxy group, an n-propoxymethoxy group, a 2-methoxyethoxy group, a 2-ethoxyethoxy group, a 2-n-propoxyethoxy group, a 3 -alkoxyalkoxy groups such as methoxy-n-propoxy group, 3-ethoxy-n-propoxy group, 3-n-propoxy-n-propoxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n-propoxy-n-butyloxy group; aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, and decanoyl group; methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butanoyl group, chain alkyloxycarbonyl groups such as n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyloxycarbonyl group; and aliphatic acyloxy groups such as formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group, nonanoyloxy group, and decanoyloxy group.

In formula (A1), ma3 is an integer of 1 or more and 10 or less. The value of ma3 is not particularly limited as long as it is 1 or more and 10 or less, and is appropriately selected depending on the structure of X. The value of ma3 is preferably 1 or more and 4 or less, and more preferably 1 or 2.

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

The organic group represented by X may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group. The organic group represented by X may be a group bonded via a bond containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Examples of bonds containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom contained in the organic group represented by X include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -S-S-, and the like are preferred.

When the organic group represented by X is an aliphatic group, the aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. When the organic group represented by X is an aliphatic group, the aliphatic group is preferably an aliphatic hydrocarbon group. When the organic group represented by X is an aliphatic group, the aliphatic group may be linear, cyclic, or a combination of a linear aliphatic group and a cyclic aliphatic group. The linear aliphatic group may be branched.

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

When the organic group represented by X is a group containing an aromatic group, examples of the group composed of X, Ar, R ^a1 , and R ^a2 in formula (A1) include groups represented by the following formulae (11) to (15).

In formula (11) to formula (15), Ar, R ^a1 , R ^a2 , ma1, ma2, and ma3 are the same as those in formula (A1). In formula (13), ma4 and ma5 are each independently an integer of 0 to 4. ma6 and ma7 are each independently an integer of 0 to 4, and the sum of ma6 and ma7 is 1 to 8. In formula (14), ma8, ma9, and ma10 are each independently an integer of 0 to 4. The sum of ma8, ma9, and ma10 is 0 to 10. ma11, ma12, and ma13 are each independently an integer of 0 to 4. The sum of ma11, ma12, and ma13 is 1 to 10. In formula (15), ma14 is an integer of 0 or more and 3 or less. ma15 is an integer of 0 or more and 5 or less. The sum of ma14 and ma15 is 0 or more and 8 or less. ma16 is an integer of 0 or more and 3 or less. ma17 is an integer of 0 or more and 5 or less. The sum of ma16 and ma17 is 1 or more and 8 or less.

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

In formula (11) to formula (15), R ^a3 is a single bond or a divalent linking group. However, the divalent linking group is not a group containing an aromatic group. Examples of the divalent linking group include an aliphatic hydrocarbon group having 1 to 20 carbon atoms, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -S-S-, and a group combining two or more selected from these groups. The number of carbon atoms in the linking group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. The aliphatic hydrocarbon group as the linking group may have one or more unsaturated bonds, may have a branch, or may contain a ring structure. Specific examples of the aliphatic hydrocarbon group as the linking group include a methylene group, an ethane-1,2-diyl group (ethylene group), an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a propane-1,1-diyl group, a propane-2,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,1 Examples of the alkyl group include a 1-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, a heptadecane-1,17-diyl group, an octadecane-1,18-diyl group, a nonadecane-1,19-diyl group, an icosane-1,20-diyl group, an ethene-1,2-diyl group (vinylene group), a propene-1,3-diyl group, an ethyne-1,2-diyl group, and a propyne-1,3-diyl group.

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

（式（Ａ１－１）中、Ｒ^ａ１、Ｒ^ａ２、Ａｒ、ｍａ１、ｍａ２、及びｍａ３は、式（Ａ１）中のこれらと同様であり、Ｙ^ａ１は、炭素原子数１以上２０以下の有機基、又は単結合であり、Ｙ^ａ２は、炭素原子数１以上２０以下の有機基であり、ｎａ１は０又は１であり、ｎａ２は０又は１である。ｎａ１が１である場合、Ｙａ１は、単結合でない。）
で表される化合物であるのが好ましい。 In order to form a resin film having a low dielectric tangent and good mechanical properties, the compound represented by formula (A1) is preferably a compound represented by the following formula (A1-1):

(In formula (A1-1), R ^a1 , R ^a2 , Ar, ma1, ma2, and ma3 are the same as those in formula (A1), Y ^a1 is an organic group having 1 to 20 carbon atoms or a single bond, Y ^a2 is an organic group having 1 to 20 carbon atoms, na1 is 0 or 1, and na2 is 0 or 1. When na1 is 1, Ya1 is not a single bond.)
It is preferable that the compound is represented by the following formula:

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

In formula (A1-1), it is preferable that na2 is 1, and it is more preferable that na1 and na2 are both 1 and Y ^a1 is an organic group. In this case, due to the high steric freedom of the ether bond, it is considered that when a cured film is formed using the photosensitive resin composition, the structural units represented by formula (A1-1) are likely to be well packed, and a cured film having excellent mechanical properties, thermal properties, electrical properties, etc. can be easily formed.

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

Specific examples of the compound represented by formula (A1) described above include the following compounds.

As described above, the diamine compound may contain a diamine compound other than the compound represented by the above formula (A1).
When the resin (A) is a polyimide resin (AI) and a polyamic acid (A-II), the ratio of the number of moles of the constituent units derived from the compound represented by formula (A1) to the number of moles of all constituent units derived from diamine compounds in the polyimide resin (AI) and the polyamic acid (A-II) is preferably 10 mol % or more and 100 mol % or less, more preferably 15 mol % or more and 100 mol % or less, and even more preferably 20 mol % or more and 100 mol % or less.

The other diamine compound is represented by the following formula (A2).
_H2NA1 - ^NH2 _... (A2)
(In formula (A2), ^A1 represents a divalent organic group. However, the divalent organic group represented by ^A1 does not correspond to the group composed of X, Ar, R ^a1 and R ^a2 in formula (A1) above.)

A ¹ is a divalent organic group. A ¹ may have one or more substituents in addition to the two amino groups.
Preferred examples of the substituent include a fluorine atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a fluorinated alkyl group having from 1 to 6 carbon atoms, a fluorinated alkoxy group having from 1 to 6 carbon atoms, a carboxy group, or a hydroxy group.
When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.

The lower limit of the number of carbon atoms in the organic group represented by ^A1 is preferably 2, more preferably 6, and the upper limit is preferably 50, more preferably 30.
^A1 may be an aliphatic group, but is preferably an organic group containing one or more aromatic rings.

When ^A1 is an organic group containing one or more aromatic rings, the organic group may be one aromatic group itself, or may be a group in which two or more aromatic groups are bonded via an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, or a bond containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Examples of the bond containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom contained in ^A1 include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -S-S-, and the like are preferred.

The aromatic ring in ^A1 bonded to the amino group is preferably a benzene ring. When the ring bonded to the amino group in ^A1 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.
The aromatic ring contained in ^A1 may be an aromatic heterocycle.

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

In (21) to (24), R ¹¹¹ represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a carboxy group, a sulfonic acid group, a hydroxy group, an alkyl group having from 1 to 4 carbon atoms, and a halogenated alkyl group having from 1 to 4 carbon atoms. In formula (24), Q ¹ is a 9,9'-fluorenylidene group, or the formula: -C ₆ H ₄ -, -C ₆ H ₄ -C ₆ H ₄ -, -O-C ₆ H ₄ -C ₆ H ₄ -O-, -O-C ₆ H ₄ -CO-C ₆ H ₄ -O-, -O-C ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, -OCO-C ₆ H ₄ -COO-, -OCO-C ₆ H ₄ -C ₆ H ₄ -COO-, -OCO-, -O-, -CO-, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -CH ₂ -, -OC ₆ H ₄ This represents one type selected from the group consisting of groups represented by -SO2 _{- C6H4} - _{O- ,} -C( _CH3 ) _{2 -} C6H4 _- C( _CH3 ) _2- , _-O -C10H6-O-, -O- _C6H4 -O-, -O-CH2-O- _, -O-( _CH2 ) ₂ -O-, -O-( _CH2 ) _{3 -} O-, -O-( _CH2 ) ₄ -O-, -O-( _CH2 ) ₅ -O-, and -O-(CH2 _{) 6} -O-.

In the examples of ^Q1 , _-C6H4- is a phenylene group, preferably an m-phenylene group or _a p-phenylene group, more preferably a p-phenylene group, and _-C10H6- is a naphthalenediyl group, preferably a naphthalene- _1,2 -diyl group, a naphthalene-1,4-diyl group, a naphthalene-2,3-diyl group, a naphthalene-2,6-diyl group, or a naphthalene-2,7-diyl group, more preferably a naphthalene-1,4-diyl group or a naphthalene-2,6-diyl group.

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

In terms of the electrical and mechanical properties of the resin film _to be formed, ^Q1 in formula (24) may _be any of _{-C6H4- C6H4-, -O-C6H4 - C6H4 - O-} , _{-O - C6H4} -CO-C6H4 _-O- , -O-C6H4- _C ( _CH3 ) _{2 - C6H4} -O-, -OCO- _{C6H4 -} COO- _{, -OCO-C6H4-C6H4 - COO-} , -OCO- _, -O-, -CO- _, -C( _CF3 ) _2- , -C( _CH3 ) _2- , _-CH2- , -O- _C6H4 - _{SO2 - C6H4} -O-, -C(CH ₃ ) ₂ -C ₆ H ₄ -C(CH ₃ ) ₂ -, -O-C ₁₀ H ₆ -O-, -O-C ₆ H 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- are preferred. From the viewpoint of improving the electrical properties and mechanical properties of the resin (A) in the photosensitive resin composition, Q ¹ in formula (24) is more preferably —O—C ₆ H ₄ —C ₆ H ₄ —O— or —O—C ₆ H ₄ —C(CH ₃ ) ₂ —C ₆ H ₄ —O—, and particularly preferably a group represented by —O—C ₆ H ₄ —C ₆ H ₄ —O— in which both —C ₆ H ₄ — are p-phenylene groups.

When an aromatic diamine compound is used as the other diamine compound represented by formula (A2), for example, the aromatic diamine compounds shown below can be suitably used.
That is, examples of the aromatic diamine compound 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' -diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl methane, 3,3'-diaminodiphenyl methane, 3,4'-diaminodiphenyl methane, 2,2-bis(4-aminophenyl)propane, bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis[N-(3-aminobenzoyl)-3 -amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfo-4,4'-diaminodiphenyl ether, 4,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene benzene, 1,3-bis(3-aminophenoxy)benzene, bis(3-amino-4-hydroxyphenyl)ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 4,4'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(4-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone nyl]sulfone, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]ketone, 2,2-bis[4-{4-amino-2-(trifluoromethyl)phenoxy}phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-amino-3-methylphenyl)fluorene, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 9,9-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 9 ,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 2,7-diaminofluorene, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(3-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-6-aminobenzoxazole, 2-(3-aminophenyl)-6-aminobenzoxazole, 1,4-bis(5-amino-2-benzoxazolyl)benzene, 1,4-bis(6-amino-2-benzoxazolyl)benzene, 1,3-bis(5-amino-2-benzoxazolyl)benzene, 1,3-bis(6-amino-2-benzoxazolyl)benzene, 2,6- Bis(4-aminophenyl)benzobisoxazole, 2,6-bis(3-aminophenyl)benzobisoxazole, bis[(3-aminophenyl)-5-benzoxazolyl], bis[(4-aminophenyl)-5-benzoxazolyl], bis[(3-aminophenyl)-6-benzoxazolyl], bis[(4-aminophenyl)-6-benzoxazolyl], N,N'-bis(3-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl , N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'-[1,4-phenylenebis(1-methylethane-1,1-diyl)]dianiline, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 4-aminobenzoic acid 4-aminophenyl ester, 1,3-bis(4-anilino)tetramethyldisiloxane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, and ortho-tolidine sulfone. Among these, 4,4'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(4-aminophenoxy)biphenyl, and 3,3'-bis(4-aminophenoxy)biphenyl are preferred from the viewpoint of improving electrical properties and mechanical properties.

In addition, a silicon-containing group which may have a chain-like aliphatic group and/or an aromatic ring can be used as A ^1. As such a silicon-containing group, typically, the following groups can be used.

