JP7786452B2 - Photosensitive resin composition - Google Patents

Description

The present invention relates to a photosensitive resin composition, a resin film obtained from the composition, a photosensitive resist film using the composition, a method for producing a substrate with a cured relief pattern, a substrate with a cured relief pattern, and a semiconductor device having a cured relief pattern.

Traditionally, polyimide resins, which combine excellent heat resistance with excellent electrical and mechanical properties, have been used as insulating materials for electronic components, and for passivation films, surface protective films, and interlayer insulating films for semiconductor devices. Among these polyimide resins, those supplied in the form of photosensitive polyimide precursors can easily form heat-resistant relief pattern coatings by applying the precursor, exposing it to light, developing it, and subjecting it to a thermal imidization process involving curing. Such photosensitive polyimide precursors have the advantage of enabling significant process reductions compared to conventional non-photosensitive polyimide resins.

Patent Documents 1 and 2 propose photosensitive resin compositions containing polyamic acid or polyimide using diamines having (meth)acryloyloxy groups.

Japanese Patent Application Laid-Open No. 2000-347404 Special Publication No. 2012-516927

In recent years, semiconductor devices have become increasingly sensitive to the need to transmit and process large amounts of information at high speeds, leading to an increase in the frequency of electrical signals. Because high-frequency electrical signals are prone to attenuation, it is necessary to reduce transmission loss. Therefore, resins used in semiconductor devices are required to have a low dielectric dissipation factor.
On the other hand, resins with low dielectric tangents tend to be brittle, and may be unable to keep up with the thermal expansion of adjacent materials during heat treatment processes such as solder reflow, resulting in breakage or reduced interlayer adhesion. Therefore, resins used in semiconductor devices are required to have high tensile elongation.

Furthermore, when forming a cured relief pattern, development is performed using a developer, typically an alkaline aqueous developer or an organic solvent developer. Photosensitive resins used to obtain cured relief patterns can be divided into positive-type resins, in which the photosensitive resin in the exposed areas dissolves in the developer after exposure and development, leaving the photosensitive resin in the unexposed areas, and negative-type resins, in which the photosensitive resin in the unexposed areas dissolves in the developer, leaving the photosensitive resin in the exposed areas. Negative-type resins, in particular, have inferior resolution compared to positive-type resins, but are easier to form thicker and more reliable films, and are used in the manufacture of semiconductor devices requiring these characteristics. However, conventional negative-type photosensitive resins containing polyamic acid have very high solubility in alkaline aqueous developers, making it difficult to control the dissolution rate and potentially making it difficult to obtain the desired relief pattern. Furthermore, negative-type photosensitive resins containing polyamic acid have a high affinity for alkaline aqueous developers, which means they tend to swell during development. This leads to issues such as the stress generated during drying, which can easily peel the formed relief pattern from the substrate. For this reason, organic solvent development is suitable for negative photosensitive resins containing polyamic acid, as it is relatively easy to control the dissolution rate and there is little risk of substrate peeling.

Therefore, there is a demand for a photosensitive resin composition that can be developed with an organic solvent and that produces a cured film having a low dielectric loss tangent and high tensile elongation.
However, the photosensitive resin compositions described in Patent Documents 1 and 2 do not satisfy all of these properties.

In view of the above circumstances, the object of the present invention is to provide a photosensitive resin composition that can be developed in an organic solvent and that produces a cured film having a low dielectric tangent and high tensile elongation, a resin film obtained from the composition, a photosensitive resist film using the composition, a method for producing a substrate with a cured relief pattern, a substrate with a cured relief pattern, and a semiconductor device having a cured relief pattern.

As a result of extensive research to achieve the above-mentioned objectives, the inventors discovered that by incorporating into a photosensitive resin composition a reaction product of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings, it is possible to obtain a photosensitive resin composition that can be developed in an organic solvent and that provides a cured film with a low dielectric tangent and high tensile elongation, thereby completing the present invention.

