JP2022190618A - Photosensitive resin composition - Google Patents

Abstract

To provide a photosensitive resin composition that can be subjected to a photolithography process to form a patterned resin film with low dielectric loss tangents, a photosensitive dry film having a photosensitive layer composed 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.SOLUTION: A photosensitive resin composition contains a resin and a photosensitizer. The resin comprises at least one selected from the group consisting of a polyimide resin containing a constitutional unit derived from a diamine compound of a specific structure having an aromatic group, a polyamic acid, a polyamide resin, a polybenzoxazole resin, and a polybenzoxazole resin precursor.SELECTED DRAWING: None

Description

The present invention provides at least one selected from the group consisting of polyimide resins, polyamic acids, polyamide resins, polybenzoxazole resins, and polybenzoxazole resin precursors containing structural units that can be derived from a diamine compound having a specific structure. , a photosensitive resin composition containing a photosensitive agent, a photosensitive dry film having a photosensitive layer made of the photosensitive resin composition, a method for producing the photosensitive dry film described above, and the photosensitive resin composition described above and a method for manufacturing a patterned resin film using

Polyimide resins, polyamide resins, and polybenzoxazole resins have properties such as excellent heat resistance, mechanical strength, insulation, and low dielectric constant. It is widely used as an insulating material and a protective material in such electric and electronic parts.

2. Description of the Related Art In recent years, communication devices such as mobile phones have been using higher frequencies. Therefore, it is required that the insulating part for insulating the metal wiring of the communication equipment is also capable of handling 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 resin, polyamide resin, and polybenzoxazole resin, in order to further reduce transmission loss as a response to higher frequencies, further reduction in dielectric loss tangent in a high frequency band and further reduction in transmission loss A low dielectric constant is required.

In addition, when various devices and electronic substrates are manufactured, it is often necessary to form insulating materials and protective materials only at desired positions. Therefore, there is a demand for a photosensitive resin composition that exhibits a low dielectric loss tangent and a low dielectric constant and that can form a patterned resin film.

From the above requirements, for example, as a photosensitive resin composition capable of forming a patterned polyimide resin film, aromatics having a specific structure having a structural unit derived from 4,4'-bis(4-aminophenoxy)biphenyl A photosensitive resin composition containing a group polyamide resin and a photopolymerization initiator (see Patent Document 1, Examples), a polyimide precursor having an unsaturated double bond in the side chain, and a specific radical generation amount A photosensitive resin composition containing a photopolymerization initiator having an oxime structure has been proposed (see Patent Document 2).

WO2019/044874 WO2021/020463

When the photosensitive resin composition described in Patent Document 1 or Patent Document 2 is used, a patterned polyimide resin film having a relatively low dielectric loss tangent can be formed by applying a photolithographic method. On the other hand, the photosensitive resin composition described in Patent Document 1 is desired to further reduce the dielectric loss tangent of the formed polyimide resin film.

The present invention has been made in view of the above problems, and a photosensitive resin composition capable of forming a patterned resin film having a low dielectric loss tangent by applying a photolithography method, and the photosensitive resin composition The purpose of the present invention is to provide a photosensitive dry film having a photosensitive layer made of a material, a method for producing the above-mentioned photosensitive dry film, and a method for producing a patterned resin film using the above-mentioned photosensitive resin composition. and

The present inventors have found that in a photosensitive resin composition containing a resin and a photosensitive agent, a polyimide resin, a polyamic acid, a polyamide resin, a polybenzo The inventors have found that the above problems can be solved by using at least one selected from the group consisting of oxazole resins and polybenzoxazole resin precursors, 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。 A first aspect of the present invention comprises a resin (A) and a photosensitive agent (C),
The resin (A) is
A polyimide resin (A-I) 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
A diamine compound, which is an aromatic compound having two amino groups bonded to an aromatic ring and having a hydroxy group bonded to the carbon atom adjacent to the carbon atom bonded to the amino group on the aromatic ring, and a dicarboxylic At least one selected from the group consisting of a polybenzoxazole resin (A-IV) derived from an acid compound or an amide-forming derivative of a dicarboxylic acid compound, and a polybenzoxazole resin precursor (AV) ,
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, and R ^a2 is 1 to 20 carbon atoms. is an aliphatic group, a hydroxy group, a carboxy group, a sulfonic acid group, or a halogen atom, and Ar is a phenyl group optionally substituted with R ^a2 or a naphthyl group optionally substituted with R ^a2 , ma1 is an integer of 0 or more and 10 or less, ma2 is an integer of 0 or more and 7 or less, and ma3 is an integer of 1 or more and 10 or less.)
It is a photosensitive resin composition containing a structural unit derived from the compound represented by.

A second aspect of the present invention has a substrate film and a photosensitive layer formed on the surface of the substrate film, and the photosensitive layer is made of the photosensitive resin composition according to the first aspect. dry film.

A third aspect of the present invention is a method for producing a photosensitive dry film, comprising applying the photosensitive resin composition according to the first aspect on a base film to form a photosensitive layer.

A fourth aspect of the present invention is a lamination step 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 by position-selectively irradiating it with actinic rays or radiation;
and a developing step of developing the exposed photosensitive layer to obtain a patterned resin film.

According to the present invention, a photosensitive resin composition capable of forming a patterned resin film having a low dielectric loss tangent by applying a photolithography method, and a photosensitive layer comprising the photosensitive resin composition It is possible to provide a dry film, a method for producing the aforementioned photosensitive dry film, and a method for producing a patterned resin film using the aforementioned 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 contains a resin (A) and a photosensitive agent (C). The resin (A) is a polyimide resin (A-I) derived from a diamine compound and a tetracarboxylic dianhydride, and a polyamic acid (A-II), a diamine compound and a dicarboxylic acid compound, or an amide of a dicarboxylic acid compound. A polyamide resin (A-III) derived from a formable derivative, as well as having two amino groups bonded on an aromatic ring, at a carbon atom at a position adjacent to the carbon atom to which the amino group on the aromatic ring is bonded A polybenzoxazole resin (A-IV) derived from a diamine compound, which is an aromatic compound to which a hydroxy group is bonded, and a dicarboxylic acid compound or an amide-forming derivative of a dicarboxylic acid compound, and a polybenzoxazole resin precursor It contains at least one selected from the group consisting of (AV).
The above 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, and R ^a2 is 1 to 20 carbon atoms. is an aliphatic group, a hydroxy group, a carboxy group, a sulfonic acid group, or a halogen atom, and Ar is a phenyl group optionally substituted with R ^a2 or a naphthyl group optionally substituted with R ^a2 , ma1 is an integer of 0 or more and 10 or less, ma2 is an integer of 0 or more and 7 or less, and ma3 is an integer of 1 or more and 10 or less.)
Including structural units derived from the compound represented by.
When the resin (A) contains structural units derived from the compound represented by the formula (A1), a resin film having a low dielectric loss tangent in a 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) undergoes a polymerization reaction between the polymerizable groups. may be a so-called polymerization initiator that promotes the When the photosensitive resin composition contains a combination of a resin (A) having a polymerizable group, a compound other than the resin (A) having a polymerizable group, and a polymerization initiator as the photosensitive agent (C), the photosensitive The flexible resin composition is insolubilized in the developer by being cured by exposure to light. That is, a photosensitive resin composition containing a combination of a resin (A) having a polymerizable group, a compound other than the resin (A) having a polymerizable group, and a polymerization initiator as a photosensitive agent (C) is a negative It corresponds to the type of photosensitive resin composition.

From the viewpoint of good photolithographic properties, the resin (A) preferably has a polymerizable group on its molecular chain that can be polymerized by the action of the photosensitizer (C). As the polymerizable group, a radically polymerizable group and a cationic polymerizable group are typically preferred, and a radically polymerizable group is more preferred.
When the resin (A) has a polymerizable group, the resin (A) usually has a radically polymerizable group on its molecular chain, and the photosensitizer (C) is a radical photopolymerization initiator (C1), Alternatively, the resin (A) has a cationic polymerizable group on its molecular chain, and the photosensitizer (C) is a cationic photopolymerization initiator (C2).

The amount of the radically polymerizable group or the cationic polymerizable group in the resin (A) is not particularly limited as long as the object of the present invention is not impaired. The amount of the radically polymerizable group or the cationically polymerizable group in the resin (A) is, for example, 0.0005 mol/g or more and 0.0500 mol/g or less as the number of moles of the functional group with respect to the weight of the resin (A). It is preferably 0.001 mol/g or more and 0.0380 mol/g or less, and further preferably 0.0015 mol/g or more and 0.0028 mol/g or less. The amount of radically polymerizable groups or cationically polymerizable groups in resin (A) can typically be measured by NMR analysis.

Also, the photosensitive agent (C) may be a component that itself is solubilized in a developer by the action of light. For example, a compound having a naphthoquinonediazide group is solubilized in an alkaline developer by the formation of a carboxyl group upon exposure. When the photosensitive resin composition contains a photosensitive agent (C) that itself is solubilized in a developer by the action of light, the photosensitive resin composition is a positive type that is solubilized in the developer by being exposed to light. corresponds to the photosensitive resin composition of

A photosensitive resin composition containing the above resin (A) and a photosensitive agent (C) provides a patterned resin film with a low dielectric loss tangent by applying a photolithography method, and also provides a photosensitive resin composition It is possible to suppress the white turbidity of the resin film to be printed using a material, and to give the resin film excellent in mechanical properties such as tensile elongation.

The essential or optional components of the photosensitive resin composition are 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。 <Resin (A)>
As described above, the resin (A) is a polyimide resin (A-I) derived from a diamine compound and a tetracarboxylic dianhydride, a polyamic acid (A-II), a diamine compound, a dicarboxylic acid compound, or a dicarboxylic acid A polyamide resin (A-III) derived from an amide-forming derivative of an acid compound, and a position adjacent to the carbon atom to which the amino group on the aromatic ring binds, having two amino groups bound on the aromatic ring. A polybenzoxazole resin (A-IV) derived from a diamine compound, which is an aromatic compound having a hydroxyl group bonded to a carbon atom of a dicarboxylic acid compound, or an amide-forming derivative of a dicarboxylic acid compound (A-IV), and polybenzo It contains at least one selected from the group consisting of oxazole resin precursors (AV).
The above 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, and R ^a2 is 1 to 20 carbon atoms. is an aliphatic group, a hydroxy group, a carboxy group, a sulfonic acid group, or a halogen atom, and Ar is a phenyl group optionally substituted with R ^a2 or a naphthyl group optionally substituted with R ^a2 , ma1 is an integer of 0 or more and 10 or less, ma2 is an integer of 0 or more and 7 or less, and ma3 is an integer of 1 or more and 10 or less.)
Including structural units derived from the compound represented by.

Polyimide resin (A-I), polyamic acid (A-II), polyamide resin (A-III), polybenzoxazole resin (A-IV), and polybenzoxazole resin precursor (AV) are described below. explain.

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

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

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

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

In Formula (A1), 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. The organic group as R ^a2 may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms.
The number of carbon atoms in the aliphatic group as R ^a2 is preferably 1 or more and 12 or less, more preferably 1 or more and 6 or less.