Specific examples of compounds having amino groups at both ends and silicon atom-containing groups include methylphenyl silicones having amino groups at both ends (e.g., X-22-1660B-3 (number average molecular weight of about 4,400) and X-22-9409 (number average molecular weight of about 1,300) manufactured by Shin-Etsu Chemical Co., Ltd.), dimethyl silicones having amino groups at both ends (e.g., X-22-161A (number average molecular weight of about 1,600), X-22-161B (number average molecular weight of about 3,000) and KF8012 (number average molecular weight of about 4,400) manufactured by Shin-Etsu Chemical Co., Ltd.; BY16-835U (number average molecular weight of about 900) manufactured by Dow Corning Toray; and Silaplane FM3311 (number average molecular weight of about 1000) manufactured by JNC Corporation).

As another diamine compound represented by formula (A2), a diamine having an oxyalkylene group can also be preferably used. Preferred examples of the oxyalkylene group include an ethyleneoxy group and a propyleneoxy group ( _-C ( _CH3 )-CH2-O-, _-CH2 - _C ( _CH3 )-O-, or _{-CH2CH2CH2 -} O-).
The diamine having an oxyalkylene group may contain two or more kinds of oxyalkylene groups in combination. When the diamine having an oxyalkylene group contains two or more kinds of oxyalkylene groups, the two or more kinds of oxyalkylene groups may be contained in the diamine in a block manner or in a random manner.
The diamine having an oxyalkylene group preferably does not contain a cyclic group, and more preferably does not contain an aromatic group.
Specific examples of diamines having an oxyalkylene group include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) EDR-176, JEFFAMINE (registered trademark) D-200, JEFFAMINE (registered trademark) D-400, JEFFAMINE (registered trademark) D-2000, and JEFFAMINE (registered trademark) D-4000, as well as 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, all of which are manufactured by HUNTSUMAN Corporation.

In addition, a dimer diamine compound is also preferred as the diamine compound because it is easy to form a cured product with a low dielectric constant and dielectric tangent in the high frequency band using a photosensitive resin composition. A dimer diamine compound is a diamine compound in which two terminal carboxy groups of a dimer acid are substituted with an aminomethyl group or an amino group. A dimer acid is a known dibasic acid obtained by an intermolecular polymerization reaction of an unsaturated fatty acid. The industrial production process for producing a dimer acid is almost standardized. Typically, a dimer acid is obtained by dimerizing an unsaturated fatty acid having 11 to 22 carbon atoms in the presence of a clay catalyst or the like. An industrially obtained dimer acid is mainly composed of a dibasic acid having 36 carbon atoms obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms, such as oleic acid, linoleic acid, and linolenic acid. Industrially obtained dimer acid may contain any amount of monomer acid having 18 carbon atoms, trimer acid having 54 carbon atoms, and other polymerized fatty acids having from 20 to 54 carbon atoms, depending on the degree of purification.
The diamine compound is preferably a diamine compound represented by the following formula (31).

In formula (31), e, f, g, and h are each an integer of 0 or more. e+f is an integer of 6 or more and 17 or less, and g+h is an integer of 8 or more and 19 or less. In formula (31), the wavy line represents a carbon-carbon single bond or a carbon-carbon double bond. However, at least one carbon-carbon double bond is present in one molecule of the compound represented by formula (31).

Furthermore, the diamine compound represented by formula (31) is preferably a compound represented by the following formula (32), since it is capable of forming a cured product having excellent elongation.

Commercially available products of the diamine compound represented by formula (31) include Versamine 551 (manufactured by BASF) and Priamine 1074 (manufactured by Croda Japan), which contain a compound represented by the following formula (33), and Versamine 552 (manufactured by BASF), Priamine 1073 (manufactured by Croda Japan), and Priamine 1075 (manufactured by Croda Japan), which contain a compound represented by the above formula (32). Such commercially available dimer diamine compounds are usually mixtures containing multiple types of amine compounds.

In addition, a tetracarboxylic dianhydride represented by the following formula (34) can be obtained by reacting a diamine compound represented by formula (31) with an acid halide derived from trimellitic anhydride. It is also preferable to use the tetracarboxylic dianhydride represented by the following formula (34) as a raw material for producing a polyimide resin (AI) and a polyamic acid (A-II).
In formula (34), i, j, k, and l are each an integer of 0 or greater. i+j is an integer of 6 or greater and 17 or less, and k+l is an integer of 8 or greater and 19 or less. In formula (34), the wavy line portion represents a carbon-carbon single bond or a carbon-carbon double bond.

As described above, the resin (A) blended in the photosensitive resin composition may have a polymerizable group on its molecular chain that can be polymerized by the action of the photosensitizer (C) in terms of photosensitivity. Typically, the polymerizable group is preferably a radically polymerizable group or a cationic polymerizable group, and more preferably a radically polymerizable group.

The bonding positions of the radically polymerizable groups or cationically polymerizable groups in the molecular chains of the polyimide resin (AI) and the polyamic acid (A-II) are not particularly limited.
The radical polymerizable group typically includes a group containing an ethylenically unsaturated double bond. As the ethylenically unsaturated double bond-containing group, a vinyl group or an alkenyl group-containing group including an alkenyl group such as an allyl group is preferable, and a (meth)acryloyl group-containing group is more preferable.
The cationic polymerizable group typically includes an epoxy group-containing group, an oxetanyl group-containing group, a vinyloxy group-containing group, etc. Among these, the epoxy group-containing group and the vinyloxy group-containing group are preferred. As the epoxy group-containing group, an alicyclic epoxy group-containing group and a glycidyl group are preferred. Note that the alicyclic epoxy group is an aliphatic cyclic group in which two carbon atoms as adjacent ring constituent atoms in the aliphatic cyclic group are bonded via an oxygen atom. In other words, the alicyclic epoxy group has an epoxy group containing a three-membered ring consisting of two carbon atoms and one oxygen atom on the aliphatic ring.

The above radically polymerizable group and cationically polymerizable group are preferably bonded to an aromatic ring in the molecular chain of the polyimide resin (AI) and the polyamic acid (A-II).
For this reason, the divalent organic group ^A1 in formula (A2) may be, for example, an aromatic group represented by any one of the above formulae (21) to (24) to which a radical polymerizable group or a cationically polymerizable group is further bonded on the aromatic ring.

Suitable examples of the radical polymerizable group bonded to an aromatic ring in the molecular chain of the polyimide resin (AI) and the polyamic acid (A-II) include groups represented by the following formula (A-a) or (A-b), which do not fall under the category of vinyloxy group-containing groups.
-(A ⁰¹ ) _na -R ⁰¹ ...(A-a)
-(A ⁰¹ ) _na -R ⁰² -A ⁰² -R ⁰¹ ...(A-b)

In formula (Aa) and formula (Ab), R ⁰¹ is an alkenyl group having 2 to 10 carbon atoms. ^{R 02} is an alkylene group having 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.

Preferable specific examples of the radical polymerizable group bonded to the aromatic ring in the main chain include:
-O-R ⁰³ ,
-O-CH ₂ CH ₂ -O-R ⁰³ ,
-O-CH ₂ CH ₂ CH ₂ -O-R ⁰³ ,
-O-CH ₂ CH ₂ CH ₂ CH ₂ -O-R ⁰³ ,
-CO-O-CH ₂ CH ₂ -O-R ⁰³ ,
-CO-O-CH ₂ CH ₂ CH ₂ -O-R ⁰³ ,
-CO-O-CH ₂ CH ₂ CH ₂ CH ₂ -O-R ⁰³ ,
-O-CH ₂ CH ₂ -NH-R ⁰³ ,
-O-CH ₂ CH ₂ CH ₂ -NH-R ⁰³ ,
-O-CH ₂ CH ₂ CH ₂ CH ₂ -NH-R ⁰³ ,
-CO-O-CH ₂ CH ₂ -NH-R ⁰³ ,
-CO-O-CH ₂ CH ₂ CH ₂ -NH-R ⁰³ ,
-CO-O-CH ₂ CH ₂ CH ₂ CH ₂ -R ⁰³ ,
-NH-R ⁰³ ,
-NH-CH ₂ CH ₂ -O-R ⁰³ ,
-NH-CH ₂ CH ₂ CH ₂ -O-R ⁰³ ,
-NH-CH ₂ CH ₂ CH ₂ CH ₂ -O-R ⁰³ ,
-CO-NH-CH ₂ CH ₂ -O-R ⁰³ ,
-CO-NH-CH ₂ CH ₂ CH ₂ -O-R ⁰³ ,
-CO-NH-CH ₂ CH ₂ CH ₂ CH ₂ -O-R ⁰³ ,
-NH-CH ₂ CH ₂ -NH-R ⁰³ ,
-NH-CH ₂ CH ₂ CH ₂ -NH-R ⁰³ ,
-NH-CH ₂ CH ₂ CH ₂ CH ₂ -NH-R ⁰³ ,
-CO-NH-CH ₂ CH ₂ -NH-R ⁰³ ,
-CO-NH- _{CH2CH2CH2 - NH} - ^R03 , and
Examples of the groups include those represented by the formula: --CO--NH--CH ₂ CH ₂ CH ₂ CH ₂ --NH--R ^03. In these groups, R ⁰³ is an allyl group or a (meth)acryloyl group.

It is preferable that the cationic polymerizable group is bonded to an aromatic ring in the molecular chain of the polyimide resin (AI) and the polyamic acid (A-II). Suitable examples of the cationic polymerizable group bonded to an aromatic ring in the molecular chain of the polyimide resin (AI) and the polyamic acid (A-II) include a vinyloxy group and groups represented by the following formulae (Ac) to (Ah).
-(A ⁰¹ ) _na -R ⁰⁴ ...(A-c)
-(A ⁰¹ ) _na -R ⁰² -R ⁰⁵ ...(A-d)
-(A ⁰¹ ) _na -R ⁰² -(CO) _nb -A ⁰³ -R ⁰⁴ ...(A-e)
-(A ⁰¹ ) _na -R ⁰² -(CO) _nb -A ⁰³ -R ⁰⁷ -R ⁰⁵ ...(A-f)
-(A ⁰¹ ) _na -R ⁰² -O-R ⁰⁶ ...(A-g)
-(A ⁰¹ ) _na -R ⁰² -(CO) _nb -A ⁰³ -R ⁰⁷ -O-R ⁰⁶ ...(A-j)

In formulae (A-c) to (A-h), R ⁰² is an alkylene group having 1 to 10 carbon atoms. R ⁰⁴ is an epoxyalkyl group having 2 to 20 carbon atoms, or an alicyclic epoxy group having 3 to 20 carbon atoms. R ⁰⁵ is an alicyclic epoxy group having 3 to 20 carbon atoms. R ⁰⁶ is a vinyl group. R ⁰⁷ is an alkylene 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 —O— or —NH—.
nb is 0 or 1.

Preferred specific examples of the cationically polymerizable group bonded to the aromatic ring in the main chain include:
-R ⁰⁷ ,
-O-CH ₂ CH ₂ -R ⁰⁷ ,
-O-CH ₂ CH ₂ CH ₂ -R ⁰⁷ ,
-O-CH ₂ CH ₂ CH ₂ CH ₂ -R ⁰⁷ ,
-CO-O-CH ₂ CH ₂ -R ⁰⁷ ,
-CO-O-CH ₂ CH ₂ CH ₂ -R ⁰⁷ ,
-CO-O-CH ₂ CH ₂ CH ₂ CH ₂ -R ⁰⁷ ,
-NH-CH ₂ CH ₂ -R ⁰⁷ ,
-NH-CH ₂ CH ₂ CH ₂ -R ⁰⁷ ,
-NH-CH ₂ CH ₂ CH ₂ CH ₂ -R ⁰⁷ ,
-CO-NH-CH ₂ CH ₂ -R ⁰⁷ ,
-CO-NH-CH ₂ CH ₂ CH ₂ -R ⁰⁷ , and
Illustrative examples include groups represented by the formula -CO-NH-CH ₂ CH ₂ CH ₂ CH ₂ -R ^07. In these groups, R ⁰⁷ is a vinyloxy group, a glycidyloxy group, an epoxycyclopentyl group, an epoxycyclohexyl group, or an epoxycycloheptyl group.