[1] A photosensitive resin composition comprising a reaction product of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings, and a solvent.
[2] The photosensitive resin composition according to [1], wherein the reaction product is a polyamic acid or a polyimide obtained by dehydrating and cyclizing a polyamic acid.
[3] The polyamic acid has at least a structural unit represented by the following formula (1):
The photosensitive resin composition according to [2], wherein the polyimide has at least a structural unit represented by the following formula (2):
[In formula (1), Ar ₁ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar ₂ represents a tetravalent organic group having three or more aromatic rings.]
[In formula (2), _Ar3 represents a divalent organic group having a photopolymerizable group and an aromatic ring, and _Ar4 represents a tetravalent organic group having three or more aromatic rings.]
[4] The photosensitive resin composition according to [3], wherein Ar ₂ in the formula (1) and Ar ₄ in the formula (2) are tetravalent organic groups represented by the following formula (3):
[In formula (3), _X1 and _X2 each independently represent a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a thioether bond, or a sulfonyl bond. _R1 and _R2 each independently represent an alkyl group having 1 to 6 carbon atoms which may be substituted. Y represents a divalent organic group represented by the following formula (3-1) or (3-2). _n1 and n2 each independently represent an integer of 0 to 3. When there are multiple R1s, the multiple _R1s may be the same or different. When there are multiple _R2s , the multiple _R2s may be the same or different. * represents a bond.]
[In formula (3-1), _Z1 represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a thioether bond, or a sulfonyl bond. _R3 and _R4 each independently represent a hydrocarbon group having 1 to 6 carbon atoms which may be substituted. m1 represents an integer of 0 to 3. n3 and n4 each independently represent an integer of 0 to 4. When there is a plurality of _Z1s , the plurality of _Z1s may be the same or different. When there is a plurality of n4s, the plurality of n4s may be the same or different. When there is a plurality of _R3s , the plurality of _R3s may be the same or different. When there is a plurality of _R4s , the plurality of _R4s may be the same or different. * represents a bond.
In formula (3-2), _Z2 represents a divalent organic group represented by the following formula (4) or (5). _R5 and _R6 each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. n5 and n6 each independently represent an integer of 0 to 4. When there are multiple _R5s , the multiple _R5s may be the same or different. When there are multiple _R6s , the multiple _R6s may be the same or different. * represents a bond.]

In formula (4), R ₇ and R ₈ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom; * represents a bond.
In formula (5), _R9 and _R10 each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms. * represents a bond.
[5] The photosensitive resin composition according to [3] or [4], wherein Ar ₁ in the formula (1) and Ar ₃ in the formula (2) are divalent organic groups represented by the following formula (6):
[In formula (6), _Z3 represents an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond; _Z4 represents a direct bond, an ester bond, or an amide bond; _Z5 represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a thioether bond, or a sulfonyl bond; m2 represents an integer of 0 or 1; _R11 represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group; _R12 represents a hydrogen atom or a methyl group; and * represents a bond.]
[6] The photosensitive resin composition according to [5], wherein Z ₃ and Z ₄ in the formula (6) are ester bonds.
[7] The photosensitive resin composition according to [5] or [6], wherein R ₁₁ in the formula (6) is a 1,2-ethylene group.
[8] The photosensitive resin composition according to any one of [1] to [7], further comprising a photoradical polymerization initiator.
[9] The photosensitive resin composition according to any one of [1] to [8], further comprising a crosslinkable compound.
[10] The photosensitive resin composition according to any one of [1] to [9], which is used for forming an insulating film.
[11] The photosensitive resin composition according to any one of [1] to [10], which is a negative photosensitive resin composition.
[12] A resin film that is a fired product of a coating film of the photosensitive resin composition according to any one of [1] to [11].
[13] The resin film according to [12], which is an insulating film.
[14] A photosensitive resist film comprising a base film, a photosensitive resin layer formed from the photosensitive resin composition according to any one of [1] to [11], and a cover film.
[15] (1) A step of applying the photosensitive resin composition according to any one of [1] to [11] onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a substrate having a cured relief pattern, comprising the step of: heat-treating the relief pattern to form a cured relief pattern.
[16] The method for producing a substrate having a cured relief pattern according to [15], wherein the developer used for the development is an organic solvent.
[17] A substrate having a cured relief pattern produced by the method according to [15] or [16].
[18] A semiconductor device comprising a semiconductor element and a cured film provided on the upper or lower part of the semiconductor element, wherein the cured film is a cured relief pattern formed from the photosensitive resin composition according to any one of [1] to [11].