Aliphatic groups for R ^a2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl. group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl chain alkyl groups such as group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group; vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1- Chain alkenyl groups such as 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; chloro methyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl Halogenated chain alkyl groups such as groups, heptafluoropropyl groups, perfluorobutyl groups, perfluoropentyl groups, perfluorohexyl groups, perfluoroheptyl groups, perfluorooctyl groups, perfluorononyl groups, and perfluorodecyl groups 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group, and 4-bromocyclohexyl group. Alkyl group; Hydroxy chain alkyl group such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, and 4-hydroxy-n-butyl group; 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group , and hydroxycycloalkyl groups such as 4-hydroxycyclohexyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n- Pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n- tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group, etc. chain alkoxy group; vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group, and 3-n-butenyloxy group chain alkenyloxy group; methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 3-methoxy-n-propyl group, 3 -ethoxy-n-propyl group, 3-n-propoxy-n-propyl group, 4-methoxy-n-butyl group, 4-ethoxy-n-butyl group, and 4-n-propoxy-n-butyl group, etc. Alkoxyalkyl group; methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 3-methoxy-n-propoxy group, 3-ethoxy - Alkoxyalkoxy such as 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 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-propoxy carbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyloxycarbonyl A chain alkyloxycarbonyl group such as a group; formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group, nonanoyloxy group, and aliphatic acyloxy groups such as decanoyloxy groups.

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 according to the structure of X. The value of ma3 is preferably 1 or more and 4 or less, 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 as X is preferably 2 or more and 80 or less, more preferably 6 or more and 50 or less. The organic group as X may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms. In addition, in the compound represented by formula (A1), two amino groups are each bonded to a carbon atom in the organic group as X.

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

When the organic group as X is an aliphatic group, the aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. When the organic group as X is an aliphatic group, the aliphatic group is preferably an aliphatic hydrocarbon group. When the organic group as X is an aliphatic group, the aliphatic group may be chain or cyclic, and may be a combination of a chain aliphatic group and a cyclic aliphatic group. good too. A chain aliphatic group may have a branch.

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

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

In formulas (11) to (15), Ar, R ^a1 , R ^a2 , ma1, ma2, and ma3 are the same as those in formula (A1). In Formula (13), ma4 and ma5 are each independently an integer of 0 or more and 4 or less. ma6 and ma7 are each independently an integer of 0 or more and 4 or less, and the sum of ma6 and ma7 is 1 or more and 8 or less. In Formula (14), ma8, ma9, and ma10 are each independently an integer of 0 or more and 4 or less. The sum of ma8, ma9, and ma10 is 0 or more and 10 or less. ma11, ma12, and ma13 are each independently an integer of 0 or more and 4 or less. The sum of ma11, ma12, and ma13 is 1 or more and 10 or less. In Expression (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 1 or more and 4 or less. is preferred.
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 ma11, ma12, and ma13 The sum is 1 or more, preferably 6 or less.
In formula (15), ma2 is preferably 0, ma14 and ma15 are each preferably 0, ma16 and ma17 are each preferably 0, 1, or 2, and the sum of ma16 and ma17 is 1 or more and 4 or less. is preferred.

In formulas (11) to (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. The divalent linking group includes 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-, groups in which two or more selected from these groups are combined, and the like. The number of carbon atoms in the linking group is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 6 or less. The aliphatic hydrocarbon group as a 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 methylene group, ethane-1,2-diyl group (ethylene group), ethane-1,1-diyl group, propane-1,3-diyl group, propane -1,2-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6- diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane- 1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group group, octadecane-1,18-diyl group, nonadecane-1,19-diyl group, icosane-1,20-diyl group, ethene-1,2-diyl group (vinylene group), propene-1,3-diyl group , ethyne-1,2-diyl group, and propyne-1,3-diyl group.

Preferred examples of the linking group include an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, an alkynylene group having 2 to 6 carbon atoms, and an alkynylene group having 1 to 6 carbon atoms. alkyleneoxy group, alkenyleneoxy group having 2 to 6 carbon atoms, alkynyleneoxy group having 2 to 6 carbon atoms, alkylenethio group having 1 to 6 carbon atoms, alkenylene having 2 to 6 carbon atoms thio group, alkynylenethio group having 2 to 6 carbon atoms, alkyleneamino group having 1 to 6 carbon atoms, alkenyleneamino group having 2 to 6 carbon atoms, alkynyleneamino group 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。 Since the formed resin film exhibits a low dielectric loss tangent and good mechanical properties, the compound represented by the formula (A1) has 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), and Y ^a1 is an organic group, 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.)
is preferably a compound represented by

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

In formula (A1-1), na2 is preferably 1, na1 and na2 are both 1, and Y ^a1 is more preferably an organic group. In this case, due to the high degree of steric freedom of the ether bond, when forming a cured film using a photosensitive resin composition, the structural unit represented by the formula (A1-1) is favorably It is considered that packing is easy and a cured film having excellent mechanical properties, thermal properties, electrical properties, etc. is 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 formula (A1) above.
When the resin (A) is a polyimide resin (A-I) and a polyamic acid (A-II), all configurations derived from the diamine compound in the polyimide resin (AI) and the polyamic acid (A-II) The ratio of the number of moles of structural units derived from the compound represented by formula (A1) to the number of moles of units is preferably 10 mol% or more and 100 mol% or less, more preferably 15 mol% or more and 100 mol% or less, 20 mol % or more and 100 mol % or less is more preferable.

Other diamine compounds are represented by the following formula (A2).
H ₂ NA ¹ -NH ₂ (A2)
(In formula (A2), A ¹ represents a divalent organic group. However, the divalent organic group as A ¹ is X, Ar, R ^a1 , and R ^a2 in formula (A1) above. It does not correspond to the constituent group.)

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

The lower limit of the number of carbon atoms in the organic group as A1 is preferably ² , more preferably 6, and the upper limit is preferably 50, more preferably 30.
A ¹ may be an aliphatic group, but is preferably an organic group containing one or more aromatic rings.

When A ¹ is an organic group containing one or more aromatic rings, the organic group may be one aromatic group itself, and two or more aromatic groups are aliphatic hydrocarbon groups and halogenated aliphatic group hydrocarbon group, or a group bonded via a bond containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. The bonds containing a heteroatom such as an oxygen atom, a sulfur atom and a nitrogen atom included in A ¹ include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, - O—, —CO—, —SO—, —SO ₂ —, —S—, and —S—S— and the like, and —COO—, —O—, —CO—, and —S— are preferred.

^The aromatic ring in A1 that bonds to the amino group is preferably a benzene ring. When the ring bonded to the amino group in A ¹ 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.
Moreover, the aromatic ring contained in A ¹ may be an aromatic heterocyclic ring.

When A ¹ is an organic group containing an aromatic ring, the organic group is a group represented by the following formulas (21) to (24) from the viewpoint of improving the electrical properties and mechanical properties of the resin film to be formed. is preferably at least one of

In (21) to (24), R ¹¹¹ is a hydrogen atom, a fluorine atom, a carboxy group, a sulfonic acid group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, and a halogen having 1 to 4 carbon atoms one selected from the group consisting of alkyl groups. In formula (24), Q ¹ is a 9,9'-fluorenylidene group, or formulas: -C ₆ H ₄ -, -C ₆ H ₄ -C ₆ H ₄ -, -OC ₆ H ₄ -C 6H4-O-, -O- _{C6H4 -} CO _{- C6H4 -} O-, -O _{- C6H4 -} C( _CH3 ) _{2 - C6H4} -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- , _-CH2- , -O- _{C6H4 -} SO2 _{- C6H4 -} O-, -C( _CH3 ) _{2 - C6H4} -C( _CH3 ) _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 ) from the group consisting of groups represented by ₃ -O-, -O-(CH ₂ ) ₄ -O-, -O-(CH ₂ ) ₅ -O-, and -O-(CH ₂ ) ₆ -O- One selected is shown.

—C ₆ H ₄ — in the examples of Q ¹ is a phenylene group, preferably an m-phenylene group and a p-phenylene group, more preferably a p-phenylene group. -C ₁₀ H ₆ - is a naphthalene diyl group, naphthalene-1,2-diyl group, naphthalene-1,4-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl and naphthalene-2,7-diyl groups are preferred, and naphthalene-1,4-diyl groups and naphthalene-2,6-diyl groups are more preferred.

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 from the viewpoint of improving the electrical properties of the resin film to be formed. Atoms or trifluoromethyl groups are particularly preferred.

Q ¹ in formula (24) is -C ₆ H ₄ -C ₆ H ₄ -, -OC ₆ H ₄ -C ₆ H ₄ from the viewpoint of the electrical and mechanical properties of the resin film to be formed. —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 -SO ₂ -C ₆ H ₄ -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 -O-C ₆ H ₄ -C ₆ H ₄ -O-,- O—C ₆ H ₄ —C(CH ₃ ) ₂ —C ₆ H ₄ —O— is more preferred, and is represented by —O—C ₆ H ₄ —C ₆ H ₄ —O— and —C ₆ H ₄ — is Groups in which both are p-phenylene groups are particularly preferred.

When an aromatic diamine compound is used as another diamine compound represented by formula (A2), for example, aromatic diamine compounds shown below can be preferably used.
That is, the aromatic diamine compounds 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(trifluoro methyl)biphenyl, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 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′-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2 , 2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2′-bis[N-(3-amino benzoyl)-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, 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, 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-diamibenzoic acid, 3,4-diaminobenzoic acid, 4-aminophenyl 4-aminobenzoic acid, 1,3-bis(4-anilino)tetramethyldisiloxane, 1,4-bis( 3-aminopropyldimethylsilyl)benzene, ortho-tolysine sulfone, and the like. Among them, 4,4'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(4-aminophenoxy)biphenyl, and 3,3'-bis (4-Aminophenoxy)biphenyl is preferred.

In addition, as A1, ^a chain-like aliphatic group and/or a silicon atom-containing group optionally having an aromatic ring can be employed. As such a silicon atom-containing group, typically the groups shown below can be used.

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

A diamine having an oxyalkylene group can also be preferably used as another diamine compound represented by formula (A2). Preferred examples of the oxyalkylene group include an ethyleneoxy group, a propyleneoxy group ₍ --C ₍ CH.sub.3)--CH.sub.2--O-- _, --CH.sub.2-- _{C ( CH.sub.3} )--O--, or --CH.sub.2CH.sub.2CH ₂ -O-).
A diamine having an oxyalkylene group may contain a combination of two or more oxyalkylene groups. When the diamine having an oxyalkylene group contains two or more oxyalkylene groups, the two or more oxyalkylene groups may be included in the diamine blockwise or randomly.
The diamines having oxyalkylene groups are preferably free of cyclic groups and more preferably free of aromatic groups.
Specific examples of diamines having an oxyalkylene group include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, and Jeffamine (manufactured by HUNTSUMAN). (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 ® D-2000, and Jeffamine® D-4000, and 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine and 1-(1- (1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine and the like.

A dimer diamine compound is also preferable as the diamine compound, since it is easy to form a cured product having a low dielectric constant and a low dielectric loss tangent in a 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 unsaturated fatty acids. Industrial manufacturing processes for producing dimer acids are largely 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. Industrially obtained dimer acids are mainly composed of dibasic acids with 36 carbon atoms obtained by dimerizing unsaturated fatty acids with 18 carbon atoms such as oleic acid, linoleic acid and linolenic acid. The industrially obtained dimer acid is a monomeric acid having 18 carbon atoms, a trimer acid having 54 carbon atoms, and other polymerized fatty acids having 20 to 54 carbon atoms, depending on the degree of purification. , may contain
As the dimer diamine compound, a diamine compound represented by the following formula (31) is preferable.

In formula (31), e, f, g, and h are each integers of 0 or greater. e+f is an integer of 6 or more and 17 or less, and g+h is 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 exists in one molecule of the compound represented by formula (31).

Further, a compound represented by the following formula (32) is preferable as the diamine compound represented by the formula (31) because a cured product having excellent elongation can be formed.