In the formula (A2), when A ¹ is an aromatic group having a radical polymerizable group or a cationically polymerizable group, specific examples of the aromatic group include the following groups.

（式（Ａ３）中、Ａ^２は炭素原子数６以上５０以下の４価の有機基である。） (Tetracarboxylic acid dianhydride)
As the tetracarboxylic dianhydride, any tetracarboxylic dianhydride that has been conventionally used in the production of polyamic acid and polyimide resins can be used without any particular limitation.
The tetracarboxylic dianhydride may be a compound represented by the following formula (A3): The tetracarboxylic dianhydride may be used alone or in combination of two or more kinds.

(In formula (A3), ^A2 is a tetravalent organic group having 6 to 50 carbon atoms.)

In formula (A3), ^A2 is a tetravalent organic group having 6 to 50 carbon atoms, and may have one or more substituents in addition to the two acid anhydride groups represented by -CO-O-CO- in formula (A3).
Preferred examples of the substituent include a fluorine atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a fluorinated alkyl group having from 1 to 6 carbon atoms, and a fluorinated alkoxy group having from 1 to 6 carbon atoms. The compound represented by formula (a1-1) may contain a carboxy group or a carboxylate group in addition to the acid anhydride group.
When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.
The same can be said about the above-mentioned substituents for one or more substituents that the aromatic group described below may have on the aromatic ring.

The number of carbon atoms constituting A ² is more preferably 8 or more, and even more preferably 12 or more. The number of carbon atoms constituting A ² is more preferably 40 or less, and even more preferably 30 or less. A ² may be an aliphatic group, an aromatic group, or a group combining these structures. A ² may contain a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom in addition to a carbon atom and a hydrogen atom. When ^{A 2} contains an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, the nitrogen atom, or the sulfur atom may be included in A ¹ as a group selected from a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -S-S-, and is more preferably included in A ¹ as a group selected from -O-, -CO-, -S-, and.

The tetracarboxylic acid dianhydride represented by formula (A3) may be an aliphatic tetracarboxylic acid dianhydride having two dicarboxylic acid anhydride groups bonded to an aliphatic group, or an aromatic tetracarboxylic acid dianhydride having at least one dicarboxylic acid anhydride group bonded to an aromatic group.
The aromatic tetracarboxylic dianhydride preferably has two dicarboxylic anhydride groups bonded to the aromatic group.

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

Examples of aromatic tetracarboxylic dianhydrides represented by formula (A3) and having two dicarboxylic anhydride groups bonded to an aromatic group include pyromellitic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, trimellitic (3,4-dicarboxyphenyl) dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, Examples of suitable dianhydrides include carboxylic acid dianhydrides, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, bis(2,3-dicarboxyphenoxy)methane dianhydride, 1,1-bis(2,3-dicarboxyphenoxy)ethane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride, 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride, 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (e.g., Rikacid TMEG100, manufactured by New Japan Chemical Co., Ltd.), and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane Chemical Co., Ltd.).
Among these aromatic tetracarboxylic dianhydrides, 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride, 4,4'-bis(3,4-dicarboxyphenyloxy)biphenyl dianhydride, 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride, 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (e.g., Rikacid TMEG100, manufactured by New Japan Chemical Co., Ltd.), and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane Chemical Co., Ltd.) are preferred, in terms of their ease of forming a cured product having excellent electrical properties.

In addition, the aromatic tetracarboxylic dianhydride is preferably biphenyltetracarboxylic dianhydride, in that it suppresses warping of the cured film of the photosensitive resin composition and provides good photolithography properties of the photosensitive resin composition.
Examples of the biphenyltetracarboxylic dianhydride include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride is preferred.

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

In the above formulae (a3-2) and (a3-3), R ^a01 , R ^a02 and R ^a03 each represent an aliphatic group optionally substituted with halogen, an oxygen atom, a sulfur atom, an aromatic group having one or more divalent elements bonded thereto, or a divalent group constituted by a combination thereof. R ^a02 and R ^a03 may be the same or different.
That is, R ^a01 , R ^a02 and R ^a03 may contain a carbon-carbon single bond, a carbon-oxygen-carbon ether bond or a halogen element (fluorine, chlorine, bromine, iodine). Examples of the compound represented by formula (a3-2) include 2,2-bis(3,4-dicarboxyphenoxy)propane dianhydride, bis(3,4-dicarboxyphenoxy)methane dianhydride, 1,1-bis(3,4-dicarboxyphenoxy)ethane dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene, 2,2-bis(3,4-dicarboxyphenoxy)hexafluoropropane dianhydride and 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride.

In the formula (a3-4), R ^a04 and R ^a05 are either an aliphatic group which may be substituted with halogen, an aromatic group via one or more divalent elements, or a halogen, or a monovalent substituent constituted by a combination thereof. R ^a04 and R ^a05 may be the same or different. As the compound represented by formula (a3-4), difluoropyromellitic dianhydride, dichloropyromellitic dianhydride, etc. can also be used.

式（ａ３－５）～式（ａ３－７）における、Ｒ^ａ０１、Ｒ^ａ０２、及びＲ^ａ０３は、前述の式（ａ３－２）、式（ａ３－３）、及び式（ａ３－４）における、Ｒ^ａ０１、Ｒ^ａ０２、及びＲ^ａ０３と同様である。
式（ａ３－５）、式（ａ３－６）、及び式（ａ３－７）における、Ｒ^ａ０６は、ラジカル重合性基、又はカチオン重合性基である。ラジカル重合性基、又はカチオン重合性基としては、それぞれ前述の基が挙げられる。
テトラカルボン酸二無水物自体が反応性に富む。例えば、エポキシ基は、カルボン酸無水物基と容易に反応してしまう。このため、Ａ^２が、式（ａ３－５）～式（ａ３－７）で表される基であるテトラカルボン酸二無水物に由来する構成単位に相当する構成単位を、ポリイミド樹脂（Ａ－Ｉ）、又はポリアミック酸（Ａ－ＩＩ）に導入する場合、ポリイミド樹脂（Ａ－Ｉ）、又はポリアミック酸（Ａ－ＩＩ）を合成した後に、ポリイミド樹脂（Ａ－Ｉ）、又はポリアミック酸（Ａ－ＩＩ）の分子鎖上に、ラジカル重合性基、又はカチオン重合性基導入するのが好ましい。 As described above, the polyimide resin (AI) and the polyamic acid (A-II) preferably have a radical polymerizable group or a cationically polymerizable group on the molecular chain.
For this reason, the tetravalent organic group ^A2 in formula (A3) may be a group represented by the following formulae (a3-5) to (a3-7).

In formulae (a3-5) to (a3-7), R ^a01 , R ^a02 , and R ^a03 are the same as R ^a01 , R ^a02 , and R ^a03 in the above-mentioned formulae (a3-2), (a3-3), and (a3-4).
In formulae (a3-5), (a3-6), and (a3-7), R ^a06 represents a radical polymerizable group or a cationically polymerizable group. Examples of the radical polymerizable group or the cationically polymerizable group include the groups described above.
Tetracarboxylic dianhydride itself is highly reactive. For example, an epoxy group easily reacts with a carboxylic anhydride group. For this reason, when introducing a structural unit corresponding to a structural unit derived from a tetracarboxylic dianhydride in which ^A2 is a group represented by formulas (a3-5) to (a3-7) into a polyimide resin (A-I) or a polyamic acid (A-II), it is preferable to synthesize the polyimide resin (A-I) or the polyamic acid (A-II) and then introduce a radical polymerizable group or a cationic polymerizable group onto the molecular chain of the polyimide resin (A-I) or the polyamic acid (A-II).

Examples of reactions for introducing a radical polymerizable group or a cationic polymerizable group include:
1) An etherification reaction between a halogen atom bonded to an aromatic ring in the molecular chain of a polyimide resin (AI) or a polyamic acid (A-II) and an alcohol compound having a radical polymerizable group or a cationically polymerizable group;
2) An esterification reaction between a hydroxy group bonded to an aromatic ring in the molecular chain of the polyimide resin (AI) or the polyamic acid (A-II) and a carboxylic acid halide having a radical polymerizable group or a cationically polymerizable group;
3) an esterification reaction between a carboxy group bonded to an aromatic ring in the molecular chain of the polyimide resin (AI) or the polyamic acid (A-II) and an organic halide having a radical polymerizable group or a cationically polymerizable group; and
4) N-substitution reaction between an amino group bonded to an aromatic ring in the molecular chain of the polyimide resin (AI) or polyamic acid (A-II) and an organic halide having a radical polymerizable group or a cationic polymerizable group. The reaction for introducing a radical polymerizable group or a cationic polymerizable group is not limited to these reactions.

For example, polyimide resin (A-I) or polyamic acid (A-II) having a hydroxy group protected by a protecting group such as an acetyl group, a carboxylate group such as a methoxycarbonyl group, or an amino group protected by a protecting group such as a tert-butoxycarbonyl group on an aromatic ring can be synthesized, and then deprotected by a known method to obtain polyimide resin (A-I) or polyamic acid (A-II) having a hydroxy group, carboxy group, amino group, or the like on an aromatic ring.

(Method for producing polyimide resin (AI) and polyamic acid (A-II))
The methods for producing the polyimide resin (A-I) and the polyamic acid (A-II) are not particularly limited. The polyimide resin (A-I) described above can typically be produced by reacting the diamine compound with a tetracarboxylic dianhydride to obtain a polyamic acid (A-II), and then imidizing the polyamic acid (A-II).
When producing the polyamic acid (A-II), the tetracarboxylic dianhydride and the diamine may each be used alone or in combination of two or more kinds.
As described above, the polyimide resin (AI) and the polyamic acid (A-II) may have a radical polymerizable group or a cationic polymerizable group. The radical polymerizable group or the cationic polymerizable group may be introduced onto the molecular chain after the synthesis of the polyamic acid (A-II) or after the synthesis of the polyimide resin (AI).
In the case where a radical polymerizable group or a cationically polymerizable group is introduced onto the molecular chain of the polyamic acid or the polyimide resin (A) after the synthesis of the polyamic acid (A-II) or the synthesis of the polyimide resin (AI), the method of introduction is not particularly limited.
A typical example of a method for introducing a radical polymerizable group or a cationically polymerizable group onto a molecular chain includes a method of reacting a polyamic acid (A-II) having a functional group such as a hydroxy group, an amino group, or a carboxy group, or a polyimide resin (A-I) with a carboxylic acid having a radical polymerizable group, a carboxylic acid halide having a radical polymerizable group, an alcohol having a radical polymerizable group, a phenol having a radical polymerizable group, an amine having a radical polymerizable group, a halogenated compound having a radical polymerizable group, a carboxylic acid having a cationically polymerizable group, a carboxylic acid halide having a cationically polymerizable group, an alcohol having a cationically polymerizable group, a phenol having a cationically polymerizable group, an amine having a cationically polymerizable group, or a halogenated compound having a cationically polymerizable group by a known method such as a condensation reaction using a known condensing agent or Williamson's etherification reaction.

From the viewpoints of the reaction and ease of availability of a compound having a radically polymerizable group or a cationic polymerizable group, it is preferable to condense a part or all of the carboxy groups of the polyamic acid (A-II) with an alcohol having a radically polymerizable group or an alcohol having a cationic polymerizable group.
In addition, even if the carboxy group of the polyamic acid (A-II) is modified with an alcohol having a radical polymerizable group or an alcohol having a cationic polymerizable group, the modified polyamic acid (A-II) is imidized by a method such as heating. In this case, imidization by ring closure proceeds while the alcohol having a radical polymerizable group or the alcohol having a cationic polymerizable group is eliminated.
The method of the condensation reaction is not particularly limited. For example, a carboxy group of the polyamic acid (A-II) can be condensed with an alcohol having a radical polymerizable group or an alcohol having a cationic polymerizable group in the presence of a condensing agent such as a carbodiimide compound.
Alternatively, a carboxy group in the polyamic acid (A-II) may be reacted with a halogenating agent such as thionyl chloride to form a halogenocarbonyl group (carboxylic acid halide group), and then the halogenocarbonyl group may be reacted with an alcohol having a radical polymerizable group or an alcohol having a cationically polymerizable group.