The present invention provides a photosensitive resin composition that can be developed in an organic solvent and that produces a cured film having a low dielectric tangent and high tensile elongation, a resin film obtained from the composition, a photosensitive resist film using the composition, a method for producing a substrate with a cured relief pattern, a substrate with a cured relief pattern, and a semiconductor device having a cured relief pattern.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention contains at least the reaction product and a solvent, and may further contain other components as required.

<Reaction Products>
The reaction product is a reaction product between an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings.
The reaction product contains, as constituent components, an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings, and may, if necessary, contain, as constituent components, other diamine compounds and other tetracarboxylic acid derivatives.
The reaction product is, for example, polyamic acid or polyimide obtained by dehydrating and cyclizing polyamic acid.

When the reaction product contains an aromatic diamine compound having a photopolymerizable group as a constituent component, photosensitivity is imparted to the resin composition containing the reaction product.
When the reaction product contains an aromatic diamine compound and a tetracarboxylic acid derivative having three or more aromatic rings as constituent components, the resulting cured film has a low dielectric tangent and a high tensile elongation.

In the aromatic diamine compound having a photopolymerizable group, the two amino groups may be bonded to one aromatic ring or to each of two aromatic rings. Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocycle.
The aromatic diamine compound may have an aromatic ring to which no amino group is bonded.

Examples of the photopolymerizable group include a radically polymerizable group, a cationically polymerizable group, and an anionically polymerizable group. Of these, the radically polymerizable group is preferred.
Examples of the radically polymerizable group include an acryloyl group, a methacryloyl group, a propenyl ether group, a vinyl ether group, and a vinyl group.

It is preferable that the reaction product contains, as a constituent component, an aromatic diamine compound having three or more aromatic rings as a diamine compound other than the aromatic diamine compound having a photopolymerizable group, since this results in a lower dielectric tangent and higher tensile elongation in the resulting cured film.

The number of aromatic rings in an aromatic diamine compound having three or more aromatic rings is not particularly limited as long as it is three or more, but may be, for example, four or more. The upper limit of the number of aromatic rings is not particularly limited, but may be, for example, eight or less, or six or less.

Regarding the counting of aromatic rings in "three or more aromatic rings," polycyclic aromatic rings formed by the condensation of two or more aromatic rings, such as naphthalene rings and anthracene rings, are counted as one aromatic ring. Therefore, a naphthalene ring is counted as one aromatic ring. On the other hand, a biphenyl ring is not a condensed ring, so it is counted as two aromatic rings. And a perylene ring is considered to be a structure formed by the condensation of two naphthalene rings, and is counted as two aromatic rings.
Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

Examples of tetracarboxylic acid derivatives in the "tetracarboxylic acid derivative" include tetracarboxylic acid dianhydrides, tetracarboxylic acid dihalides, tetracarboxylic acid dialkyl esters, and tetracarboxylic acid dialkyl ester dihalides, with tetracarboxylic acid dianhydrides being particularly preferred.

As a tetracarboxylic acid derivative having three or more aromatic rings, an aromatic tetracarboxylic acid derivative having three or more aromatic rings is preferred. An aromatic tetracarboxylic acid refers to a compound in which a total of four carboxy groups are bonded to the same or different aromatic rings.

The number of aromatic rings in a tetracarboxylic acid derivative having three or more aromatic rings is not particularly limited as long as it is three or more, but may be, for example, four or more. The upper limit of the number of aromatic rings is not particularly limited, but may be, for example, eight or less, or six or less.

The ratio of the aromatic diamine compound having a photopolymerizable group to all diamine compounds constituting the reaction product is not particularly limited, but from the viewpoint of obtaining sufficient photosensitivity, it is preferably 10 to 100 mol %, more preferably 50 to 100 mol %.
The ratio of the aromatic tetracarboxylic acid derivative having three or more aromatic rings to the total amount of the tetracarboxylic acid derivatives constituting the reaction product is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 20 to 100 mol %, more preferably 50 to 100 mol %.