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

Further, a tetracarboxylic dianhydride represented by the following formula (34) is obtained by reacting a diamine compound represented by the formula (31) with an acid halide derived from trimellitic anhydride. It is also preferable to use a 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 Equation (34), i, j, k, and l are each integers of 0 or greater. i+j is an integer of 6 or more and 17 or less, and k+l is 8 or more and 19 or less. In formula (34), the wavy line represents a carbon-carbon single bond or a carbon-carbon double bond.

As described above, the resin (A) incorporated in the photosensitive resin composition may have a polymerizable group on its molecular chain that can be polymerized by the action of the photosensitive agent (C) from the viewpoint of photosensitivity. good. As the polymerizable group, a radically polymerizable group and a cationic polymerizable group are typically preferred, and a radically polymerizable group is more preferred.

The bonding position of the radically polymerizable group or the cationic polymerizable group in the molecular chains of the polyimide resin (AI) and polyamic acid (A-II) is not particularly limited.
Radically polymerizable groups typically include groups containing ethylenically unsaturated double bonds. As the ethylenically unsaturated double bond-containing group, alkenyl group-containing groups including alkenyl groups such as vinyl groups and allyl groups are preferred, and (meth)acryloyl group-containing groups are more preferred.
Typical cationic polymerizable groups include epoxy group-containing groups, oxetanyl group-containing groups, vinyloxy group-containing groups and the like. Among these, an epoxy group-containing group and a vinyloxy group-containing group are preferred. The epoxy group-containing group is preferably an alicyclic epoxy group-containing group or a glycidyl group. The alicyclic epoxy group is an aliphatic cyclic group in which two carbon atoms as adjacent ring-constituting atoms in the aliphatic cyclic group are bonded through an oxygen atom. That is, an alicyclic epoxy group has an epoxy group containing a three-membered ring consisting of two carbon atoms and one oxygen atom on an aliphatic ring.

The above radically polymerizable group and cationic polymerizable group are preferably bonded to aromatic rings in the molecular chains of the polyimide resin (AI) and polyamic acid (A-II).
Therefore, the divalent organic group A ¹ in formula (A2) is, for example, on the aromatic ring of the aromatic groups represented by the above formulas (21) to (24), further a radically polymerizable group, or It may be a group to which a cationic polymerizable group is bonded.

Preferable examples of the radically polymerizable group bonded to the aromatic ring in the molecular chain of the polyimide resin (A-I) and the polyamic acid (A-II) include the following formula (A-a) or the following formula (A- A group represented by b) which does not correspond to a vinyloxy group-containing group can be mentioned.
-(A ⁰¹ ) _na -R ⁰¹ (Aa)
-(A ⁰¹ ) _na -R ⁰² -A ⁰² -R ⁰¹ (Ab)

In formulas (Aa) and (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;

Suitable specific examples of the radically polymerizable group that bonds to the aromatic ring in the main chain include:
—OR ⁰³ ,
—O—CH ₂ CH ₂ —OR ⁰³ ,
—O—CH ₂ CH ₂ CH ₂ —OR ⁰³ ,
—O—CH ₂ CH ₂ CH ₂ CH ₂ —OR ⁰³ ,
—CO—O—CH ₂ CH ₂ —OR ⁰³ ,
—CO—O—CH ₂ CH ₂ CH ₂ —OR ⁰³ ,
—CO—O—CH ₂ CH ₂ CH ₂ CH ₂ —OR ⁰³ ,
-O _- ^CH2CH2 _- NH-R03,
-O _{- CH2CH2CH2 -} NH- ^R03 ,
-O _{- CH2CH2CH2CH2 -} NH _- ^R03 ,
-CO-O _- ^CH2CH2 _- NH-R03,
-CO-O _{- CH2CH2CH2 -} NH- ^R03 ,
-CO _- O _{- CH2CH2CH2CH2 -} ^R03 ,
—NH—R ⁰³ ,
—NH—CH ₂ CH ₂ —OR ⁰³ ,
-NH _{- CH2CH2CH2 -} ^OR03 ,
^-NH _{- CH2CH2CH2CH2 - OR03} ,
—CO—NH—CH ₂ CH ₂ —OR ⁰³ ,
—CO—NH—CH ₂ CH ₂ CH ₂ —OR ⁰³ ,
^-CO -NH _{- CH2CH2CH2CH2 - OR03} ,
-NH _- ^CH2CH2 _- NH-R03,
-NH _{- CH2CH2CH2 -} NH- ^R03 ,
-NH _{- CH2CH2CH2CH2 -} NH _- ^R03 ,
-CO _- NH- ^CH2CH2 _- NH-R03,
—CO—NH—CH ₂ CH ₂ CH ₂ —NH—R ⁰³ , and
A group represented by -CO-NH-CH ₂ CH ₂ CH ₂ CH ₂ -NH-R ⁰³ can be mentioned. ^R03 in these groups is an allyl group or a (meth)acryloyl group.

It is preferably bonded to an aromatic ring in the molecular chains of polyimide resin (AI) and polyamic acid (A-II). Suitable examples of the polyimide resin (A-I) and the cationically polymerizable group that binds to the aromatic ring in the molecular chain of the polyamic acid (A-II) include a vinyloxy group and the following formulas (Ac) to formula Groups represented by (Ah) can be mentioned.
-(A ⁰¹ ) _na -R ⁰⁴ (Ac)
-(A ⁰¹ ) _na -R ⁰² -R ⁰⁵ (Ad)
-(A ⁰¹ ) _na -R ⁰² -(CO) _nb -A ⁰³ -R ⁰⁴ (Ae)
-(A ⁰¹ ) _na -R ⁰² -(CO) _nb -A ⁰³ -R ⁰⁷ -R ⁰⁵ (Af)
-(A ⁰¹ ) _na -R ⁰² -OR ⁰⁶ (Ag)
-(A ⁰¹ ) _na -R ⁰² -(CO) _nb -A ⁰³ -R ⁰⁷ -OR ⁰⁶ (Aj)

In formulas (Ac) to (Ah), 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;

Suitable specific examples of the cationically polymerizable group that binds to the aromatic ring in the main chain include:
-R ⁰⁷ ,
-O _- ^CH2CH2 _- R07,
-O _{- CH2CH2CH2 -} ^R07 ,
^-O _{- CH2CH2CH2CH2 - R07} ,
-CO-O _- ^CH2CH2 _- R07,
-CO-O _{- CH2CH2CH2 -} ^R07 ,
-CO _- O _{- CH2CH2CH2CH2 -} ^R07 ,
-NH _- ^CH2CH2 _- R07,
-NH _{- CH2CH2CH2 -} ^R07 ,
^-NH _{- CH2CH2CH2CH2 - R07} ,
-CO-NH _- ^CH2CH2 _- R07,
—CO—NH—CH ₂ CH ₂ CH ₂ —R ⁰⁷ , and
A group represented by -CO-NH-CH ₂ CH ₂ CH ₂ CH ₂ -R ⁰⁷ can be mentioned. R ⁰⁷ in these groups is a vinyloxy group, a glycidyloxy group, an epoxycyclopentyl group, an epoxycyclohexyl group, or an epoxycycloheptyl group.

When A ¹ in formula (A2) is an aromatic group having a radically 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 dianhydride)
As the tetracarboxylic dianhydride, any tetracarboxylic dianhydride conventionally used in the production of polyamic acid and polyimide resin can be used without particular limitation.
Tetracarboxylic dianhydrides include compounds represented by the following formula (A3). Tetracarboxylic dianhydrides may be used singly or in combination of two or more.

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

In formula (A3), A ² is a tetravalent organic group having 6 to 50 carbon atoms, and the acid anhydride group represented by two -CO-O-CO- in formula (A3) In addition, it may have one or more substituents.
Preferable examples of the substituent include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and the number of carbon atoms. Fluorinated alkoxy groups of 1 to 6 are preferred. In addition, the compound represented by formula (a1-1) may contain a carboxy group and a carboxylic acid ester group in addition to the acid anhydride group.
When the substituent is a fluorinated alkyl group or fluorinated alkoxy group, it is preferably a perfluoroalkyl group or perfluoroalkoxy group.
The same applies to the substituents described above and one or more substituents that the aromatic group described later may have on the aromatic ring.

The number of carbon atoms constituting ^A2 is more preferably 8 or more, still more preferably 12 or more. In addition, the number of carbon atoms constituting ^A2 is more preferably 40 or less, even more preferably 30 or less. ^A2 may be an aliphatic group, an aromatic group, or a group combining these structures. ^A2 may contain a halogen atom, an oxygen atom, a nitrogen atom and a sulfur atom in addition to the carbon atom and the hydrogen atom. When ^A2 contains an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, the nitrogen atom, or the sulfur atom is a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N=N-, -CH= may be included in A ¹ as a group selected from N—, —COO—, —O—, —CO—, —SO—, —SO ₂ —, —S—, and —S—S—; ^A group selected from —O—, —CO—, —S—, and is more preferably included in A1.

The tetracarboxylic dianhydride represented by the formula (A3) is an aliphatic tetracarboxylic dianhydride having two dicarboxylic anhydride groups that bind to an aliphatic group, but also binds to an aromatic group. It may be an aromatic tetracarboxylic dianhydride having at least one dicarboxylic anhydride 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. Examples of aliphatic tetracarboxylic dianhydrides having no alicyclic structure include 1,2,3,4-tetracarboxylic dianhydrides (e.g., Rikacid BT-100, manufactured by Shin Nippon Rika Co., Ltd.). mentioned.
Aliphatic tetracarboxylic dianhydrides having an alicyclic structure include cyclobutanetetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4 ,5-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride (for example , Enehyde (registered trademark) CpODA, manufactured by Eneos), 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), 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2 ,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione (eg, Rikashid TDA-100, manufactured by Shin Nippon Rika Co., Ltd.).

Examples of the aromatic tetracarboxylic dianhydride having two dicarboxylic anhydride groups bonded to the aromatic group represented by the formula (A3) include pyromellitic dianhydride, 1,4-bis(3 ,4-dicarboxyphenoxy)benzene dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4' -biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, trimellitic acid (3,4-dicarboxyphenyl) dianhydride, 1 , 2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4 ,9,10-perylenetetracarboxylic dianhydride, 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 (eg, Rikashid TMEG100, manufactured by Shin Nippon Rika Co., Ltd.), and 1 ,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (eg, 10BTA, manufactured by Kurogane Kasei Co., Ltd.) and the like.
Among these aromatic tetracarboxylic dianhydrides, 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride is easily formed into a cured product with excellent electrical properties. substance, 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 (for example, Rikacid TMEG100, manufactured by Shin Nippon Rika Co., Ltd.), and 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (eg, 10BTA, manufactured by Kurogane Kasei Co., Ltd.) is preferred.

In addition, the aromatic tetracarboxylic dianhydride is biphenyltetracarboxylic dianhydride in terms of suppressing warping of the cured film of the photosensitive resin composition and good photolithography properties of the photosensitive resin composition. is also preferred.
Biphenyltetracarboxylic dianhydrides include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2' ,3,3′-biphenyltetracarboxylic dianhydride, and 3,3′,4,4′-biphenyltetracarboxylic dianhydride is preferred.

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

In formulas (a3-2) and (a3-3) above, R ^a01 , R ^a02 and R ^a03 are each an optionally halogen-substituted aliphatic group, an oxygen atom, a sulfur atom, one or more Any aromatic group through a divalent element, or a divalent group composed of 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). Compounds represented by formula (a3-2) include 2,2-bis(3,4-dicarboxyphenoxy)propane dianhydride, bis(3,4-dicarboxyphenoxy)methane dianhydride, 1, 1-bis(3,4-dicarboxyphenoxy)ethane dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene, 2,2-bis(3,4-dicarboxyphenoxy)hexafluoropropane dianhydride, and 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride.