Examples of alcohols having a radical polymerizable group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, 2-hydroxy-3-tert-butyloxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-hydroxy-3-cyclohexyloxypropyl (meth)acrylate. mono(meth)acrylates of diols such as 1-(2-(meth)acryloyloxyethyl)-2-(2-hydroxypropyl) phthalate, ... (meth)acrylates of polyols having a hydroxyl group, such as glycerin-1,2-di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate; hydroxyalkyl group-substituted (meth)acrylamides, such as N-(2-hydroxyethyl)(meth)acrylamide; hydroxyl group-containing ketones, such as (hydroxymethyl)vinyl ketone and (2-hydroxyethyl)vinyl ketone; ton; 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, elidolinoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and alkenyl alcohol such as erucyl alcohol.
In the specification of the present application, (meth)acrylate means both acrylate and methacrylate.
Examples of alcohols having a cationically polymerizable group include monoglycidyl ethers of glycols such as 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; glycidyl alcohol; and epoxy alkanes substituted with a hydroxy group such as 3,4-epoxy-1-butanol.

The amounts of the tetracarboxylic dianhydride and the diamine compound used in synthesizing the polyamic acid (A-II) are not particularly limited, but the amount of the diamine compound used is preferably 0.8 mol or more and 1.2 mol or less, more preferably 0.9 mol or more and 1.1 mol or less, and particularly preferably 0.95 mol or more and 1.05 mol or less, relative to 1 mol of the tetracarboxylic dianhydride.
The weight average molecular weight of the polyamic acid (A-II) obtained may be appropriately set according to its application. The weight average molecular weight of the resin can be measured as a weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography). The weight average molecular weight of the polyamic acid (A-II) is, for example, 5000 or more, preferably 15000 or more, and more preferably 250,000,000 or more in terms of the above polystyrene, from the viewpoint of obtaining a cured film having good mechanical properties. On the other hand, the weight average molecular weight of the polyamic acid (A-II) obtained is, for example, 100,000 or less, preferably 80,000 or less, and more preferably 50,000 or less in terms of the above polystyrene, from the viewpoint of improving developability.
The weight average molecular weight can be adjusted to the above-mentioned value by adjusting the amounts of the tetracarboxylic dianhydride and the diamine compound mixed together, and reaction conditions such as the solvent and reaction temperature.

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

Examples of organic solvents used in the reaction of tetracarboxylic dianhydride with diamine compounds include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyramide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylisobutyric acid amide, methoxy-N,N-dimethylpropionamide, butoxy-N,N-dimethylpropionamide, N-methylcaprolactam, N,N'-dimethylpropyleneurea, N,N,N',N'-tetramethylurea, and pyridine; dimethylsulfoxide; sulfolane; γ-butyrolactone, γ-valerolactone, δ-valerolactone, esters such as methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate; carbonates such as ethylene carbonate and propylene carbonate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetonitrile; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, and tetrahydrofuran; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, and o-dichlorobenzene; hexane, heptane, benzene, toluene, and xylene.
These organic solvents may be used alone or in combination of two or more.

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

The temperature at which the tetracarboxylic dianhydride and the diamine compound are reacted is not particularly limited as long as the reaction proceeds smoothly. Typically, the reaction temperature between the tetracarboxylic dianhydride and the diamine compound is preferably from -5°C to 120°C, more preferably from 0°C to 80°C, and particularly preferably from 0°C to 50°C. The time for reacting the tetracarboxylic dianhydride and the diamine compound varies depending on the reaction temperature, but typically, it is preferably from 30 minutes to 20 hours, more preferably from 1 hour to 8 hours, and particularly preferably from 2 hours to 6 hours.

When polyamic acid (A-II) is produced by the above method, ring closure may occur in a portion of the polyamic acid, and imidization may progress partially. For convenience, a resin with an imidization rate of 50% or less is referred to as polyamic acid (A-II), and a resin with an imidization rate of more than 50% is referred to as polyimide resin (A-I).

In addition, when the tetracarboxylic dianhydride and/or diamine compound has a radical polymerizable group-containing group containing an ethylenically unsaturated double bond, a small amount of a polymerization inhibitor may be used to prevent crosslinking between the ethylenically unsaturated double bonds during the reaction. Examples of the polymerization inhibitor include phenols such as hydroquinone, 4-methoxyphenol, tert-butylpyrocatechol, and bis-tert-butylhydroxytoluene, and phenothiazine. The amount of the polymerization inhibitor used is preferably, for example, 0.01 mol % or more and 5 mol % or less based on the number of moles of the ethylenically unsaturated double bond.

By the method described above, a solution containing the polyamic acid (A-II) is obtained.
The resulting polyamic acid (A-II) is imidized by ring closure to produce a polyimide resin (AI).
The method of imidization is not particularly limited. The imidization may be performed by heating or using an imidizing agent.

When imidization is carried out by heating, heating may be carried out on a solution or suspension of the polyamic acid (A-II), or on the polyamic acid (A-II) in a solid state.
When the solution of polyamic acid (A-II) is heated to carry out the imidization, it is preferable to carry out the heating while removing water generated as a by-product during the imidization.
The heating conditions for imidization are not particularly limited as long as the polyamic acid (A-II) or the polyimide resin (AI) is not decomposed and the imidization proceeds satisfactorily.
When a solution of polyamic acid (A-II) is heated, typically, the heating temperature is preferably from 80° C. to 220° C., more preferably from 100° C. to 200° C., and particularly preferably from 120° C. to 180° C. When a solid polyamic acid (A-II) is heated, typically, the heating temperature is preferably from 180° C. to 400° C., and more preferably from 200° C. to 350° C.
The heating time varies depending on the heating temperature, but is typically preferably from 1 hour to 24 hours, more preferably from 2 hours to 12 hours.

When the polyamic acid (A-II) is imidized with an imidizing agent, the imidization is usually carried out by adding the imidizing agent to a solution or suspension of the polyamic acid (A-II). As an organic solvent that can be used when imidizing with an imidizing agent, for example, the same organic solvent as that which can be used in preparing the polyamic acid (A-II) can be used.
When imidization is performed using an imidizing agent, the concentration of polyamic acid (A-II) in a solution or suspension of polyamic acid (A-II) is not particularly limited. Typically, the concentration of polyamic acid (A-II) in a solution or suspension of polyamic acid (A-II) is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 30% by mass or less.
The amount of the imidizing agent used is not particularly limited and is selected depending on the type of the imidizing agent so that the polyamic acid (A-II) is imidized to a desired degree.
The reaction temperature when imidization is performed using an imidizing agent is not particularly limited. The reaction temperature is, for example, preferably 0° C. or higher and 100° C. or lower, and more preferably 5° C. or higher and 50° C. or lower.
The time for the imidization reaction when an imidizing agent is used is not particularly limited. The imidization reaction is preferably carried out for about 30 minutes to 24 hours, more preferably for 1 hour to 12 hours, and even more preferably for 2 hours to 6 hours, depending on the type of the imidizing agent.

Imidizing agents include dehydrating agents such as acetic anhydride, propionic anhydride, benzoic anhydride, trifluoroacetic anhydride, acetyl chloride, tosyl chloride, mesyl chloride, ethyl chloroformate, triphenylphosphine and dibenzimidazolyl disulfide, dicyclohexylcarbodiimide, carbodiimidazole, 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline, and oxalic acid N,N'-disuccinimidyl ester, and basic compounds such as pyridine, picoline, 2,6-lutidine, collidine, 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.

[Polyamide resin (A-III)]
The polyamide resin (A-III) is a resin derived from a diamine compound and a dicarboxylic acid compound or an amide-forming derivative of a dicarboxylic acid compound.

(Diamine Compound)
As the diamine compound, the same compounds as those explained for the polyimide resin (AI) and the polyamic acid (A-II) can be used.
As described above, the resin (A) to be blended in the photosensitive resin composition may have a polymerizable group on its molecular chain that can be polymerized by the action of the photosensitizer (C) from the viewpoint of photosensitivity. Typically, the polymerizable group is preferably a radical polymerizable group or a cation polymerizable group, and more preferably a radical polymerizable group.

The bonding position of the radical polymerizable group or the cationic polymerizable group in the molecular chain of the polyamide resin (A-III) is not particularly limited. The radical polymerizable group and the cationic polymerizable group are as described above for the polyimide resin (AI) and the polyamic acid (A-II).
The amount of radically polymerizable groups or cationic polymerizable groups in the polyamide resin (A-III) is similar to the amount of radically polymerizable groups or cationic polymerizable groups in the polyimide resin (AI) and the polyamic acid (A-II).

(Dicarboxylic acid compounds and amide-forming derivatives of dicarboxylic acid compounds)
As the dicarboxylic acid compound, various dicarboxylic acid compounds that have conventionally been used as raw materials for polyamide resins can be used without any particular limitation.
As the dicarboxylic acid compound, for example, an aliphatic dicarboxylic acid having 2 to 50 carbon atoms, or an aromatic carboxylic acid having 8 to 50 carbon atoms is preferable.

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

Suitable examples of the dicarboxylic acid compound 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, and alkyl, alkoxy, or halogen-substituted derivatives thereof.
The alkyl group as the substituent is preferably an alkyl group having from 1 to 4 carbon atoms. The alkoxy group as the substituent is preferably an alkoxy group having from 1 to 4 carbon atoms.
When the dicarboxylic acid compound is substituted with an alkyl group, an alkoxy group, or a halogen, the number of substitutions is preferably 1 or more and 4 or less, more preferably 1 or 2, and even more preferably 1.

In addition, dicarboxylic acid compounds having two carboxy groups and two carboxylic acid ester groups or two carboxylic acid amide groups, which are obtained by reacting a monohydroxy compound or a monoamino compound with the acid anhydride group of the carboxylic acid dianhydride described for the polyimide resin (A-I) and the polyamic acid (A-II), can also be suitably used as the dicarboxylic acid compound.

Suitable examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphthalic dianhydride, phenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, trimellitic (3,4-dicarboxyphenyl) dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, [5,5'-(1,4-phenylene)bisnorbornane]-2,2 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione (e.g., Rikacid TDA-100, New Japan Chemical Co., Ltd.), 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride, As dicarboxylic acid compounds corresponding to aromatic tetracarboxylic acid dianhydride such as 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride, 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride, 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (e.g., Rikacid TMEG100, manufactured by New Japan Chemical Co., Ltd.), and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (e.g., 10BTA, manufactured by Kurogane Chemical Co., Ltd.), dicarboxylic acid compounds obtained by reacting these aromatic tetracarboxylic acid dianhydrides with an alcohol represented by R ^a21 -OH or an amine represented by R ^a21 -NH ₂ are preferred.
R ^a21 is a monovalent organic group.
Such a dicarboxylic acid compound has two pairs of a carboxy group and a group represented by --CO--X ^a --R ^a21 , which are located on adjacent carbon atoms in the dicarboxylic acid compound. X ^a is --O-- or --NH.

The monovalent organic group represented by R ^a21 preferably has 1 or more and 20 or less, more preferably has 1 or more and 16 or less, further preferably has 1 or more and 12 or less, and particularly preferably has 1 or more and 8 or less carbon atoms.
Examples of the monovalent organic group represented by R ^a21 include an alkyl group having from 1 to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, an alkoxyalkyl group having from 2 to 20 carbon atoms, an alkoxyalkoxyalkyl group having from 3 to 20 carbon atoms, a (meth)acryloyloxyalkyl group having from 4 to 20 carbon atoms, a (meth)acryloyloxyalkyloxyalkyl group having from 5 to 20 carbon atoms, a glycidyloxyalkyl group having from 4 to 20 carbon atoms, and a glycidyloxyalkyloxyalkyl group having from 5 to 20 carbon atoms.

The dicarboxylic acid compound having two pairs of a carboxy group and a group represented by -CO-X ^a -R ^a21 has isomers which differ in the position of the carboxy group and the position of the group represented by -CO-X ^a -R ^a21 . As the dicarboxylic acid compound, one of such isomers may be used alone, or two or more of them may be used in combination.
As an example, a dicarboxylic acid compound corresponding to pyromellitic dianhydride has isomers represented by the following formula (a4-a1) and the following formula (a4-a2). Also, a dicarboxylic acid compound corresponding to 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride has isomers represented by the following formula (a4-b1), the following formula (a4-b2), and the following formula (a4-b3).
In the following formulae (a4-a1), (a4-a2), and (a4-b1) to (a4-b3), X ^a and R ^a21 are as defined above.