The reaction product is preferably polyamic acid or a polyimide obtained by dehydrating and cyclizing polyamic acid. From the perspective of obtaining a finer relief pattern, a polyimide obtained by dehydrating and cyclizing polyamic acid is more preferable. Here, the imidization rate of the polyimide does not need to be 100%. The imidization rate may be, for example, 90% or more, 95% or more, or 98% or more.

The polyamic acid preferably has at least a structural unit represented by the following formula (1).
The polyimide preferably has at least a structural unit represented by the following formula (2).
[In formula (1), Ar ₁ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar ₂ represents a tetravalent organic group having three or more aromatic rings.]
[In formula (2), _Ar3 represents a divalent organic group having a photopolymerizable group and an aromatic ring, and _Ar4 represents a tetravalent organic group having three or more aromatic rings.]

<<Ar ₁ and Ar ₃ >>
_Ar1 and _Ar3 are divalent organic groups having a photopolymerizable group and an aromatic ring, and are not particularly limited as long as they achieve the effects of the present invention. The divalent organic group having a photopolymerizable group and an aromatic ring is a residue obtained by removing two amino groups from an aromatic diamine compound having a photopolymerizable group.
Examples of the photopolymerizable group include the photopolymerizable groups described above.

Ar ₁ and Ar ₃ are preferably divalent organic groups represented by the following formula (6).
[In formula (6), _Z3 represents an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), or a urea bond (-NHCONH-), _Z4 represents a direct bond, an ester bond (-COO-), or an amide bond (-NHCO-). _Z5 represents a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), a urea bond (-NHCONH-), a thioether bond (-S-), or a sulfonyl bond (-SO ₂ -). m2 represents an integer of 0 or 1. _R11 represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group, and _R12 represents a hydrogen atom or a methyl group. * represents a bond.]

Examples of alkylene groups having 2 to 6 carbon atoms that may be substituted with hydroxyl groups include 1,1-ethylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,2-butylene, 2,3-butylene, 1,2-pentylene, 2,4-pentylene, 1,2-hexylene, 1,2-cyclopropylene, 1,2-cyclobutylene, 1,3-cyclobutylene, 1,2-cyclopentylene, 1,2-cyclohexylene, and alkylene groups in which at least some of the hydrogen atoms have been substituted with hydroxyl groups (e.g., 2-hydroxy-1,3-propylene).

_Z3 is preferably an ester bond.
_Z4 is preferably an ester bond.
R ₁₁ is preferably a 1,2-ethylene group.

Examples of the divalent organic group represented by formula (6) include the following divalent organic groups.
In the formula, * represents a bond, and the two bonds are located, for example, at meta positions relative to the substituent having the photopolymerizable group.

<< _Ar2 and _Ar4 >>
_Ar2 in formula (1) and _Ar4 in formula (2) are not particularly limited as long as they are tetravalent organic groups having three or more aromatic rings and exhibiting the effects of the present invention. However, from the viewpoint of suitably obtaining the effects of the present invention, they are preferably divalent organic groups represented by the following formula (3):
[In formula (3), _X1 and _X2 each independently represent a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), a urea bond (-NHCONH-), a thioether bond (-S-), or a sulfonyl bond ( _-SO2- ). _R1 and _R2 each independently represent an alkyl group having 1 to 6 carbon atoms which may be substituted. Y represents a divalent organic group represented by the following formula (3-1) or (3-2). _n1 and n2 each independently represent an integer of 0 to 3. When there are multiple R1s, the multiple _R1s may be the same or different. When there are multiple _R2s , the multiple _R2s may be the same or different. * represents a bond.]

Examples of the optionally substituted alkyl group having 1 to 6 carbon atoms in _R1 and _R2 include alkyl groups having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. In this specification, unless otherwise specified, the alkyl group may be linear, branched, or cyclic, or may be a combination of two or more of these.
Examples of the substituent in the optionally substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, a nitro group, a nitroso group, an oxo group, a thioxy group, and an alkoxy group having 1 to 6 carbon atoms.
The term "1 to 6 carbon atoms" in the "optionally substituted alkyl group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkyl group" excluding the substituents. The number of substituents is not particularly limited.