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

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 polyamic acid (A-II) preferably have a radically polymerizable group or a cationically polymerizable group on their molecular chains.
Therefore, the tetravalent organic group A ² in formula (A3) may be a group represented by formulas (a3-5) to (a3-7) below.

R ^a01 , R ^a02 , and R ^a03 in formulas (a3-5) to (a3-7) are , R ^a01 , R ^a02 , and R ^a03 .
R ^a06 in formulas (a3-5), (a3-6), and (a3-7) is a radically polymerizable group or a cationically polymerizable group. Examples of the radically polymerizable group and the cationically polymerizable group include the groups described above.
Tetracarboxylic dianhydride itself is highly reactive. For example, epoxy groups readily react with carboxylic anhydride groups. For this reason, A ² is a structural unit corresponding to a structural unit derived from a tetracarboxylic dianhydride, which is a group represented by formulas (a3-5) to (a3-7), is added to a polyimide resin (A- I) or polyamic acid (A-II), after synthesizing the polyimide resin (AI) or polyamic acid (A-II), polyimide resin (AI) or polyamic acid (A It is preferable to introduce a radically polymerizable group or a cationically polymerizable group onto the molecular chain of -II).

Examples of reactions for introducing a radically polymerizable group or a cationically polymerizable group include:
1) Etherification of a halogen atom bonded to an aromatic ring in the molecular chain of polyimide resin (AI) or polyamic acid (A-II) with an alcohol compound having a radically polymerizable group or a cationically polymerizable group reaction,
2) Ester of hydroxy group bonded to aromatic ring in molecular chain of polyimide resin (AI) or polyamic acid (A-II) and carboxylic acid halide having radically polymerizable group or cationically polymerizable group chemical reaction,
3) Esterification of a carboxy group bonded to an aromatic ring in the molecular chain of polyimide resin (AI) or polyamic acid (A-II) with an organic halide having a radically polymerizable group or a cationically polymerizable group reaction, and
4) N- between an amino group bonded to an aromatic ring in the molecular chain of polyimide resin (AI) or polyamic acid (A-II) and an organic halide having a radically polymerizable group or a cationically polymerizable group Substitution reaction etc. are mentioned. The reaction for introducing a radically polymerizable group or a cationically polymerizable group is not limited to these reactions.

In addition, for example, a hydroxy group protected by a protecting group such as an acetyl group, a carboxylic acid ester group such as a methoxycarbonyl group, an amino group protected by a protecting group such as a tert-butoxycarbonyl group, etc. are on the aromatic ring. After synthesizing the polyimide resin (A-I) or polyamic acid (A-II) having a hydroxy group, a carboxy group, or an amino group, etc. on the aromatic ring by deprotecting by a well-known method Polyimide resin (AI) or polyamic acid (A-II) can be obtained.

(Method for producing polyimide resin (A-I) and polyamic acid (A-II))
The method for producing the polyimide resin (AI) and the polyamic acid (A-II) is not particularly limited. The polyimide resin (A-I) described above is typically obtained by reacting the above diamine compound with a tetracarboxylic dianhydride to obtain a polyamic acid (A-II), and then the polyamic acid ( A-II) can be prepared by imidating.
When producing the polyamic acid (A-II), each of the tetracarboxylic dianhydride and the diamine may be used alone or in combination of two or more.
Polyimide resin (A-I) and polyamic acid (A-II) may have a radically polymerizable group or a cationically polymerizable group, as described above. A radically polymerizable group or a cationically polymerizable group may be introduced onto the molecular chain after synthesis of the polyamic acid (A-II) or after synthesis of the polyimide resin (AI).
After synthesizing the polyamic acid (A-II) or after synthesizing the polyimide resin (AI), a radically polymerizable group or a cationically polymerizable group is introduced onto the molecular chain of the polyamic acid or the polyimide resin (A). In that case, the introduction method is not particularly limited.
A typical example of a method for introducing a radically polymerizable group or a cationically polymerizable group onto a molecular chain is a polyamic acid (A-II) having a functional group such as a hydroxy group, an amino group, or a carboxyl group, or a polyimide resin ( AI), a carboxylic acid having a radically polymerizable group, a carboxylic acid halide having a radically polymerizable group, alcohols having a radically polymerizable group, phenols having a radically polymerizable group, and amines having a radically polymerizable group , halogenated compounds having a radically polymerizable group, carboxylic acids having a cationically polymerizable group, carboxylic acid halides having a cationically polymerizable group, alcohols having a cationically polymerizable group, phenols having a cationically polymerizable group, cations Examples include a method of reacting an amine having a polymerizable group or a halogen compound having a cationically polymerizable group by a known method such as condensation reaction using a well-known condensing agent or Williamson's etherification reaction.

In view of the ease of reaction and availability of a compound having a radically polymerizable group or a cationically polymerizable group, some or all of the carboxyl groups of the polyamic acid (A-II) are replaced with alcohols 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 radically polymerizable group or an alcohol having a cationically polymerizable group, the modified polyamic acid (A-II) is is imidized by a method such as heating. In this case, imidization by ring closure proceeds while alcohols having a radically polymerizable group or alcohols having a cationically polymerizable group are eliminated.
The condensation reaction method is not particularly limited. For example, a carboxyl group of polyamic acid (A-II) and an alcohol having a radically polymerizable group or an alcohol having a cationically polymerizable group can be condensed in the presence of a condensing agent such as a carbodiimide compound. can.
Further, the carboxyl group possessed by the polyamic acid (A-II) is reacted with a halogenating agent such as thionyl chloride to form a halogenocarbonyl group (carboxylic acid halide group), and then having a halogenocarbonyl group and a radically polymerizable group. Alcohols or alcohols having a cationic polymerizable group may be reacted.

Alcohols having a radically polymerizable group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 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, 2-hydroxy-3-cyclohexyl Oxypropyl (meth)acrylate, 3-hydroxypropan-2-yl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxy Diols mono( meth)acrylate; glycerin-1,3-di(meth)acrylate, glycerin-1,2-di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta (Meth) acrylates of polyols having a hydroxyl group such as (meth) acrylate; hydroxyalkyl group-substituted (meth) acrylamides such as N-(2-hydroxyethyl) (meth) acrylamide; (hydroxymethyl) vinyl ketone, and (2- hydroxyl group-containing ketones such as vinyl ketone; 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 , elalide linoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and erucyl alcohol.
In the specification of the present application, (meth)acrylate means both acrylate and methacrylate.
Examples of alcohols having a cationic polymerizable group include ethylene glycol monoglycidyl ether, 1,3-propanediol monoglycidyl ether, propylene glycol monoglycidyl ether, 1,4-butanediol monoglycidyl ether, 1,5-pentanediol monoglycidyl ether. Monoglycidyl ethers of glycols such as glycidyl ether, 1,6-hexanediol monoglycidyl ether, diethylene glycol monoglycidyl ether, and dipropylene glycol monoglycidyl ether, glycidyl alcohol, and 3,4-epoxy-1-butanol. Epoxyalkanes substituted with hydroxy groups are mentioned.

The amounts of the tetracarboxylic dianhydride and the diamine compound used in synthesizing the polyamic acid (A-II) are not particularly limited, but 0.8 mol of the diamine compound is used per 1 mol of the tetracarboxylic dianhydride. It is preferable to use 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.
Moreover, the weight average molecular weight of the obtained polyamic acid (A-II) may be appropriately set according to its use. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent weight average molecular weight by GPC (gelvameation chromatography). The weight average molecular weight of the polyamic acid (A-II) is, for example, 5000 or more, preferably 15000 or more, more preferably 250000000 or more in terms of polystyrene conversion, from the viewpoint of obtaining a cured film having good mechanical properties. On the other hand, the weight average molecular weight of the obtained polyamic acid (A-II) is, for example, 100,000 or less, preferably 80,000 or less, more preferably 50,000 or less in terms of polystyrene, from the viewpoint of improving developability.
The weight-average molecular weight may be set to the value described above by adjusting the compounding amounts of the tetracarboxylic dianhydride and the diamine compound, and the reaction conditions such as the solvent and the reaction temperature.

The reaction between the tetracarboxylic dianhydride and the diamine compound is usually carried out in an organic solvent. The organic solvent used for the reaction of the tetracarboxylic dianhydride and the diamine compound is an organic solvent that can dissolve the tetracarboxylic dianhydride and the diamine compound and that does not react with the tetracarboxylic dianhydride and the diamine compound. is not particularly limited. An organic solvent can be used individually or in mixture of 2 or more types.

Examples of organic solvents used in the reaction between the tetracarboxylic dianhydride and the diamine compound include 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-dimethylisobutyamide , methoxy-N,N-dimethylpropionamide, butoxy-N,N-dimethylpropionamide, N-methylcaprolactam, N,N'-dimethylpropyleneurea, N,N,N',N'-tetramethylurea, and nitrogen-containing polar solvents such as pyridine; dimethyl sulfoxide; sulfolane; Esters such as 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; Ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethers such as 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 singly or in combination of two or more.

Among these organic solvents, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Nitrogen-containing polar solvents such as diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, and N,N,N',N'-tetramethylurea are preferred.

The temperature at which the tetracarboxylic dianhydride and the diamine compound are reacted is not particularly limited as long as the reaction proceeds well. Typically, the reaction temperature between the tetracarboxylic dianhydride and the diamine compound is preferably −5° C. or higher and 120° C. or lower, more preferably 0° C. or higher and 80° C. or lower, and particularly preferably 0° C. or higher and 50° C. or lower. . The time for reacting the tetracarboxylic dianhydride and the diamine compound varies depending on the reaction temperature, but is typically preferably 30 minutes or more and 20 hours or less, more preferably 1 hour or more and 8 hours or less, and 2 hours. More than 6 hours or less is particularly preferable.

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

In addition, when the tetracarboxylic dianhydride and/or diamine compound has a radical polymerizable group-containing group containing an ethylenically unsaturated double bond, the purpose of preventing cross-linking between the ethylenically unsaturated double bonds during the reaction Also, a small amount of a polymerization inhibitor may be used. Polymerization inhibitors include phenols such as hydroquinone, 4-methoxyphenol, tert-butylpyrocatechol, and bis-tert-butylhydroxytoluene, and phenothiazine. The amount of the polymerization inhibitor used is preferably 0.01 mol % or more and 5 mol % or less with respect to the number of moles of ethylenically unsaturated double bonds.

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

When imidization is performed by heating, the heating may be performed on a solution or suspension of the polyamic acid (A-II), or may be performed on the solid polyamic acid (A-II). good.
When imidization is performed by heating a solution of polyamic acid (A-II), it is preferable to perform heating while removing water produced as a by-product during imidization.
The heating conditions for imidization are not particularly limited as long as the polyamic acid (A-II) or polyimide resin (AI) does not decompose and imidization proceeds satisfactorily.
When the solution of polyamic acid (A-II) is heated, the heating temperature is typically preferably 80° C. or higher and 220° C. or lower, more preferably 100° C. or higher and 200° C. or lower, and 120° C. or higher and 180° C. or lower. is particularly preferred. When the solid polyamic acid (A-II) is heated, the heating temperature is typically preferably 180° C. or higher and 400° C. or lower, more preferably 200° C. or higher and 350° C. or lower.
Although the heating time depends on the heating temperature, it is typically preferably from 1 hour to 24 hours, more preferably from 2 hours to 12 hours.