Dicarboxylic acid compounds corresponding to the tetracarboxylic acid dianhydrides represented by the above formulae (a3-2) to (a3-4) include compounds represented by the following formulae (a4-2a) to (a4-2c), (a4-3a) to (a4-3c), and (a4-4a) to (a4-4c). In formulae (a4-2a) to (a4-2c), (a4-3a) to (a4-3c), and (a4-4a) to (a4-4c), R ^a01 to R ^a05 are the same as those in formulae (a3-2) to (a3-4). In formulae (a4-2a) to (a4-2c), (a4-3a) to (a4-3c), and (a4-4a) to (a4-4c), X ^a and R ^a21 are as defined above.

Dicarboxylic acid compounds corresponding to the tetracarboxylic acid dianhydrides represented by the above formulae (a3-5) to (a3-7) include compounds represented by the following formulae (a4-5a) to (a4-5c), (a4-6a) to (a4-6c), (a4-7a), and (a4-7b). In formulae (a4-5a) to (a4-5c), (a4-6a) to (a4-6c), (a4-7a), and (a4-7b), R ^a01 to R ^a03 , R ^a06 , m1, and m2 are the same as those in formulae (a3-5) to (a3-7). In formulae (a4-5a) to (a4-5c), (a4-6a) to (a4-6c), (a4-7a), and (a4-7b), X ^a and R ^a21 are as defined above.

Examples of monohydroxy compounds that give dicarboxylic acid compounds by reacting with tetracarboxylic dianhydrides include alkane monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol; phenols or naphthols such as phenol, p-cresol, m-cresol, o-cresol, α-naphthol, and β-naphthol; monoethers of glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, 1,3-propanediol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; alcohols having the aforementioned radical polymerizable group; and alcohols having the aforementioned cationic polymerizable group.

The reaction between the tetracarboxylic dianhydride and the monohydroxy compound or monoamino compound can be carried out in the same manner as the reaction between the tetracarboxylic dianhydride and the diamine compound described above as the method for producing the polyamic acid (II). The reaction between the tetracarboxylic dianhydride and the monohydroxy compound or monoamino compound can be carried out in the presence of an organic base such as pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, 1,4-azabicyclo[2,2,2]octane, etc. These bases may be used alone or in combination of two or more.
The amount of the monohydroxy compound or monoamino compound used is preferably from 1.8 mol to 2.2 mol, more preferably from 2 mol to 2.1 mol, per mol of the tetracarboxylic dianhydride.
A dicarboxylic acid compound is obtained by reacting a tetracarboxylic acid dianhydride with the above-mentioned monohydroxy compound or monoamino compound. In the production of a dicarboxylic acid compound, depending on the production conditions, only one of the dicarboxylic acid anhydride groups may react with a monohydroxy compound or monoamino compound to produce a monocarboxylic acid compound having a dicarboxylic acid anhydride group, or a part of the tetracarboxylic acid dianhydride may react with moisture in the reaction system to produce a tetracarboxylic acid compound or a tricarboxylic acid compound.
As long as a resin can be obtained, a dicarboxylic acid compound including at least one selected from the above monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds can be used in the production of polyamide resin (A-III).
When the dicarboxylic acid compound contains at least one selected from the above monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds as an impurity, the content of the at least one selected from the above monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds as an impurity in the dicarboxylic acid compound is preferably 30 mass% or less, more preferably 10 mass% or less, still more preferably 5 mass% or less, and particularly preferably 1 mass% or less, based on the mass of the dicarboxylic acid compound including the mass of the impurity.

(Method for producing polyamide resin (A-III))
The method for producing the polyamide resin (A-III) is not particularly limited.
A preferred method for producing the polyamide resin (A-III) is, for example, a method in which a diamine compound and a dicarboxylic acid compound are condensed with a condensing agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, or N,N'-disuccinimidyl carbonate.

Another preferred method is a method in which a dicarboxylic acid compound or an acid halide of a dicarboxylic acid compound is condensed with a diamine compound in the presence of a base. In this method, a condensing agent may be used together with the base, if necessary.
As the acid halide, acid chlorides and acid bromides are preferred, and acid chlorides are more preferred.
Examples of the base include pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, 1,4-azabicyclo[2,2,2]octane, and the like.
Examples of the condensing agent 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'-tetramethyluronium tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl)diphenyl phosphonate, and 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)4-methoxymorpholinium chloride hydrate.

Specifically, a dicarboxylic acid compound or an acid halide of a dicarboxylic acid compound is reacted with a diamine compound in the presence of the above-mentioned base in an organic solvent at, for example, −20° C. or higher and 150° C. or lower, preferably 0° C. or higher and 50° C. or lower, for 30 minutes to 24 hours, preferably 1 hour to 4 hours.
The amount of the base used is preferably 2 to 4 times the number of moles of the dicarboxylic acid compound or the acid halide of the dicarboxylic acid compound, from the viewpoints of easy removal and easy production of a high molecular weight compound.

Also preferred is a method in which a carboxy group of a dicarboxylic acid compound is converted to an active group, and then a compound having an active group derived from the dicarboxylic acid compound is condensed with a diamine compound. Examples of the active group derived from the carboxy group in the activated dicarboxylic acid compound include a phenoxycarbonyl group, a (2-thioxo-2,3-dihydrobenzoxazol-3-yl)carbonyl group, a 1H-1,2,3-triazol-1-ylcarbonyl group, a 1H-benzotriazol-1-yloxycarbonyl group, a 1H-imidazol-1-ylcarbonyl group, a succinimidyloxycarbonyl group, and a 3H-1,2,3-triazolo[4,5-b]pyridin-3-yloxycarbonyl group.
When the active group derived from a carboxy group contains an aromatic ring, the aromatic ring may be substituted with one or more substituents selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a trifluoromethyl group, a chlorine atom, a bromine atom, an iodine atom, a phenoxy group, and a nitro group.

[Polybenzoxazole resin (A-IV) and polybenzoxazole resin precursor (A-V)]
The polybenzoxazole resin precursor (A-V) is a resin derived from a diamine compound, which is an aromatic compound having two amino groups bonded to an aromatic ring and a hydroxyl group bonded to a carbon atom adjacent to the carbon atom to which the amino groups on the aromatic ring are bonded, and a dicarboxylic acid compound or an amide-forming derivative of a dicarboxylic acid compound.
Such polybenzoxazole resin precursors (AV) have a hydroxy group on the aromatic ring at a position adjacent to the carbon atom to which the carbonyl group in the carboxylic acid amide bond (--CO--NH--) is bonded.
Polybenzoxazole resin (A-IV) is produced by ring-closing the polybenzoxazole resin precursor (AV).
The diamine compound and the dicarboxylic acid compound will be described below.

（式（Ａ１）中、Ｘは、炭素原子数１以上１００以下の有機基であり、Ｒ^ａ１は、ヒドロキシ基、カルボキシ基、又はハロゲン原子であり、Ｒ^ａ２は、炭素原子数１以上２０以下の脂肪族基、ヒドロキシ基、カルボキシ基、スルホン酸基、又はハロゲン原子であり、Ａｒは、Ｒ^ａ２で置換されていてもよいフェニル基、又はＲ^ａ２で置換されていてもよいナフチル基であり、ｍａ１は、０以上１０以下の整数であり、ｍａ２は、０以上７以下の整数であり、ｍａ３は、１以上１０以下の整数である。）
で表される化合物に由来する構成単位を含む。 (Diamine Compound)
As described above, the resin (A) is represented by the following formula (A1):

(In formula (A1), X is an organic group having 1 to 100 carbon atoms, R ^a1 is a hydroxy group, a carboxy group, or a halogen atom, R ^a2 is an aliphatic group having 1 to 20 carbon atoms, a hydroxy group, a carboxy group, a sulfonic acid group, or a halogen atom, Ar is a phenyl group which may be substituted with R ^a2 , or a naphthyl group which may be substituted with R ^a2 , ma1 is an integer of 0 to 10, ma2 is an integer of 0 to 7, and ma3 is an integer of 1 to 10.)
The compound includes a structural unit derived from the compound represented by the formula:

When resin (A) is polybenzoxazole resin (A-IV) and polybenzoxazole resin precursor (A-V), the ratio of the number of moles of the structural units derived from the compound represented by formula (A1) to the number of moles of all structural units derived from the diamine compound in polybenzoxazole resin (A-IV) and polybenzoxazole resin precursor (A-V) is preferably 10 mol% or more and 100 mol% or less, more preferably 15 mol% or more and 100 mol% or less, and even more preferably 20 mol% or more and 100 mol% or less.

（式（Ａ２－１）中、Ａ^３は、１以上の芳香環を含む４価の有機基を表す。ただし、Ａ^３としての２価の有機基は、前述の式（Ａ１）における、Ｘ、Ａｒ、Ｒ^ａ１、及びＲ^ａ２で構成される基には該当しない。式（Ａ２－１）で表される化合物において、２つのアミノ基は、それぞれＡ^３としての有機基中の芳香族基に結合する。式（Ａ２－１）で表される化合物において、２つのヒドロキシ基は、それぞれ、芳香族基中のアミノ基が結合する炭素原子に隣接する位置の炭素原子に結合する。） The other diamine compound is represented by the following formula (A2-1).

(In formula (A2-1), ^A3 represents a tetravalent organic group containing one or more aromatic rings. However, the divalent organic group represented by ^A3 does not correspond to the group composed of X, Ar, R ^a1 , and R ^a2 in formula (A1) above. In the compound represented by formula (A2-1), the two amino groups are each bonded to an aromatic group in the organic group represented by ^A3 . In the compound represented by formula (A2-1), the two hydroxyl groups are each bonded to a carbon atom in the aromatic group adjacent to the carbon atom to which the amino group is bonded.)

As described above, the resin (A) blended in the photosensitive resin composition may have a polymerizable group on its molecular chain that can be polymerized by the action of the photosensitizer (C) in terms of photosensitivity. Typically, the polymerizable group is preferably a radically polymerizable group or a cationic polymerizable group, and more preferably a radically polymerizable group.

(Dicarboxylic acid compounds and amide-forming derivatives of dicarboxylic acid compounds)
As the dicarboxylic acid compound and the amide-forming derivative of the dicarboxylic acid compound, the same compounds as the dicarboxylic acid compound and the amide-forming derivative of the dicarboxylic acid compound described for the polyamide resin (A-III) can be used.

(Method for producing polybenzoxazole resin (A-IV) and polybenzoxazole resin precursor (A-V))
The polybenzoxazole resin precursor (AV) can be produced by reacting the above-mentioned diamine compound with the dicarboxylic acid compound in the same manner as in the production method of the polyamide resin (A-III).
The polybenzoxazole resin precursor (AV) thus obtained is subjected to ring closure by heating to obtain a polybenzoxazole resin (A-IV). The heating temperature is, for example, preferably 120° C. or higher and 350° C. or lower, and more preferably 150° C. or higher and 350° C. or lower.
Also, the polybenzoxazole resin (A-IV) can be obtained by chemically ring-closing the polybenzoxazole resin precursor (AV) by the action of a dehydrating agent.

The main chain terminals of the resin (A) may be capped with a terminal capping agent for the purposes of improving the storage stability of the photosensitive resin composition, further improving the mechanical properties of a film formed using the photosensitive resin composition, improving the reproducibility of polymerization when producing the resin (A), etc. Examples of the terminal capping agent include monoamines, acid anhydrides, monocarboxylic acids, monoacid halides, and monoactive ester compounds.
The monoamine used for terminal blocking may be a known compound. Examples of the monoamine include aromatic monoamines such as aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 3-hydroxyaniline, 4-hydroxyaniline, 3-aminothiophenol, and 4-aminothiophenol, aliphatic monoamines having 3 to 20 carbon atoms and which may have a branched structure, such as hexylamine and octylamine, monoamines having an alicyclic structure, such as cyclohexylamine, and aminosilanes, such as trimethoxyaminopropylsilane and triethoxyaminopropylsilane.
Among the acid anhydrides, monoacid halides, and monoactive ester compounds used as end-capping agents, acid anhydrides are preferred. As the acid anhydride, known acid anhydrides and derivatives thereof 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 derivatives thereof.
From the viewpoint of excellent mechanical properties of a film formed using the photosensitive resin composition and excellent developability of the photosensitive resin composition, the introduction rate of the end-capping agent in the resin (A) is preferably 40 mol % or less, more preferably 20 mol % or less, and even more preferably 10 mol % or less, based on the number of moles of all monomers.