[In formula (3-1), _Z1 represents a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), a urea bond (-NHCONH-), a thioether bond (-S-), or a sulfonyl bond ( _-SO2- ). _R3 and _R4 each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. m1 represents an integer of 0 to 3. _n3 and n4 each independently represent an integer of 0 to 4. When there are multiple Z1s, the multiple _Z1s may be the same or different. When there are multiple n4s, the multiple n4s may be the same or different. When there are multiple _R3s , the multiple _R3s may be the same or different. When there are multiple _R4s , the multiple _R4s may be the same or different. * represents a bond.
In formula (3-2), _Z2 represents a divalent organic group represented by the following formula (4) or (5). _R5 and _R6 each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. n5 and n6 each independently represent an integer of 0 to 4. When there are multiple _R5s , the multiple _R5s may be the same or different. When there are multiple _R6s , the multiple _R6s may be the same or different. * represents a bond.]

Examples of the optionally substituted hydrocarbon group having 1 to 6 carbon atoms in _R3 , _R4 , _R5 , and _R6 include an optionally substituted alkyl group having 1 to 6 carbon atoms and an optionally substituted phenyl group. Examples of the substituent include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, a nitro group, a nitroso group, an oxo group, a thioxy group, and an alkoxy group having 1 to 6 carbon atoms.
The term "carbon atom number 1 to 6" in the "optionally substituted hydrocarbon group having carbon atoms 1 to 6" refers to the number of carbon atoms in the "hydrocarbon group" excluding substituents. The number of substituents is not particularly limited.

Specific examples of the optionally substituted alkyl group having 1 to 6 carbon atoms for _R3 , R4, _R5 and _R6 include _the optionally substituted alkyl groups having 1 to 6 carbon atoms exemplified in the description of _R1 and _R2 .

In formula (4), R ₇ and R ₈ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom; * represents a bond.
In formula (5), _R9 and _R10 each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms. * represents a bond.

Examples of the hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom in _R7 and _R8 include an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogenated phenyl group. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenation in the halogenated alkyl group having 1 to 6 carbon atoms and the halogenated phenyl group may be partial or complete.

Examples of the substituent in the optionally substituted alkylene group having 1 to 6 carbon atoms in _R and _R include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, a nitro group, a nitroso group, an oxo group, a thioxy group, an alkoxy group having 1 to 6 carbon atoms, and the like.
Examples of the optionally substituted alkylene group having 1 to 6 carbon atoms include an alkylene group having 1 to 6 carbon atoms and a halogenated alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group.
The "number of carbon atoms" in the "optionally substituted alkylene group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkylene group" excluding the substituents. The number of substituents is not particularly limited.

Examples of the substituent in the optionally substituted arylene group having 6 to ₁₀ carbon atoms in _R and R include a halogen atom, an optionally halogenated alkyl group having 1 to 6 carbon atoms, an optionally halogenated alkoxy group having 1 to 6 carbon atoms, etc. The halogenation may be partial or complete.
Examples of the arylene group include a phenylene group and a naphthylene group.
The term "6 to 10 carbon atoms" in the "optionally substituted arylene group having 6 to 10 carbon atoms" refers to the number of carbon atoms in the "arylene group" excluding the substituents. The number of substituents is not particularly limited.

Examples of the divalent organic group represented by formula (4) include divalent organic groups represented by the following formulas:
In the formula, * represents a bond.

Examples of the divalent organic group represented by formula (5) include divalent organic groups represented by the following formulas:
In the formula, R ₁₃ to R ₁₅ each independently represent a halogen atom, an alkyl group of 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkoxy group of 1 to 6 carbon atoms which may be substituted with a halogen atom. n13 represents an integer of 0 to 5. n14 and n15 each independently represent an integer of 0 to 4. When there is a plurality of _{R 13s} , the plurality of R _13s may be the same or different. When there is a plurality of R _14s , the plurality of R _14s may be the same or different. When there is a plurality of R _15s , the plurality of R _15s may be the same or different. * represents a bond.