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

Examples of imidizing agents include acetic anhydride, propionic anhydride, benzoic anhydride, trifluoroacetic anhydride, acetyl chloride, tosyl chloride, mesyl chloride, ethyl chloroformate, triphenylphosphine and dibenzimidazolyl disulfide, dicyclohexylcarbodiimide, carbodiimidazole, Dehydrating agents such as 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline and oxalic acid N,N'-disuccinimidyl ester, 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 and other basic compounds.

[Polyamide resin (A-III)]
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 described for the polyimide resin (AI) and polyamic acid (A-II) can be used.
As described above, the resin (A) incorporated in the photosensitive resin composition may have a polymerizable group on its molecular chain that can be polymerized by the action of the photosensitive agent (C) from the viewpoint of photosensitivity. good. As the polymerizable group, a radically polymerizable group and a cationic polymerizable group are typically preferred, and a radically polymerizable group is more preferred.

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

(Dicarboxylic acid compound and amide-forming derivative of dicarboxylic acid compound)
As the dicarboxylic acid compound, various dicarboxylic acid compounds conventionally used as raw materials for polyamide resins can be used without particular limitation.
As the dicarboxylic acid compound, for example, aliphatic dicarboxylic acids having 2 to 50 carbon atoms and aromatic carboxylic acids having 8 to 50 carbon atoms are preferable.

Amide-forming derivatives of dicarboxylic acid compounds include dicarboxylic acid halides of dicarboxylic acid compounds and activated dicarboxylic acid compounds. As the dicarboxylic acid halide, dicarboxylic acid chloride and dicarboxylic acid bromide are preferred, and dicarboxylic acid chloride is more preferred. Active groups derived from carboxyl groups in the activated dicarboxylic acid compounds include phenoxycarbonyl group, (2-thioxo-2,3-dihydrobenzoxazol-3-yl)carbonyl group, 1H-1,2,3 -triazol-1-ylcarbonyl group, 1H-benzotriazol-1-yloxycarbonyl group, 1H-imidazol-1-ylcarbonyl group, succinimidyloxycarbonyl group, and 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 is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group. group, trifluoromethyl group, chlorine atom, bromine atom, iodine atom, phenoxy group, and nitro group.

Suitable examples of dicarboxylic acid compounds include adipic acid, sebacic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4- naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, and alkyl, alkoxy or halogen substituted products thereof.
As the alkyl group as a substituent, an alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group as a substituent, an alkoxy group having 1 or more and 4 or less carbon atoms is preferable.
When the aforementioned 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.

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

Pyromellitic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 4,4′-oxydiphthalic dianhydride, which are suitable examples of aromatic tetracarboxylic dianhydrides 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetra carboxylic acid dianhydride, 2,2′,3,3′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4, 4′-diphenyl sulfide tetracarboxylic dianhydride, trimellitic acid (3,4-dicarboxyphenyl) dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, [5,5′-(1 ,4-phenylene)bisnorbornane]-2,2′,3,3′-tetracarboxylic dianhydride (eg, Enehyde (registered trademark) BzDA, manufactured by Eneos), 1,3,3a,4,5, 9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione (for example, Rikacid TDA-100, manufactured by Shin Nippon Rika Co., Ltd.), 2, 2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenylcarbonyloxy)biphenyl dianhydride, 2,6-bis (3,4-dicarboxyphenylcarbonyloxy)naphthalene dianhydride, 1,2-bis(3,4-dicarboxyphenylcarbonyloxy)ethane dianhydride (for example, Rikacid TMEG100, manufactured by Shin Nippon Rika Co., Ltd.), and Dicarboxylic acid compounds corresponding to 1,10-bis(3,4-dicarboxyphenylcarbonyloxy)decane dianhydride (eg, 10BTA, manufactured by Kurogane Kasei Co., Ltd.) include these aromatic tetracarboxylic dianhydrides. A dicarboxylic acid compound obtained by reacting an alcohol represented by R ^a21 —OH or an amine represented by R ^a21 —NH ₂ with a compound is 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 located on adjacent carbon atoms in the dicarboxylic acid compound. X ^a is -O- or -NH.

The number of carbon atoms in the monovalent organic group as R ^a21 is preferably 1 or more and 20 or less, more preferably 1 or more and 16 or less, still more preferably 1 or more and 12 or less, and particularly preferably 1 or more and 8 or less.
The monovalent organic group as R ^a21 includes an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 2 or more carbon atoms. 20 or less alkoxyalkyl groups, 3 to 20 carbon atom alkoxyalkoxyalkyl groups, 4 to 20 carbon atom (meth)acryloyloxyalkyl groups, 5 to 20 carbon atom (meth)acryloyloxyalkyl groups Examples include an oxyalkyl group, a glycidyloxyalkyl group having 4 to 20 carbon atoms, and a glycidyloxyalkyloxyalkyl group having 5 to 20 carbon atoms.

In the dicarboxylic acid compound having two pairs of a carboxy group and a group represented by —CO—X ^a —R ^a21 , the position of the carboxy group and the position of —CO—X ^a —R ^a21 are There are isomers that differ in the position of the group. As the above dicarboxylic acid compound, one kind of such isomers may be used alone, or two or more kinds thereof may be used in combination.
As an example, with respect to a dicarboxylic acid compound corresponding to pyromellitic dianhydride, a compound represented by the following formula (a4-a1) and a compound represented by the following formula (a4-a2) are isomers. exist. Further, with regard to the dicarboxylic acid compound corresponding to 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, the isomers are a compound represented by the following formula (a4-b1) and the following formula ( There are a compound represented by a4-b2) and a compound represented by the following formula (a4-b3).
In formulas (a4-a1), (a4-a2), and formulas (a4-b1) to (a4-b3) below, X ^a and R ^a21 are as described above.

Dicarboxylic acid compounds corresponding to the tetracarboxylic dianhydrides represented by the above formulas (a3-2) to (a3-4) include the following formulas (a4-2a) to (a4-2c), formula Compounds represented by formulas (a4-3a) to (a4-3c) and formulas (a4-4a) to (a4-4c) are exemplified. In formulas (a4-2a) to (a4-2c), formulas (a4-3a) to (a4-3c), and formulas (a4-4a) to (a4-4c), R ^a01 to R ^a05 are , and formulas (a3-2) to (a3-4). In formulas (a4-2a) to (a4-2c), formulas (a4-3a) to (a4-3c), and formulas (a4-4a) to (a4-4c), X ^a and R ^a21 is as described above.

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

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; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono Glycols such as ethyl 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. Ethers; alcohols having the aforementioned radically polymerizable group; and alcohols having the aforementioned cationically polymerizable group.

The reaction between the tetracarboxylic dianhydride and the above monohydroxy compound or monoamino compound is performed in the same manner as the reaction between the tetracarboxylic dianhydride and the diamine compound described above as the method for producing polyamic acid (II). It can be carried out. The reaction between the tetracarboxylic dianhydride and the above monohydroxy compound or monoamino compound includes organic It may be carried out in the presence of a base. These bases may be used alone, or two or more of them may be used simultaneously.
The amount of the monohydroxy compound or monoamino compound used is preferably 1.8 mol or more and 2.2 mol or less, more preferably 2 mol or more and 2.1 mol or less, relative to 1 mol of the tetracarboxylic dianhydride.
A dicarboxylic acid compound is obtained by reacting a tetracarboxylic dianhydride with the above monohydroxy compound or monoamino compound. In the production of a dicarboxylic acid compound, depending on the production conditions, only one of the dicarboxylic anhydride groups reacts with the monohydroxy compound or monoamino compound to produce a monocarboxylic acid compound having a dicarboxylic anhydride group, or to form a tetracarboxylic acid compound. Part of the carboxylic acid dianhydride reacts with moisture in the reaction system to produce a tetracarboxylic acid compound or a tricarboxylic acid compound.
As long as the resin can be obtained, a dicarboxylic acid compound containing at least one selected from the above monocarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds can be used for the production of the polyamide resin (A-III). can.
When the dicarboxylic acid compound contains at least one selected from the above monocarboxylic acid compound, tricarboxylic acid compound, and tetracarboxylic acid compound as an impurity, the above monocarboxylic acid compound as an impurity in the dicarboxylic acid compound The content of at least one selected from , tricarboxylic acid compounds, and tetracarboxylic acid compounds is preferably 30% by mass or less, more preferably 10% by mass or less, relative to the mass of the dicarboxylic acid compound containing the mass of impurities. , is more preferably 5% by mass or less, and particularly preferably 1% by mass or less.

(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) includes, for example, a method of condensing a diamine compound and a dicarboxylic acid compound with a condensing agent. Condensing agents include, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'- and disuccinimidyl carbonate.

Another preferred method is a method of condensing a dicarboxylic acid compound or an acid halide of a dicarboxylic acid compound with a diamine compound in the presence of a base. In this method, if necessary, a condensing agent may be used together with the base.
Acid halides are preferably acid chlorides and acid bromides, more preferably acid chlorides.
Bases include pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, 1,4-azabicyclo[2,2,2]octane and the like.
Condensing agents include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinyl methylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(benzotriazol-1-yl)-N,N, N′,N′-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate, and 4-(4,6-dimethoxy-1,3 ,5-triazin-2-yl)4-methoxymorpholium chloride hydrate and the like.

Specifically, a dicarboxylic acid compound or an acid halide of a dicarboxylic acid compound and a diamine compound are mixed in an organic solvent in the presence of the above base, for example, at -20°C or higher and 150°C or lower, preferably at 0°C. The reaction is carried out at 50° C. or less for 30 minutes or more and 24 hours or less, preferably 1 hour or more and 4 hours or less.
The amount of the base to be used is an amount that can be easily removed, and from the viewpoint that a high molecular weight product can be easily obtained, the amount of the base is 2 to 4 times the mole number of the dicarboxylic acid compound or the acid halide of the dicarboxylic acid compound. is preferably

It is also preferable to convert the carboxy group of the dicarboxylic acid compound into an active group, and then condense the compound having the active group derived from the dicarboxylic acid compound with the diamine compound. Active groups derived from carboxyl groups in the activated dicarboxylic acid compounds include phenoxycarbonyl group, (2-thioxo-2,3-dihydrobenzoxazol-3-yl)carbonyl group, 1H-1,2,3 -triazol-1-ylcarbonyl group, 1H-benzotriazol-1-yloxycarbonyl group, 1H-imidazol-1-ylcarbonyl group, succinimidyloxycarbonyl group, and 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 is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group. group, trifluoromethyl group, chlorine atom, bromine atom, iodine atom, phenoxy group, and nitro group.

[Polybenzoxazole resin (A-IV) and polybenzoxazole resin precursor (AV)]
The polybenzoxazole resin precursor (AV) has two amino groups bonded on the aromatic ring, and a hydroxy group is bonded to the carbon atom adjacent to the carbon atom to which the amino group on the aromatic ring is bonded. It is a resin derived from a diamine compound, which is an aromatic compound containing a dicarboxylic acid compound, and a dicarboxylic acid compound or an amide-forming derivative of a dicarboxylic acid compound.
Such a polybenzoxazole resin precursor (AV) has a hydroxy group on the aromatic ring 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 closure of polybenzoxazole resin precursor (AV).
The diamine compound and the dicarboxylic acid compound are 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) 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, and R ^a2 is 1 to 20 carbon atoms. is an aliphatic group, a hydroxy group, a carboxy group, a sulfonic acid group, or a halogen atom, and Ar is a phenyl group optionally substituted with R ^a2 or a naphthyl group optionally substituted with R ^a2 , ma1 is an integer of 0 or more and 10 or less, ma2 is an integer of 0 or more and 7 or less, and ma3 is an integer of 1 or more and 10 or less.)
Including a structural unit derived from the compound represented by.