<Monomer Compound (B)>
When the resin (A) has a radical polymerizable group, the photosensitive resin composition may contain, together with the polyimide resin (A), a monomer compound having an ethylenically unsaturated double bond as the monomer compound (B). Such a monomer compound (B) may be a monofunctional monomer compound or a polyfunctional monomer compound, and is preferably a polyfunctional monomer compound.

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

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

Also, urethane (meth)acrylates described in JP-B-48-41708, JP-B-50-6034, and JP-A-51-37193; polyester (meth)acrylates described in JP-A-48-64183, JP-B-49-43191, and JP-A-52-30490; epoxy (meth)acrylates which are reaction products of epoxy resins and (meth)acrylic acid; compounds described in paragraphs [0254] to [0257] of JP-A-2008-292970; epoxy groups such as glycidyl (meth)acrylate and ethylenically unsaturated alkyl groups in polyfunctional carboxylic acids; Polyfunctional (meth)acrylates obtained by reacting a compound having a group; compounds and cardo resins having a fluorene ring and two or more groups having an ethylenically unsaturated bond, as described in JP-A-2010-160418, JP-A-2010-129825, and Japanese Patent No. 4364216, etc.; unsaturated compounds described in JP-B-43946, JP-B-1-40337, and JP-B-1-40336; vinylphosphonic acid compounds described in JP-A-2-25493; compounds containing a perfluoroalkyl group described in JP-A-61-22048; and photopolymerizable monomers and oligomers described in the Journal of the Japan Adhesion Association, vol. 20, No. 7, pp. 300-308 (1984) are also preferably used.

Among these monomer compounds having an ethylenically unsaturated double bond, polyfunctional monomer compounds having three or more functionalities are preferred, polyfunctional monomer compounds having four or more functionalities are more preferred, and polyfunctional monomer compounds having five or more functionalities are even more preferred, because they tend to increase the adhesion of the cured product to the substrate and the strength of the cured product.

When the resin (A) has a vinyloxy group-containing group as a cationic polymerizable group, the photosensitive resin composition may contain a vinyl ether compound as a monomer compound (B) together with the resin (A). Such a vinyl ether compound may be a monofunctional compound having one vinyloxy group, or a polyfunctional compound having two or more vinyloxy groups.

When the resin (A) has an epoxy group-containing group as a cationically polymerizable group, the photosensitive resin composition may contain various epoxy compounds as the monomer compound (B).

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

<Photosensitizer (C)>
The photosensitive resin composition contains a type of photosensitizer (C) according to the type of resin (A). When the resin (A) has a radical polymerizable group on its molecular chain or when the photosensitive resin composition contains a monomer compound (B) having a radical polymerizable group together with the resin (A), a photoradical polymerization initiator (C1) is used as the photosensitizer (C). When the resin (A) has a cationic polymerizable group 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 any conventionally known photopolymerization initiator can be used.

Specific examples of the photoradical polymerization initiator (C1) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinofumab), ... phenyl)-butan-1-one, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-2-(benzoyloximimino)-1-propanone, 1-phenyl-1,2-butadione-2-(o -methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, ethanone, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime (Irgacure OXE02, manufactured by BASF Japan Co., Ltd.), (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), 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), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid 2-Isoamyl anthraquinone, 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-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 2-aminoanthraquinone Quinones, β-chloroanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, 4-hydroxybenzophenone, Benzophenone, 4-phenylbenzophenone, fluorenone, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, 2-hydroxy-2-methylpropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, 2-phenylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxy Acetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 4-azidobenzalacetophenone, 2,6-bis(p-azidobenzylidene)cyclohexane, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis -(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl )-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone t, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propeneaminium chloride monohydrate, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenyl sulfone, etc. These photoradical polymerization initiators (C1) can be used alone or in combination of two or more.
From the viewpoint of good sensitivity, the photoradical polymerization initiator (C1) is preferably an oxime ester-based photopolymerization initiator.

Among the photoradical polymerization initiators (C1), oxime ester compounds are preferred in terms of the sensitivity of the photosensitive resin composition.
The oxime ester compound is preferably a compound having a partial structure represented by the following formula (c1).

（式（ｃ１）中、
ｎ１は、０、又は１であり、
Ｒ^ｃ２は、一価の有機基であり、
Ｒ^ｃ３は、水素原子、置換基を有してもよい炭素原子数１以上２０以下の脂肪族炭化水素基、又は置換基を有してもよいアリール基であり、
＊は結合手である。）

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

Typical examples of the cationic photopolymerization initiator (C2) include onium salts. Examples of the cationic photopolymerization initiator (C2) include oxonium salts, ammonium salts, phosphonium salts, sulfonium salts, and iodonium salts, with sulfonium salts and iodonium salts being preferred, and sulfonium salts being more preferred.

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. The content of the photoradical polymerization initiator (C1) or the photocationic polymerization initiator (C2) in the photosensitive resin composition is typically 0.01 to 20 parts by mass, preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total of the mass of the resin (A) and the mass of the monomer compound (B).

The photosensitive resin composition may also contain a quinone diazide group-containing compound (C3) as the photosensitizer (C). The photosensitive resin composition containing the quinone diazide group-containing compound (C3) is a positive-type photosensitive resin composition that becomes soluble in an alkaline developer upon exposure to light.

The quinone diazide group-containing compound (C3) can be appropriately selected from compounds having a quinone diazide group that have been conventionally incorporated into various positive-type photosensitive resin compositions. The quinone diazide group-containing compound (C3) may be used alone or in combination of two or more kinds.

The quinone diazide group-containing sulfonic acid used as the quinone diazide group-containing compound (C3) is not particularly limited, but examples thereof include naphthoquinone diazide sulfonic acids such as naphthoquinone-1,2-diazide-5-sulfonic acid and naphthoquinone-1,2-diazide-4-sulfonic acid; orthoanthraquinone diazide sulfonic acid, and naphthoquinone diazide sulfonic acid is preferred. The quinone diazide group-containing sulfonic acid, preferably the above ester compound of naphthoquinone diazide sulfonic acid, dissolves well in a solvent that is usually used when the photosensitive resin composition is used as a solution. When these compounds are blended with the quinone diazide group-containing compound (C3) as the quinone diazide group-containing compound, a highly sensitive positive-type photosensitive resin composition is easily obtained.

The method for producing the above ester compound as the quinone diazide group-containing compound (C3) is not particularly limited, and examples include a method in which a quinone diazide group-containing sulfonic acid is added as a sulfonyl chloride such as naphthoquinone-1,2-diazide-sulfonyl chloride, and condensed in a solvent such as dioxane in the presence of an alkali such as triethanolamine, an alkali carbonate, or an alkali hydrogen carbonate to completely or partially esterify the compound.

From the viewpoint of the sensitivity of the photosensitive resin composition, the content of the quinone diazide group-containing compound (C3) is preferably within the following range. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of resin (A). The upper limit is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less, per 100 parts by mass of resin (A).

<Organic solvent (S)>
The photosensitive resin composition may contain an organic solvent (S) for the purpose of adjusting the coating property, etc. The type of organic solvent (S) is not particularly limited as long as it dissolves the resin (A) and other components well.

Specific examples of organic solvents (S) that have good solubility for the resin (A) include nitrogen-containing polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylisobutyric acid amide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylpropionamide, N,N-dimethylisobutyramide, and N,N-dimethylpropylene urea; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, diisobutyl ketone, cyclopentanone, Ketones such as cyclohexanone and isophorone; γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, isopentyl acetate, n-pentyl formate, n-butyl propionate, isopropyl butyrate, ethyl butyrate, n-butyl butyrate, methyl methoxylate, ethyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate , ethyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, methyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and other esters; diacetone alcohol, and 3-methyl-3-methoxybutanoate. alcohols such as alcohol; 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, diethylene glycol dimethyl ether; aromatic ethers such as anisole; cyclic ethers such as dioxane and tetrahydrofuran; cyclic esters such as ethylene carbonate and propylene carbonate; aromatic solvents such as anisole, toluene, and xylene; aliphatic hydrocarbons such as limonene; and sulfoxides such as dimethyl sulfoxide.

The amount of organic solvent (S) used is not particularly limited as long as a uniform liquid photosensitive resin composition can be prepared. The photosensitive resin composition may be in the form of a suspension or a solution, and is preferably a solution. Typically, the organic solvent (S) is used so that the solids concentration of the photosensitive resin composition is preferably 15% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 45% by mass or less.

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

As the sensitizer, known compounds can be used. Examples of the sensitizer 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.

As the polymerization inhibitor, known compounds can be used. Examples of the polymerization inhibitor include compounds having a phenolic hydroxyl group, nitroso compounds, N-oxide compounds, quinone compounds, N-oxyl compounds, and phenothiazine compounds. More specifically, the polymerization inhibitor is preferably 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, and more preferably Irganox 1010, 2,6-di-tert-butyl-p-cresol, and 4-methoxyphenol.

From the viewpoint of achieving both excellent developability of the photosensitive resin composition and good antioxidant effect, the amount of polymerization inhibitor used is preferably 0.005% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.5% by mass or less, and even more preferably 0.03% by mass or more and 0.3% by mass or less, based on the mass of resin (A).

The nitrogen-containing heterocyclic compound stabilizes the metal surface by coordinating with the metal surface, thereby improving the adhesion of the film formed using the photosensitive resin composition to the metal surface. Known compounds can be used as the nitrogen-containing heterocyclic compound. Examples of the nitrogen-containing interheterocyclic compound include imidazole, pyrazole, indazole, carbazole, triazole, pyrazoline, pyrazolidine, tetrazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid, and derivatives thereof. Specific examples of the nitrogen-containing interheterocyclic compound that are preferable from the viewpoint of coordination with the metal include triazoles such as 1H-benzotriazole, 4-methyl-1H-methylbenzotriazole, 5-methyl-1H-methylbenzotriazole, 4-carboxy-1H-methylbenzotriazole, and 5-carboxy-1H-methylbenzotriazole, and triazoles such as 1H-tetrazole, 5-methyl-1H-tetrazole, and 5-phenyl-1H-tetrazole.

From the viewpoint of achieving both excellent developability of the photosensitive resin composition and improved adhesion of the film formed using the photosensitive resin composition to a substrate or the like, the amount of the nitrogen-containing heterocyclic compound used is preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.05% by mass or more and 3% by mass or less, based on the mass of the resin (A).

By blending a silane coupling agent in the photosensitive resin composition, the adhesion of the film formed using the photosensitive resin composition to the substrate or the like can be improved. As the silane coupling agent, a known compound can be used. As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(epoxycyclohexyl)ethyltrimethoxysilane, 2-(epoxycyclohexyl)triethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, tris(3-triethoxysilylpropyl)isocyanurate, a reaction product of 3-aminopropyltrimethoxysilane and an acid anhydride, a reaction product of 3-aminopropyltriethoxysilane and an acid anhydride, and the like can be mentioned.
Examples of acid anhydrides to be reacted with 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane include succinic anhydride, maleic anhydride, nadic anhydride, 3-hydroxyphthalic anhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, and 4,4'-oxydiphthalic dianhydride.

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

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

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

When the resin (A) is a resin that can be converted into a polyimide resin or a benzoxazole resin by heating, the photosensitive resin composition of the resin (A) may contain a cyclization promoter. The cyclization promoter promotes the production of a polyimide resin or a polybenzoxazole resin by cyclization of the polyamic acid (A-II), the polyamide resin (A-III) containing a structural unit derived from a dicarboxylic acid compound that can be synthesized by the reaction of a tetracarboxylic dianhydride with a monohydroxy compound, or the polybenzoxazole resin precursor (A-V).
When the photosensitive resin composition contains a cyclization accelerator, the mechanical properties and weather resistance reliability of the film formed by generating a polyimide resin or a benzoxazole resin by cyclization using the photosensitive resin composition are improved. As the cyclization accelerator, a known thermal base generator or thermal acid generator is used.

The amount of each additive used is not particularly limited as long as it does not impede the object of the present invention. The amount of additives not described above may be appropriately adjusted within a range of, for example, 0.001% by mass to 60% by mass, and preferably 0.01% by mass to 5% by mass, based on the mass of the solid content of the photosensitive resin composition.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition can be prepared by uniformly mixing the essential components and optional components as described above in desired amounts. The mixing method is not particularly limited. In order to remove foreign matter from the photosensitive resin composition, it is preferable to filter the photosensitive resin composition through a filter.

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

The substrate film is preferably one that is light-transmitting. Specific examples include polyethylene terephthalate (PET) film, polypropylene (PP) film, and polyethylene (PE) film, with polyethylene terephthalate (PET) film being preferred due to its excellent balance of light transmittance and breaking strength.

The above-mentioned photosensitive resin composition is applied onto a substrate film to form a photosensitive layer, thereby producing a photosensitive dry film.
When forming a photosensitive layer on a substrate film, the photosensitive resin composition is applied onto the substrate film using an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, or the like, so that the film thickness after drying is preferably 0.5 μm or more and 300 μm or less, more preferably 1 μm or more and 300 μm or less, and particularly preferably 3 μm or more and 100 μm or less, and then dried.

The photosensitive dry film may further have a protective film on the photosensitive layer. Examples of such a protective film include a polyethylene terephthalate (PET) film, a polypropylene (PP) film, and a polyethylene (PE) film.

<Method for manufacturing patterned resin film>
a lamination step of laminating a photosensitive layer made of the photosensitive resin composition on a substrate;
an exposure step of exposing the photosensitive layer to actinic rays or radiation in a position-selective manner;
A patterned resin film can be produced by a method including a development step of developing the exposed photosensitive layer to obtain a patterned resin film.

The substrate on which the photosensitive layer is laminated is not particularly limited, and any conventionally known substrate can be used, such as a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed. The substrate can also be a silicon substrate or a glass substrate.

The photosensitive layer is laminated on the substrate, for example, as follows. That is, a liquid photosensitive resin composition is applied onto the substrate, and the solvent is removed by heating to form a photosensitive layer of a desired thickness. The thickness of the photosensitive layer is not particularly limited as long as the resist pattern to be the mold can be formed with a desired thickness. The thickness of the photosensitive layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm to 300 μm, particularly preferably 1 μm to 150 μm, and most preferably 3 μm to 100 μm.
The above-mentioned photosensitive dry film may also be applied onto a substrate to laminate a photosensitive layer onto the substrate.

The photosensitive resin composition can be applied to a substrate by a method such as spin coating, slit coating, roll coating, screen printing, or applicator. It is preferable to prebake the photosensitive layer. The prebake conditions vary depending on the type and blending ratio of each component in the photosensitive resin composition, the coating film thickness, etc., but are usually 70° C. to 200° C., preferably 80° C. to 150° C., and 2 minutes to 120 minutes.
The photosensitive layer formed as described above is selectively irradiated (exposed) with actinic rays or radiation, for example, ultraviolet rays or visible rays having a wavelength of 300 nm or more and 500 nm or less, through a mask having a predetermined pattern.

Examples of radiation sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, argon gas lasers, etc. Radiation includes microwaves, infrared rays, visible light, ultraviolet rays, X-rays, gamma rays, electron beams, proton beams, neutron beams, ion beams, etc. The radiation dose varies depending on the composition of the photosensitive resin composition and the film thickness of the photosensitive layer, but is, for example, 100 mJ/ ^cm2 or more and 10,000 mJ/ ^cm2 or less when an ultra-high pressure mercury lamp is used.

Next, the exposed photosensitive layer is developed according to a conventional method, and unnecessary portions are dissolved and removed to form a resin film patterned in a predetermined shape. In this case, a developer according to the components contained in the photosensitive resin composition is used. When the photosensitive resin composition contains a resin having an alkali-soluble group such as polyamic acid (A-II) as the resin (A) or when the photosensitive resin composition contains a quinone diazide group-containing compound (C3), an alkaline aqueous solution is used as the developer. When the photosensitive resin composition contains a resin having a radical polymerizable group or a cationic polymerizable group as the resin (A) and does not contain or contains only a small amount of a component that is soluble in an alkaline aqueous solution or a component that is solubilized in an alkaline aqueous solution by exposure, the above-mentioned organic solvent (S) can be used as the developer.

Examples of alkaline developers that can be used include aqueous solutions of alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (tetramethylammonium hydroxide), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonane. In addition, aqueous solutions of the above-mentioned alkaline solutions to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant has been added can also be used as the developer.

The development time varies depending on the composition of the photosensitive resin composition and the film thickness of the photosensitive layer, but is usually between 1 minute and 30 minutes. The development method may be any of the puddle method, dipping method, paddle method, spray development method, etc.

After development, washing is performed for 30 to 90 seconds as necessary, and the patterned resin film is dried using an air gun, oven, or the like. In this way, a resin film patterned into the desired shape is formed on the surface of the substrate. There are no particular limitations on the cleaning solvent. For example, water or alcohols can be used as the cleaning solvent in the case of alkaline development. When development is performed with an organic solvent, an organic solvent (S) can be used as long as it does not cause solvent shock.

In the case where the resin film contains polyamic acid (A-II), polyamide resin (A-III) containing a constitutional unit derived from a dicarboxylic acid compound that can be synthesized by a reaction between a tetracarboxylic dianhydride and a monohydroxy compound, or polybenzoxazole resin precursor (A-V), after development, the developed coating film may be baked as necessary to convert the polyamide resin (A-III) containing a constitutional unit derived from a dicarboxylic acid compound that can be synthesized by a reaction between a tetracarboxylic dianhydride and a monohydroxy compound or the polyamic acid (A-II) into a polyimide resin (A), or convert the polybenzoxazole resin precursor (A-V) into a polybenzoxazole resin (A-IV).
The baking temperature is as described above for the resin (A). In addition, from the viewpoint of preventing oxidation of the cured film and obtaining a cured film having good mechanical properties, baking is preferably performed under an inert gas atmosphere such as nitrogen or argon.

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

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

In Examples 1 to 11 and Comparative Examples 1 and 2, the following DA1 to DA6 were used as diamine compounds.

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

After the dicarboxylic acid solution containing 0.1 mol of di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid was cooled to 0°C, a solution consisting of 42.30 g (0.21 mol) of dicyclohexylcarbodiimide and 42 g of NMP and a diamine solution consisting of 36.84 g (0.10 mol) of the above DA1 and 43 g of NMP were dropped into the dicarboxylic acid solution. After the dropwise addition was completed, the resulting reaction solution was stirred at room temperature for 4 hours to carry out a condensation reaction. After the reaction was completed, 19.7 g of methanol was injected into the reaction solution, and the precipitate was removed by filtration to obtain a reaction solution. The resulting reaction solution was dropped into an aqueous solution of isopropyl alcohol to precipitate a brown polyamide resin powder. The precipitated powder was collected by filtration and then washed three times with isopropyl alcohol. The washed powder was dried under reduced pressure to obtain a polyamide resin that is a polycondensation product of the di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid and the above DA1. The obtained polyamide resin has a 2-(methacryloyloxy)ethoxycarbonyl group as a radical polymerizable group.

The obtained polyamide resin was dissolved in γ-butyrolactone to a concentration of 30% by mass, and then 5% by mass of an oxime ester initiator (Irgacure OXE02 (BASF Japan)) based on the mass of the polyamide resin, 0.05% by mass of a polymerization inhibitor (Irganox 1010 (BASF Japan)) based on the mass of the polyamide resin, 0.02% by mass of a surfactant (Polyflow No. 77 (Kyoeisha Chemical Co., Ltd.)) based on the mass of the polyamide resin, and 3% by mass of N-[3-(triethoxysilyl)propyl]phthalamide based on the mass of the polyamide resin were added to the obtained solution to obtain a photosensitive resin composition.

Example 2
Except for changing the diamine compound to 34.26 g (0.093 mol) of the above DA1 and 2.58 g (0.007 mol) of DA4, the same procedure as in Example 1 was followed to obtain a polyamide resin which is a polycondensation product of the di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid, the above DA1 and DA4, and a photosensitive resin composition containing the polyamide resin.

Example 3
Except for changing the diamine compound to 31.32 g (0.085 mol) of the above DA1 and 5.53 g (0.015 mol) of DA4, the same procedure as in Example 1 was followed to obtain a polyamide resin which is a polycondensation product of the di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid, the above DA1 and DA4, and a photosensitive resin composition containing the polyamide resin.

Example 4
Except for changing the diamine compound to 28.74 g (0.078 mol) of the above DA1 and 8.11 g (0.022 mol) of DA4, the same procedure as in Example 1 was followed to obtain a polyamide resin which is a polycondensation product of the di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid, the above DA1 and DA4, and a photosensitive resin composition containing the polyamide resin.

Example 5
Except for changing the diamine compound to 11.79 g (0.032 mol) of the above DA1 and 21.37 g (0.058 mol) of DA4, the same procedure as in Example 1 was followed to obtain a polyamide resin which is a polycondensation product of the di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid and the above DA1 and DA4, and a photosensitive resin composition containing the polyamide resin.

Example 6
Except for changing the diamine compound to 8.84 g (0.024 mol) of the above DA1 and 28.00 g (0.076 mol) of DA4, the same procedure as in Example 1 was followed to obtain a polyamide resin which is a polycondensation product of the di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid and the above DA1 and DA4, and a photosensitive resin composition containing the polyamide resin.

Example 7
Except for changing the diamine compound to 4.42 g (0.012 mol) of the above DA1 and 30.21 g (0.082 mol) of DA4, the same procedure as in Example 1 was followed to obtain a polyamide resin which is a polycondensation product of the di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid, the above DA1 and DA4, and a photosensitive resin composition containing the polyamide resin.

Example 8
Except for changing the diamine compound to 2.95 g (0.008 mol) of the above DA1 and 33.90 g (0.092 mol) of DA4, the same procedure as in Example 1 was followed to obtain a polyamide resin which is a polycondensation product of the di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid and the above DA1 and DA4, and a photosensitive resin composition containing the polyamide resin.

Example 9
Except for changing the diamine compound to 39.25 g (0.10 mol) of the above DA2, the same procedure as in Example 1 was carried out to obtain a polyamide resin which is a polycondensation product of di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid and the above DA2, and a photosensitive resin composition containing the polyamide resin.

Example 10
Except for changing the diamine compound to 30.04 g (0.10 mol) of the above DA7, the same procedure as in Example 1 was followed to obtain a polyamide resin which is a polycondensation product of the di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid and the above DA7, and a photosensitive resin composition containing the polyamide resin.

Example 11
Except for changing the diamine compound to 7.68 g (0.035 mol) of the above DA3 and 23.95 g (0.065 mol) of DA4, the same procedure as in Example 1 was followed to obtain a polyamide resin which is a polycondensation product of the di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid and the above DA3 and DA4, and a photosensitive resin composition containing the polyamide resin.

Example 12
Into a three-neck flask, 15.57 g of DA1 as a diamine component, 6.43 g of DA6, and 250 g of NMP were added. The contents of the flask were then stirred to dissolve DA1 and DA6 in NMP. Thereafter, 40 g of 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride (BPADA) was added to the solution in the flask, and the reaction solution in the flask was stirred at room temperature for 24 hours. Thereafter, 0.88 g of 5-norbornene-2,3-dicarboxylic anhydride was added to the reaction solution as an end-capping agent, and the reaction solution was stirred at room temperature for 4 hours to obtain a polyamic acid.
In addition, the numerical values in the parentheses to the right of the following formulas indicate the molar ratios (mol %) of each structural unit in the resin.
<Polyamic acid production>

33 g of carbodiimidazole was added to the reaction solution containing the polyamic acid, and the reaction solution was stirred at room temperature for 4 hours to convert the polyamic acid into a polyimide resin.
The reaction solution after stirring was dropped into 5 kg of water to generate a precipitate. The generated precipitate was collected by filtration. The collected precipitate was washed three times with 2 kg of water and then dried under reduced pressure at 50° C. to obtain a polyimide resin having a carboxy group, which is composed of a structural unit in the following formula:
<Imidization>

The obtained polyimide resin having a carboxy group, 8.25 g of 2-hydroxyethyl methacrylate, 25.0 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC-HCl), and 5.15 g of 4-dimethylaminopyridine (DMAP) were added to 250 g of NMP in a three-neck flask, and the reaction solution was stirred at room temperature for 6 hours.
The reaction solution after stirring was dropped into 2 kg of methanol to generate a precipitate. The generated precipitate was collected by filtration. The collected precipitate was washed three times with 2 kg of methanol and then dried under reduced pressure at 50°C to obtain a polyimide resin having a methacryloyl group at the side chain end, which is composed of the structural unit shown in the following formula.
The obtained polyimide resin was subjected to ¹ H-NMR measurement. The imidization was confirmed by the disappearance of the peak corresponding to the amide bond, and the introduction of the theoretical amount of methacryloyl groups into the polyimide resin was confirmed from the integral ratio of all aromatics and the integral ratio of double bonds.
<Introduction of methacryloyl group>

A photosensitive resin composition was obtained in the same manner as in Example 1, except that the polyamide resin was replaced with the polyimide resin obtained by the above method.