When the resin (A) is a polybenzoxazole resin (A-IV) and a polybenzoxazole resin precursor (AV), the polybenzoxazole resin (A-IV) and the polybenzoxazole resin precursor ( The ratio of the number of moles of 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 AV) is preferably 10 mol% or more and 100 mol% or less, 15 mol % or more and 100 mol % or less is more preferable, and 20 mol % or more and 100 mol % or less is even more preferable.

（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。） Other diamine compounds are represented by the following formula (A2-1).

(In formula (A2-1), A ³ represents a tetravalent organic group containing one or more aromatic rings. However, the divalent organic group as A ³ is X , Ar, R ^a1 and R ^a2 In the compound represented by formula (A2-1), the two amino groups are each an aromatic group in the organic group as A ³ In the compound represented by formula (A2-1), the two hydroxy groups are each bonded to the carbon atom adjacent to the carbon atom to which the amino group in the aromatic group is bonded.)

As described above, the resin (A) incorporated in the photosensitive resin composition may have a polymerizable group on its molecular chain that can be polymerized by the action of the photosensitive agent (C) from the viewpoint of photosensitivity. good. As the polymerizable group, a radically polymerizable group and a cationic polymerizable group are typically preferred, and a radically polymerizable group is more preferred.

(Dicarboxylic acid compound and amide-forming derivative of dicarboxylic acid compound)
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 (AV))
The polybenzoxazole resin precursor (AV) can be produced by reacting the aforementioned diamine compound and dicarboxylic acid compound in the same manner as the method for producing the polyamide resin (A-III).
Polybenzoxazole resin (A-IV) is obtained by ring-closing the polybenzoxazole resin precursor (AV) thus obtained by heating. The heating temperature is, for example, preferably 120° C. or higher and 350° C. or lower, more preferably 150° C. or higher and 350° C. or lower.
Alternatively, a polybenzoxazole resin (A-IV) can be obtained by chemically closing the ring by allowing a dehydrating agent to act on the polybenzoxazole resin precursor (AV).

The purpose is to improve the storage stability of the photosensitive resin composition, further improve the mechanical properties of the film formed using the photosensitive resin composition, improve the reproducibility of polymerization when producing the resin (A), etc. As such, the main chain end of the resin (A) may be blocked with a terminal blocking agent. Terminal blockers include monoamines, acid anhydrides, monocarboxylic acids, monoacid halides, monoactive ester compounds, and the like.
A known compound can be used as the monoamine used for terminal blocking. Examples of monoamines include aromatic monoamines such as aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 3-hydroxyaniline, 4-hydroxyaniline, 3-aminothiophenol, and 4-aminothiophenol. and aliphatic monoamines having 3 to 20 carbon atoms which may have a branched structure such as hexylamine and octylamine, monoamines having an alicyclic structure such as cyclohexylamine, trimethoxyaminopropylsilane, and Aminosilanes such as triethoxyaminopropylsilane can be mentioned.
Among the acid anhydrides, monoacid halides, and monoactive ester compounds used as terminal blocking agents, acid anhydrides are preferred. As the acid anhydride, known acid anhydrides and derivatives thereof can be used. For example, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, xo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and derivatives thereof.
The introduction rate of the end blocking agent in the resin (A) is the number of moles of all monomers from the viewpoint of excellent mechanical properties of the film formed using the photosensitive resin composition and excellent developability of the photosensitive resin composition. is preferably 40 mol % or less, more preferably 20 mol % or less, and even more preferably 10 mol % or less.

<Monomer compound (B)>
When the resin (A) has a radically polymerizable group, the photosensitive resin composition contains a monomer compound having an ethylenically unsaturated double bond as the monomer compound (B) together with the polyimide resin (A). good too. Such a monomer compound (B) may be a monofunctional monomer compound or a polyfunctional monomer compound, 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, 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-hydroxy Propyl 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, half (meth)acrylate of a phthalic acid derivative, and the like. These monofunctional photopolymerizable monomers can be used alone or in combination of two or more.

Examples of polyfunctional monomer compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol. Di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6 - hexane glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane di(meth)acrylate ) acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(3-(meth)acryloyloxypropyl) ether, glycerin di(meth)acrylate, glycerin ethylene oxide (EO) Tri(meth)acrylate of adduct, tri(meth)acrylate of glycerin propylene oxide (PO) adduct, tri(meth)acrylate of glycerin EO/PO coadduct, tri(meth)acrylate of trimethylolpropane ethylene EO adduct Acrylate, tri(meth)acrylate of trimethylolpropane PO adduct, tri(meth)acrylate of trimethylolpropane EO/PO coadduct, tri(meth)acrylate of trimethylolethane EO adduct, trimethylolethane PO adduct tri(meth)acrylate of trimethylolethane EO/PO co-adduct tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate , pentapentaerythritol undeca ( meth)acrylate, pentapentaerythritol dodeca(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 1,3,5-adamantanetriol di(meth)acrylate, 1,3,5-adamantanetriol tri(meth)acrylate, 1,4-cyclohexanedimethanol di(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2- Bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy) Phenyl]fluorene, 9,9-bis[4-(2-(meth)acryloyloxypropoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)-3 , 5-dimethylphenyl]fluorene, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalate diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly( meth)acrylates, urethane (meth)acrylates (i.e. tolylene diisocyanate), reaction products of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate, tri((meth)acryloyloxyethyl)isocyanurate , methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, polyfunctional monomer compounds such as condensates of polyhydric alcohol and N-methylol(meth)acrylamide, and triacryl formal. These polyfunctional monomer compounds can be used singly or in combination of two or more.

In addition, urethane (meth)acrylates described in JP-B-48-41708, JP-B-50-6034, and JP-A-51-37193; -43191, and polyester (meth) acrylates described in JP-B-52-30490; Epoxy (meth) acrylates which are reaction products of epoxy resin and (meth) acrylic acid; JP 2008- Compounds described in paragraphs [0254] to [0257] of 292970; polyfunctional (meth)obtained by reacting a polyfunctional carboxylic acid with a compound having an epoxy group and an ethylenically unsaturated group such as glycidyl (meth)acrylate. ) Acrylate; JP 2010-160418, JP 2010-129825, and a compound having two or more groups having an ethylenically unsaturated bond having a fluorene ring, described in JP 4364216, etc. and cardo resin; unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, and JP-B-1-40336; vinyl phosphonic acid compounds described in JP-A-2-25493 compounds containing perfluoroalkyl groups described in JP-A-61-22048; Japan Adhesive Association, vol. 20, No. 7, 300-308 (1984) are also preferably used.

Among these monomer compounds having an ethylenically unsaturated double bond, trifunctional or higher polyfunctional monomer compounds are preferable, and tetrafunctional The above polyfunctional monomer compounds are more preferable, and polyfunctional monomer compounds having a functionality of 5 or more are more preferable.

When the resin (A) has a vinyloxy group-containing group as the cationically polymerizable group, the photosensitive resin composition may contain a vinyl ether compound as the 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 the 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 the object of the present invention is not impaired. The content of the monomer compound (B) in the photosensitive resin composition is 0.1 parts by mass or more and 50 parts by mass when the mass of the photosensitive resin composition excluding the mass of the solvent (S) described later is 100 parts by mass. The amount is 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.

<Photosensitizer (C)>
The photosensitive resin composition contains a type of photosensitive agent (C) corresponding to the type of resin (A). When the resin (A) has a radically polymerizable group on its molecular chain, or the photosensitive resin composition contains a monomer compound (B) having a radically polymerizable group together with the resin (A), the photosensitive agent (C) As a photoradical polymerization initiator (C1) is used. 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 radical photopolymerization initiator (C1) and the cationic photopolymerization initiator (C2) are not particularly limited, and conventionally known photopolymerization initiators can be used.

Specific examples of the radical photopolymerization initiator (C1) include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl ]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-1-{4-[ 4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one , 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl )-butan-1-one, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-2-(benzoyloximeimino)-1-propanone, 1-phenyl-1,2-butadione-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxy carbonyl)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), (9-ethyl-6-nitro-9H-carbazole-3 -yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- yl]-, 1-(0-acetyloxime), 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (Irgacure OXE01, manufactured by BASF Japan), N CI-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, 2-isoamyl 4-dimethylaminobenzoate, 4 - ethyl 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, β-chloroanthraquinone, 1,2-benzanthraquinone, 2,3-diphenyl anthraquinone, anthrone, benzantrone, dibenzsuberone, methylene anthrone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o- chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4' -dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, 4-hydroxybenzophenone, 4-phenylbenzophenone, fluorenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, 2-hydroxy -2-methylpropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, 2-phenylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy -3-(3,4-dimethyl-9-oxo-9H-thioxanthene-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-methoxy Phenyl)-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)styryl Phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, 4- Benzoyl-4′-methyl-diphenylsulfide, 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 -propene aminium chloride monohydrate, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenyl sulfone and the like. These radical photopolymerization initiators (C1) can be used alone or in combination of two or more.
From the viewpoint of good sensitivity, the radical photopolymerization initiator (C1) is preferably an oxime ester photopolymerization initiator.

Among the radical photopolymerization initiators (C1), oxime ester compounds are preferred from the viewpoint of the sensitivity of the photosensitive resin composition.
As the oxime ester compound, a compound having a partial structure represented by the following formula (c1) is preferable.

（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 optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group,
* is a bond. )

Photocationic polymerization initiators (C2) typically include onium salts. The photocationic polymerization initiator (C2) includes oxonium salts, ammonium salts, phosphonium salts, sulfonium salts and iodonium salts, preferably sulfonium salts and iodonium salts, more preferably sulfonium salts.

The content of the radical photopolymerization initiator (C1) or the cationic photopolymerization initiator (C2) in the photosensitive resin composition is not particularly limited as long as the photosensitive resin composition has desired photolithography properties. The content of the photoradical polymerization initiator (C1) or the photocationic polymerization initiator (C2) in the photosensitive resin composition is typically the mass of the resin (A) and the mass of the monomer compound (B). is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 1 to 10 parts by mass.

The photosensitive resin composition may also contain a quinonediazide group-containing compound (C3) as a photosensitizer (C). The photosensitive resin composition containing the quinonediazide group-containing compound (C3) is a positive photosensitive resin composition that is solubilized in an alkaline developer by exposure.

The quinonediazide group-containing compound (C3) can be appropriately selected from compounds having a quinonediazide group conventionally blended in various positive photosensitive resin compositions. The quinonediazide group-containing compound (C3) may be used alone or in combination of two or more.

The quinonediazide group-containing sulfonic acid used as the quinonediazide group-containing compound (C3) is not particularly limited, but examples include naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4- naphthoquinonediazide sulfonic acid such as sulfonic acid; orthoanthraquinone diazide sulfonic acid, etc.; The ester compound of a quinonediazide group-containing sulfonic acid, preferably naphthoquinonediazide sulfonic acid, is well soluble in a solvent commonly used when the photosensitive resin composition is used as a solution. When these compounds are used as the quinonediazide group-containing compound (C3) and blended with the quinonediazide group-containing compound (C3), a highly sensitive positive photosensitive resin composition can be easily obtained.

The method for producing the ester compound as the quinonediazide group-containing compound (C3) is not particularly limited, and for example, a quinonediazide group-containing sulfonic acid is added as a sulfonyl chloride such as naphthoquinone-1,2-diazide-sulfonyl chloride. and condensing in a solvent such as dioxane in the presence of an alkali such as triethanolamine, alkali carbonate, or alkali hydrogencarbonate to effect complete or partial esterification.

The content of the quinonediazide group-containing compound (C3) is preferably within the following ranges from the viewpoint of the sensitivity of the photosensitive resin composition. The lower limit is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the 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, relative to 100 parts by mass of the resin (A).

<Organic solvent (S)>
The photosensitive resin composition may contain an organic solvent (S) for the purpose of adjusting coatability. The type of organic solvent (S) is not particularly limited as long as the resin (A) and other components are well dissolved.

Specific examples of the organic solvent (S) include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methyl- 2-pyrrolidone, N-ethyl-2-pyrrolidone, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylisobutyamide, 3-methoxy-N,N-dimethylpropionamide, Nitrogen-containing polar solvents such as 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylpropionamide, N,N-dimethylisobutyramide, N,N-dimethylpropylene urea; acetone, methyl ethyl ketone, methyl isobutyl ketone, Ketones such as 2-heptanone, 3-heptanone, diisobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl- γ-butyrolactone, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, isopentyl acetate, n-pentyl formate, n-butyl propionate, isopropyl butyrate, Ethyl butyrate, n-butyl butyrate, methyl methoxychlorate, ethyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy methyl propionate, 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 esters such as acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate; diacetone alcohol, and 3-methyl-3- alcohols such as methoxybutanol; Glycol ethers such as recall 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; fragrances 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; sulfoxides of.

The amount of the 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 a suspension or a solution, preferably a solution. Typically, the organic solvent (S) is used so that the solid content concentration of the photosensitive resin composition is preferably 15% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 45% by mass or less. be done.

<Other ingredients>
The photosensitive resin composition may contain various additives other than the components described above, if necessary. Additives include colorants, dispersants, sensitizers, adhesion promoters, polymerization inhibitors, antioxidants, UV absorbers, anti-coagulants, antifoaming agents, surfactants, imidization accelerators, adhesion Nitrogen-containing heterocyclic compounds as improvers, silane coupling agents, and the like can be mentioned. In addition, the photosensitive resin composition may contain various fillers or reinforcing materials as necessary.

A known compound can be used as the sensitizer. Sensitizers include, for example, bis(dimethylamino)benzophenone, bis(diethylamino)benzophenone, diethylthioxanthone, N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-4-methyl Coumarin, N-phenylmorpholine, and derivatives thereof.

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

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

The nitrogen-containing heterocyclic compound coordinates with and stabilizes the metal surface, thereby improving the adhesion of the film formed using the photosensitive resin composition to the metal surface. A known compound can be used as the nitrogen-containing heterocyclic compound. Nitrogen-containing intercompounds include, for example, imidazole, pyrazole, indazole, carbazole, triazole, pyrazoline, pyrazolidine, tetrazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid, and derivatives thereof. Specific examples of preferred nitrogen-containing hetero-compounds from the viewpoint of coordination with metals include 1H-benzotriazole, 4-methyl-1H-methylbenzotriazole, 5-methyl-1H-methylbenzotriazole, 4-carboxy- triazoles such as 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 It is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 3% by mass or less, relative to the mass of the resin (A).

By adding the silane coupling agent to the photosensitive resin composition, the adhesion of the film formed using the photosensitive resin composition to a substrate or the like can be improved. A known compound can be used as the silane coupling agent. Silane coupling agents include, 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, reaction product of 3-aminopropyltrimethoxysilane and acid anhydride, reaction product of 3-aminopropyltriethoxysilane and acid anhydride, etc. be done.
Acid anhydrides to be reacted with 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane include succinic anhydride, maleic anhydride, nadic anhydride, 3-hydroxyphthalic anhydride, pyromellitic acid di anhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2′,3,3′-benzophenonetetracarboxylic dianhydride, and 4,4′-oxydiphthalic dianhydride etc.

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

By adding a surfactant to the photosensitive resin composition, the coating property of the photosensitive resin composition is improved, and the wettability of the photosensitive resin composition with the substrate is improved. A known compound can be used as the surfactant. Examples of surfactants include fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.

The amount of the surfactant used is preferably 0.001% by mass or more and 1% by mass or less with respect to the mass of the 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 accelerator. The cyclization accelerator is a polyamic acid (A-II) or a polyamide resin (A-III) containing structural units derived from a dicarboxylic acid compound that can be synthesized by reacting a tetracarboxylic dianhydride with a monohydroxy compound. , promotes the formation of a polyimide resin or a polybenzoxazole resin by cyclization of the polybenzoxazole resin precursor (AV).
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 benzoxazole resin by cyclization using the photosensitive resin composition are improved. improves. 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 the object of the present invention is not impaired. The amount of the additives not described above may be adjusted appropriately within the range of, for example, 0.001% by mass or more and 60% by mass or less based on the mass of the solid content of the photosensitive resin composition. , preferably 0.01% by mass or more and 5% by mass or less.

<Method for preparing photosensitive resin composition>
A photosensitive resin composition can be prepared by uniformly mixing the above-described essential components and, if necessary, optional components in desired amounts. A mixing method is not particularly limited. For the purpose of removing foreign substances in the photosensitive resin composition, it is preferable to filter the photosensitive resin composition with a filter.

≪Photosensitive dry film≫
A 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 aforementioned photosensitive resin composition.

As the substrate film, one having light transmittance is preferable. Specific examples thereof include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, etc., but polyethylene terephthalate (PET) film is preferred in that it has an excellent balance between light transmittance and breaking strength.

A photosensitive dry film is produced by applying the aforementioned photosensitive resin composition onto a substrate film to form a photosensitive layer.
When forming the photosensitive layer on the base film, an applicator, bar coater, wire bar coater, roll coater, curtain flow coater, etc. are used to form a layer having a thickness of preferably 0.5 μm after drying on the base film. The photosensitive resin composition is applied to a thickness of 300 μm or more, more preferably 1 μm or more and 300 μm or less, particularly preferably 3 μm or more and 100 μm or less, and dried.

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

<<Method for producing patterned resin film>>
A lamination step of laminating a photosensitive layer made of the aforementioned photosensitive resin composition on a substrate;
an exposure step of exposing the photosensitive layer by position-selectively irradiating it with actinic rays or radiation;
A patterned resin film can be produced by a method including a developing 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 conventionally known substrates can be used. can be done. A silicon substrate, a glass substrate, or the like can also be used as the substrate.

The photosensitive layer is laminated on the substrate, for example, as follows. That is, a photosensitive layer having a desired thickness is formed by applying a liquid photosensitive resin composition onto a substrate and removing the solvent by heating. The thickness of the photosensitive layer is not particularly limited as long as a resist pattern to be a template 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 or more and 300 μm or less, particularly preferably 1 μm or more and 150 μm or less, and most preferably 3 μm or more and 100 μm or less.
Alternatively, the aforementioned photosensitive dry film may be applied onto a substrate and a photosensitive layer may be laminated onto the substrate.

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

Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, and the like can be used as radiation sources. Radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, gamma rays, electron beams, proton beams, neutron beams, ion beams, and the like. Although the dose of radiation varies depending on the composition of the photosensitive resin composition, the film thickness of the photosensitive layer, and the like, it is 100 mJ/cm ² or more and 10000 mJ/cm ² or less when using an ultra-high pressure mercury lamp, for example.

Next, the exposed photosensitive layer is developed according to a conventionally known method, and unnecessary portions are dissolved and removed to form a resin film patterned into a predetermined shape. At this time, a developer is used according to the components contained in the photosensitive resin composition. When the photosensitive resin composition contains a resin (A) having an alkali-soluble group such as polyamic acid (A-II), or when the photosensitive resin composition contains a quinonediazide group-containing compound (C3), An alkaline aqueous solution is used as the developer. The photosensitive resin composition contains a resin (A) having a radically polymerizable group or a cationically polymerizable group, and contains a component that is soluble in an alkaline aqueous solution or a component that is solubilized in an alkaline aqueous solution by exposure. If the organic solvent (S) is not present or is contained only in a small amount, the above-mentioned organic solvent (S) can be used as the developer.

Alkaline developers include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, and methyldiethylamine. , dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (tetramethylammonium hydroxide), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1, Aqueous solutions of alkalis such as 5-diazabicyclo[4,3,0]-5-nonane can be used. Further, an aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the above alkalis can be used as a developer.

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

After development, washing is performed for 30 seconds or more and 90 seconds or less as needed, and the patterned resin film is dried using an air gun, an oven, or the like. Thus, a resin film patterned into a desired shape is formed on the surface of the substrate. The cleaning solvent is not particularly limited. As an example, water, alcohols, etc. can be used as a washing solvent in the case of alkali development. When developing with an organic solvent, the (S) organic solvent can be used as long as solvent shock does not occur.

The resin film contains a polyamic acid (A-II), a polyamide resin (A-III) containing structural units derived from a dicarboxylic acid compound that can be synthesized by the reaction of a tetracarboxylic dianhydride and a monohydroxy compound, or a polybenzo When the oxazole resin precursor (AV) is contained, after development, if necessary, the developed coating film is baked to react with the tetracarboxylic dianhydride and the monohydroxy compound. Polyamide resin (A-III) or polyamic acid (A-II) containing structural units derived from dicarboxylic acid compounds that can be synthesized can be converted into polyimide resin (A), or polybenzoxazole resin precursor (AV) may be converted to polybenzoxazole resin (A-IV).
The baking temperature is as described above for resin (A). Moreover, the baking is preferably performed in an inert gas atmosphere such as nitrogen or argon from the viewpoint of preventing oxidation of the cured film and obtaining a cured film having good mechanical properties.

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

[EXAMPLES] Hereafter, although an Example demonstrates this invention in detail, the scope of this invention is not limited to these Examples.

In Examples 1 to 11 and Comparative Examples 1 and 2, DA1 to DA6 below 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). To the resulting solution were added 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. After the addition, the solution was stirred at room temperature for 16 hours to give the di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid.

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

The resulting 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)), 0.05% by mass of a polymerization inhibitor (Irganox 1010 (BASF Japan)) with respect to the mass of the polyamide resin, and 0.02% by mass of a surfactant ( Polyflow No. 77 (Kyoeisha Chemical Co., Ltd.)) and 3% by mass of N-[3-(triethoxysilyl)propyl]phthalamide relative to the mass of the polyamide resin were added to obtain a photosensitive resin composition. .

[Example 2]
4,4'- A polyamide resin which is a polycondensate of di-2-methacryloyloxyethyl ester of oxydiphthalic acid, the above DA1 and DA4, and a photosensitive resin composition containing the polyamide resin were obtained.

[Example 3]
4,4'- A polyamide resin which is a polycondensate of di-2-methacryloyloxyethyl ester of oxydiphthalic acid, the above DA1 and DA4, and a photosensitive resin composition containing the polyamide resin were obtained.

[Example 4]
4,4'- A polyamide resin which is a polycondensate of di-2-methacryloyloxyethyl ester of oxydiphthalic acid, the above DA1 and DA4, and a photosensitive resin composition containing the polyamide resin were obtained.

[Example 5]
4,4'- A polyamide resin which is a polycondensate of di-2-methacryloyloxyethyl ester of oxydiphthalic acid, the above DA1 and DA4, and a photosensitive resin composition containing the polyamide resin were obtained.

[Example 6]
4,4'- A polyamide resin which is a polycondensate of di-2-methacryloyloxyethyl ester of oxydiphthalic acid, the above DA1 and DA4, and a photosensitive resin composition containing the polyamide resin were obtained.