Example 13
A polyamide resin and a photosensitive resin composition were obtained in the same manner as in Example 1, except that 31.02 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride was changed to 52.05 g (0.10 mol) of 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride.

Example 14
A polyamide resin and a photosensitive resin composition were obtained in the same manner as in Example 1, except that 31.02 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride was changed to 29.42 g (0.10 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride.

Example 15
A polyamide resin and a photosensitive resin composition were obtained in the same manner as in Example 1, except that 31.02 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride was replaced with 39.04 g (0.075 mol) of 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride and 5.45 g (0.025 mol) of pyromellitic dianhydride.

Example 16
A polyamide resin and a photosensitive resin composition were obtained in the same manner as in Example 1, except that 31.02 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride was changed to 53.44 g (0.10 mol) of 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride.

Example 17
A polyamide resin and a photosensitive resin composition were obtained in the same manner as in Example 1, except that 31.02 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride was changed to 7.76 g (0.025 mol) of 4,4'-oxydiphthalic dianhydride and 40.08 g (0.075 mol) of 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride.

Example 18
A polyamide resin and a photosensitive resin composition were obtained in the same manner as in Example 1, except that 31.02 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride was changed to 15.51 g (0.050 mol) of 4,4'-oxydiphthalic dianhydride and 26.72 g (0.050 mol) of 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride.

Example 19
A polyamide resin and a photosensitive resin composition were obtained in the same manner as in Example 1, except that 31.02 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride was changed to 23.27 g (0.075 mol) of 4,4'-oxydiphthalic dianhydride and 13.36 g (0.025 mol) of 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride.

Example 20
A polyamide resin and a photosensitive resin composition were obtained in the same manner as in Example 1, except that 31.02 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride was changed to 50.84 g (0.1 mol) of 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride.

Example 21
A polyamide resin and a photosensitive resin composition were obtained in the same manner as in Example 1, except that 31.02 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride was changed to 15.51 g (0.050 mol) of 4,4'-oxydiphthalic dianhydride and 25.42 g (0.050 mol) of 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride.

Example 22
A polyamide resin and a photosensitive resin composition were obtained in the same manner as in Example 1, except that 31.02 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride was changed to 23.27 g (0.075 mol) of 4,4'-oxydiphthalic dianhydride and 12.71 g (0.025 mol) of 2,6-bis(3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride.

Example 23
A polyamide resin and a photosensitive resin composition were obtained in the same manner as in Example 1, except that 23.27 g (0.075 mol) of 4,4'-oxydiphthalic dianhydride was changed to 23.27 g (0.075 mol) of 4,4'-oxydiphthalic dianhydride and 11.11 g (0.025 mol) of 2,2-bis(3,4-dicarboxyphenoxy)hexafluoropropane dianhydride.

Comparative Example 1
Except for changing the diamine compound to 36.84 g (0.1 mol) of the above DA4, the same procedure as in Example 1 was followed to obtain a polyamide resin which is a polycondensation product of the di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic dianhydride and the above DA4, and a photosensitive resin composition containing the polyamide resin.

Comparative Example 2
Except for changing the diamine compound to 20.02 g (0.1 mol) of the above DA5, the same procedure as in Example 13 was followed to obtain a polyamide resin which is a polycondensation product of the di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic dianhydride and the above DA5, and a photosensitive resin composition containing the polyamide resin.

The photosensitive resin compositions obtained in Examples 1 to 23, Comparative Example 1, and Comparative Example 2 were used to perform a photosensitivity evaluation, an evaluation of the dielectric tangent of the resin film, an evaluation of the appearance of the resin film, and a tensile test of the resin film according to the following methods. The results of these evaluations are shown in Table 1.

<Photosensitivity Evaluation>
The photosensitive resin composition was applied onto a copper substrate using a spin coater, and then baked at 80° C. for 300 seconds to obtain a coating film with a thickness of 12 μm. The coating film was exposed to light from 100 mJ/cm ² to 4000 mJ/cm ² at a focus of 0 μm using a ghi-line exposure machine (manufactured by Ultratech) through a negative mask capable of forming via holes with an opening diameter of 50 μm. The exposed coating film was developed by immersing it in cyclopentanone for 60 seconds. The developed, patterned resin film was observed, and the photosensitivity was evaluated according to the following criteria.
A: A via hole having an opening diameter of 50 μm was formed.
x: A via hole having an opening diameter of 50 μm was formed.

<Dielectric tangent evaluation>
After the photosensitive resin composition was applied onto a silicon wafer by a spin coater, the thin film of the photosensitive resin composition was baked at 90°C for 240 seconds. The baked coating film was exposed to an integrated light dose of 2000 mJ/ ^cm2 using a high-pressure mercury lamp. The exposed film was heated to 230°C at a heating rate of 5°C/min in a nitrogen atmosphere in an inert oven, and the coating film was heated at the same temperature for 1 hour. When the temperature dropped to 100°C, the wafer was removed and immersed in a 2 wt% aqueous hydrofluoric acid solution for 5 to 30 minutes, and the resin film was peeled off from the wafer to obtain a resin film made of a polyimide resin in which the resin obtained in each example was imidized by ring closure. However, since the photosensitive resin composition obtained in Example 12 contains a polyimide resin, when the photosensitive resin composition of Example 12 is used, baking under the above conditions was not performed after exposure, and baking was performed for 30 minutes at 180°C to remove the solvent. The thickness of the resin film after peeling was 10 μm.

The dielectric loss tangent (tan δ) of the obtained film was measured by the method described in the Technical Report of the Institute of Electronics, Information and Communication Engineers, vol. 118, no. 506, MW2018-158, pp. 13-18, March 2019, "Study on evaluation of millimeter-wave complex dielectric constant of photosensitive insulating film by cylindrical cavity resonator method" (Kohei Takahagi (Utsunomiya University), Kazuaki Ebisawa (Tokyo Ohka Kogyo Co., Ltd.), Yoshinori Kogami (Utsunomiya University), Takashi Shimizu (Utsunomiya University)). Using a network analyzer HP8510C (manufactured by Keysight Corporation), the measurement was performed by the cavity resonator method under the conditions of room temperature 25 ° C, humidity 50%, frequency 36 GHz, and sample thickness 10 μm. Based on the measured value of the dielectric loss tangent, the dielectric loss tangent was evaluated according to the following criteria.
A: The dielectric tangent value is less than 0.008.
B: The dielectric tangent value is 0.008 or more and less than 0.011.
C: The dielectric tangent value is 0.011 or more and less than 0.014.
D: Dielectric tangent value is 0.014 or more.

<Appearance Evaluation>
The appearance of the film obtained in the same manner as in the evaluation of the dielectric loss tangent was visually observed. When no cloudiness was observed, it was judged as ◯, and when cloudiness was observed, it was judged as ×.

<Tensile test>
A rectangular test piece having a width of 1 cm and a length of 5 cm was cut out from the film obtained in the same manner as in the evaluation of the dielectric tangent. A tensile test was performed using the obtained test piece and a tensile tester (EZ-test, manufactured by Shimadzu Corporation) under conditions of a chuck distance of 2 cm and a tensile speed of 1 mm/min to measure the tensile elongation. The tensile elongation was calculated according to the following formula.
Tensile elongation (%) = (chuck distance at break (cm) / 2 (cm) - 1) x 100
Regarding the tensile elongation, 40% or more was judged as ⊚, 30% or more but less than 40% was judged as ◯, and less than 30% was judged as x.

According to Examples 1 to 23, it is found that a photosensitive resin composition containing a polyamide resin having a structural unit of the specific structure represented by the above-mentioned formula (A1) and having a polymerizable group such as a methacryloyl group, and an oxime ester compound as a photosensitizer gives a resin film that exhibits good photosensitivity, has a low dielectric tangent, has a good appearance without cloudiness, and is excellent in tensile strength.
On the other hand, according to Comparative Example 1 and Comparative Example 2, it is found that a photosensitive resin composition containing a polyamide resin or a polyimide resin that does not contain a structural unit having the specific structure represented by the above-mentioned formula (A1) cannot form a resin film having a low dielectric tangent.

Claims (8)

Contains a resin (A) and a photosensitizer (C),
The resin (A) is
A polyimide resin (AI) derived from a diamine compound and a tetracarboxylic dianhydride, and a polyamic acid (A-II), and
(A-III ) is a polyamide resin derived from a diamine compound and a dicarboxylic acid compound or an amide-forming derivative of a dicarboxylic acid compound;
The resin (A) is represented by the following formula (A1-1):

(In formula (A1-1), R ^a1 is a hydroxy group, a carboxy group, or a halogen atom; R ^a2 is an aliphatic group having 1 to 20 carbon atoms, a hydroxy group, a carboxy group, a sulfonic acid group, or a halogen atom; Ar is a phenyl group which may be substituted with R ^a2 , or a naphthyl group which may be substituted with R ^a2 ; ma1 is an integer of 0 to 10; ma2 is an integer of 0 to 7; ma3 is an integer of 1 to 10; Y ^a1 is an organic group having 1 to 20 carbon atoms or a single bond; Y ^a2 is an organic group having 1 to 20 carbon atoms; na1 is 0 or 1, na2 is 0 or 1, and when na1 is 1, Ya1 is not a single bond .)
A photosensitive resin composition comprising a structural unit (a1) derived from a compound represented by the following formula: 2. The photosensitive resin composition according to claim 1, wherein the resin (A) has a radical polymerizable group on its molecular chain and the photosensitizer (C) is a photoradical polymerization initiator (C1), or the resin (A) has a cationic polymerizable group on its molecular chain and the photosensitizer (C) is a photocationic polymerization initiator ( C2 ). 3. The photosensitive resin composition according to claim 2 , wherein the resin (A) has a radically polymerizable group on its molecular chain, and the photoradical polymerization initiator (C1) is an oxime ester-based photopolymerization initiator. 3. The photosensitive resin composition according to claim 1, wherein a ratio of the number of moles of the structural unit (a1) to the number of moles of all structural units derived from the diamine compound in the resin (A) is 10 mol% or more and 100 mol% or less. A photosensitive dry film comprising a base film and a photosensitive layer formed on a surface of the base film, the photosensitive layer being made of the photosensitive resin composition according to any one of claims 1 to 4 . A method for producing a photosensitive dry film, comprising applying the photosensitive resin composition according to any one of claims 1 to 4 onto a substrate film to form a photosensitive layer. A lamination step of laminating a photosensitive layer made of the photosensitive resin composition according to any one of claims 1 to 4 on a substrate;
an exposure step of exposing the photosensitive layer to actinic rays or radiation in a position-selective manner;
and a developing step of developing the photosensitive layer after exposure to obtain a patterned resin film. the resin (A) includes the polyamic acid (A-II) or the polyamide resin (A-III ) including a structural unit derived from a dicarboxylic acid compound that can be synthesized by reacting a tetracarboxylic dianhydride with a monohydroxy compound;
The method for producing a patterned resin film according to claim 7, further comprising baking the patterned resin film to convert the polyamic acid (A-II) or the polyamide resin (A-III) containing a constitutional unit derived from a dicarboxylic acid compound that can be synthesized by a reaction between a tetracarboxylic dianhydride and a monohydroxy compound into a polyimide resin (A-I).