[Example 7]
4,4'- A polyamide resin which is a polycondensate of di-2-methacryloyloxyethyl ester of oxydiphthalic acid, the above DA1 and DA4, and a photosensitive resin composition containing the polyamide resin were obtained.

[Example 8]
4,4'- A polyamide resin which is a polycondensate of di-2-methacryloyloxyethyl ester of oxydiphthalic acid, the above DA1 and DA4, and a photosensitive resin composition containing the polyamide resin were obtained.

[Example 9]
di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid and di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid , a polyamide resin which is a polycondensate with the above DA2, and a photosensitive resin composition containing the polyamide resin were obtained.

[Example 10]
Di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic acid and the above A polyamide resin which is a polycondensation product of No. DA7 and a photosensitive resin composition containing the polyamide resin were obtained.

[Example 11]
4,4'- A polyamide resin which is a polycondensation product of di-2-methacryloyloxyethyl ester of oxydiphthalic acid, the above DA3 and DA4, and a photosensitive resin composition containing the polyamide resin were obtained.

[Example 12]
15.57 g of DA1 as the diamine component, 6.43 g of DA6, and 250 g of NMP were added to a three-necked flask. The contents of the flask were then stirred to dissolve DA1 and DA6 in the NMP. Then, 40 g of 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride (BPADA) is added to the solution in the flask, and the reaction solution in the flask is stirred at room temperature for 24 hours. was doing After that, 0.88 g of 5-norbornene-2,3-dicarboxylic anhydride was added as a terminal blocking agent to the reaction liquid, and the reaction liquid was stirred at room temperature for 4 hours to obtain a polyamic acid.
In the formulas below, the numbers on the bottom right of parentheses indicate the molar ratio (mol%) of each structural unit in the resin.
<Polyamic acid generation>

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 stirred reaction solution was dropped into 5 kg of water to form a precipitate. The precipitate that formed was collected by filtration. The collected precipitate was washed with 2 kg of water three times and then dried under reduced pressure at 50° C. to obtain a polyimide resin having a carboxyl group and having structural units represented by the following formula.
<Imidation>

A three-necked flask was charged with the obtained polyimide resin having a carboxyl group, 8.25 g of 2-hydroxyethyl methacrylate, and 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, and the reaction solution was stirred at room temperature for 6 hours.
The stirred reaction solution was dropped into 2 kg of methanol to form a precipitate. The precipitate that formed was collected by filtration. The collected precipitate was washed with 2 kg of methanol three times and then dried under reduced pressure at 50° C. to obtain a polyimide resin having a methacryloyl group at the end of a side chain and having a structural unit represented by the following formula.
The obtained polyimide resin was subjected to ¹ H-NMR measurement, and imidization was confirmed by the disappearance of the peak corresponding to the amide bond. It was confirmed that it was introduced into the polyimide resin.
<Introduction of methacryloyl group>

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

[Example 13]
To 31.02 g (0.10 mol) of 4,4′-oxydiphthalic dianhydride was added 52.05 g (0.10 mol) of 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride. 10 mol), and a polyamide resin and a photosensitive resin composition were obtained in the same manner as in Example 1.

[Example 14]
Except for changing 31.02 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride to 29.42 g (0.10 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride obtained a polyamide resin and a photosensitive resin composition in the same manner as in Example 1.

[Example 15]
To 31.02 g (0.10 mol) of 4,4′-oxydiphthalic dianhydride was added 39.04 g (0.10 mol) of 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane dianhydride. 075 mol) and 5.45 g (0.025 mol) of pyromellitic dianhydride were used to obtain a polyamide resin and a photosensitive resin composition in the same manner as in Example 1.

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

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

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

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

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

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

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

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

[Comparative Example 1]
Di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic dianhydride in the same manner as in Example 1, except that the diamine compound was changed to 36.84 g (0.1 mol) of the above DA4. and a polyamide resin which is a polycondensate with the above DA4, and a photosensitive resin composition containing the polyamide resin.

[Comparative Example 2]
Di-2-methacryloyloxyethyl ester of 4,4'-oxydiphthalic dianhydride in the same manner as in Example 13, except that the diamine compound was changed to 20.02 g (0.1 mol) of the above DA5. and a polyamide resin which is a polycondensate with the above DA5, and a photosensitive resin composition containing the polyamide resin.

Using the obtained photosensitive resin compositions of Examples 1 to 23, Comparative Example 1, and Comparative Example 2, according to the following methods, evaluation of photosensitivity, evaluation of dielectric loss tangent of the resin film, and appearance of the resin film Evaluation and a tensile test of the resin film were performed. These evaluation results are shown in Table 1.

<Photosensitivity evaluation>
After the photosensitive resin composition was applied onto the copper substrate by a spin coater, it was baked at 80° C. for 300 seconds to obtain a coating film having a thickness of 12 μm. The coating film was exposed to 100 mJ/cm ² to 4000 mJ/cm ² with a focus of 0 μm using a ghi ray exposure machine (manufactured by Ultratech) through a negative mask capable of forming a via hole 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 via hole with an opening diameter of 50 μm was formed.
x: A via hole with an opening diameter of 50 µm was formed.

<Dielectric loss tangent evaluation>
After applying the photosensitive resin composition onto a silicon wafer with 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 with an integrated light quantity of 2000 mJ/cm ² using a high-pressure mercury lamp. The exposed film was heated to 230° C. at a rate of 5° C./min in an inert oven under a nitrogen atmosphere, and the coating film was heated at the same temperature for 1 hour. When the temperature drops to 100° C., the wafer is taken out and immersed in a 2 wt % hydrofluoric acid aqueous solution for 5 to 30 minutes. A resin film made of a polyimide resin was obtained. However, since the photosensitive resin composition obtained in Example 12 contains a polyimide resin, when using the photosensitive resin composition of Example 12, after exposure, baking under the above conditions is not performed, and the solvent Baking was performed at 180° C. for 30 minutes for the purpose of removing the . The film thickness of the resin film after peeling was 10 μm.

The dielectric loss tangent (tan δ) of the obtained film was calculated in IEICE Technical Report vol. 118, no. 506, MW2018-158, pp. 13-18, March 2019, Investigation on Millimeter Wave Complex Permittivity Evaluation by Cavity Resonator Method” (Kohei Takahagi (Utsunomiya University), Kazuaki Ebisawa (Tokyo Ohka Kogyo Co., Ltd.), Yoshinori Furukami (Utsunomiya University), Takashi Shimizu (Utsunomiya University)) It was measured by the method described. Using a network analyzer HP8510C (manufactured by Keysight), measurement was performed by the cavity resonator method under the conditions of room temperature of 25° C., humidity of 50%, frequency of 36 GHz, and sample thickness of 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 loss tangent value is less than 0.008.
B: Dielectric loss tangent value is 0.008 or more and less than 0.011.
C: A dielectric loss tangent value of 0.011 or more and less than 0.014.
D: The dielectric loss tangent value is 0.014 or more.

<Appearance evaluation>
The appearance of the film obtained in the same manner as the dielectric loss tangent evaluation was visually observed. A case where cloudiness was not observed was evaluated as ◯, and a case where cloudiness was observed was evaluated as x.

<Tensile test>
A strip-shaped 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 the evaluation of the dielectric loss tangent. Using the obtained test piece and a tensile tester (EZ-test, manufactured by Shimadzu Corporation), a tensile test was performed under conditions of a chuck distance of 2 cm and a tensile speed of 1 mm/min to measure the tensile elongation. Tensile elongation was obtained according to the following formula.
Tensile elongation (%) = (distance between chucks at break (cm) / 2 (cm) - 1) x 100
Regarding the tensile elongation, 40% or more was judged as ⊚, 30% or more and less than 40% was judged as ◯, and less than 30% was judged as x.

According to Examples 1 to 23, a polyamide resin containing a specific structural unit represented by the above formula (A1) and having a polymerizable group such as a methacryloyl group, and an oxime ester as a photosensitizer It can be seen that the photosensitive resin composition containing the compound exhibits good photosensitivity, has a low dielectric loss tangent, has a good appearance without white turbidity, and gives a resin film excellent in tensile strength.
On the other hand, according to Comparative Examples 1 and 2, a photosensitive resin composition containing a polyamide resin or a polyimide resin that does not contain a specific structural unit represented by the above formula (A1) has a dielectric loss tangent of It can be seen that a low resin film cannot be formed.

Claims (9)

including a resin (A) and a photosensitive agent (C),
The resin (A) is
A polyimide resin (A-I) 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
a diamine compound which is an aromatic compound having two amino groups bonded to an aromatic ring and having a hydroxy group bonded to the carbon atom adjacent to the carbon atom bonded to the amino group on the aromatic ring; , a polybenzoxazole resin (A-IV) derived from a dicarboxylic acid compound, or an amide-forming derivative of a dicarboxylic acid compound, and at least one selected from the group consisting of a polybenzoxazole resin precursor (AV) including
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, and R ^a2 is 1 to 20 carbon atoms. is an aliphatic group, a hydroxy group, a carboxy group, a sulfonic acid group, or a halogen atom, and Ar is a phenyl group optionally substituted with R ^a2 or a naphthyl group optionally substituted with R ^a2 , ma1 is an integer of 0 or more and 10 or less, ma2 is an integer of 0 or more and 7 or less, and ma3 is an integer of 1 or more and 10 or less.)
A photosensitive resin composition comprising a structural unit (a1) derived from a compound represented by: The compound represented by the formula (A1) is 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), and Y ^a1 is an organic group, 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.)
is a compound represented by
Claim 1, wherein the resin (A) comprises at least one selected from the group consisting of the polyimide resin (AI), the polyamic acid (A-II), and the polyamide resin (A-III). The photosensitive resin composition according to . The resin (A) has a radically polymerizable group on its molecular chain, and the photosensitive agent (C) is a photoradical polymerization initiator (C1), or the resin (A) is on its molecular chain 3. The photosensitive resin composition according to claim 1, wherein the photosensitive agent (C) is a photocationic polymerization initiator (C2). 4. The photosensitive resin composition according to claim 3, wherein the resin (A) has a radically polymerizable group on its molecular chain, and the radical photopolymerization initiator (C1) is an oxime ester photopolymerization initiator. . Claims 1 to 3, wherein the 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. The photosensitive resin composition according to any one of items 1 and 2. It has a base film and a photosensitive layer formed on the surface of the base film, and the photosensitive layer is composed of the photosensitive resin composition according to any one of claims 1 to 5. dry film. A method for producing a photosensitive dry film, comprising applying the photosensitive resin composition according to any one of claims 1 to 5 on 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 5 on a substrate;
an exposure step of position-selectively irradiating the photosensitive layer with an actinic ray or radiation for exposure;
and a developing step of developing the exposed photosensitive layer to obtain a patterned resin film. The resin (A) is the polyamic acid (A-II), the polyamide resin (A-III) containing structural units derived from a dicarboxylic acid compound that can be synthesized by reacting a tetracarboxylic dianhydride and a monohydroxy compound. ), or the polybenzoxazole resin precursor (AV),
After obtaining the patterned resin film, the resin film is baked, and a dicarboxylic acid compound that can be synthesized by reacting the polyamic acid (A-II) or the tetracarboxylic dianhydride with a monohydroxy compound. The polyamide resin (A-III) containing structural units derived from is converted into a polyimide resin (A-I), or the polybenzoxazole resin precursor (A-V) is converted into a polybenzoxazole resin (A-IV) 9. The method of manufacturing a patterned resin film according to claim 8, comprising converting to .