Specific examples of the alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom in R ₁₃ to R ₁₅ include an alkyl group having 1 to 6 carbon atoms and a halogenated alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenation in the halogenated alkyl group having 1 to 6 carbon atoms may be partial or complete.
Specific examples of the alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom for R ₁₃ to R ₁₅ include an alkoxy group formed from an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom.

Examples of _Ar2 and _Ar4 include tetravalent organic groups represented by the following formulas.
In the formula, * represents a bond.

<Other structural units>
The polyamic acid may have a structural unit other than the structural unit represented by formula (1). Examples of the other structural unit include a structural unit represented by the following formula (1′).
The polyimide may have a structural unit other than the structural unit represented by formula (2). Examples of the other structural unit include a structural unit represented by the following formula (2').
[In formula (1′), Ar _1′ represents a divalent organic group having a photopolymerizable group and an aromatic ring, or a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _2′ represents a tetravalent organic group having three or more aromatic rings, or a tetravalent organic group not having three or more aromatic rings, except for the case where Ar _1′ is a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _2′ is a tetravalent organic group having three or more aromatic rings.]
[In formula (2'), Ar3 _' represents a divalent organic group having a photopolymerizable group and an aromatic ring, or a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar4 _' represents a tetravalent organic group having three or more aromatic rings, or a tetravalent organic group not having three or more aromatic rings, except when Ar3 _' is a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar4 _' is a tetravalent organic group having three or more aromatic rings.]

Combinations of Ar _1′ and Ar _2′ include the following combinations (i) to (iii).
(i): A combination in which Ar _1' represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _2' represents a tetravalent organic group having no three or more aromatic rings. (ii): A combination in which Ar _1' represents a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _2' represents a tetravalent organic group having no three or more aromatic rings. (iii): A combination in which Ar _1' represents a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _2' represents a tetravalent organic group having three or more aromatic rings.

Combinations of Ar _3′ and Ar _4′ include the following combinations (iv) to (vi).
(iv): A combination in which Ar _3' represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _4' represents a tetravalent organic group having no three or more aromatic rings. (v): A combination in which Ar _3' represents a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _4' represents a tetravalent organic group having no three or more aromatic rings. (vi): A combination in which Ar _3' represents a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _4' represents a tetravalent organic group having three or more aromatic rings.

<<Ar _1′ and Ar _3′ >>
Examples of the divalent organic group having a photopolymerizable group and an aromatic ring in Ar _1′ and Ar _3′ include the divalent organic groups having a photopolymerizable group and an aromatic ring exemplified in the description of Ar ₁ and Ar ₃ .
The divalent organic group other than the photopolymerizable group and the divalent organic group having an aromatic ring in Ar _1′ and Ar _3′ is not particularly limited, but a divalent organic group having three or more aromatic rings is preferred because it provides a lower dielectric tangent and higher tensile elongation in the resulting cured film.
The divalent organic group having three or more aromatic rings is not particularly limited, but is preferably a divalent organic group represented by the following formula (13).
[In formula (13), _X21 and _X22 each independently represent a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), a urea bond (-NHCONH-), a thioether bond (-S-), or a sulfonyl bond ( _-SO2- ). _R21 and _R22 each independently represent an alkyl group having 1 to 6 carbon atoms which may be substituted. _Y20 represents a divalent organic group represented by the following formula (13-1) or (13-2). _n21 and n22 each independently represent an integer of 0 to 4. When there are multiple R21s, the multiple _R21s may be the same or different. When there are multiple _R22s , the multiple _R22s may be the same or different. * represents a bond.]

Specific examples of the optionally substituted alkyl group having 1 to 6 carbon atoms for R ₂₁ and R ₂₂ include the optionally substituted alkyl groups having 1 to 6 carbon atoms exemplified in the description of R ₁ and R ₂ .
The term "1 to 6 carbon atoms" in the "optionally substituted alkyl group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkyl group" excluding the substituents. The number of substituents is not particularly limited.

[In formula (13-1), Z ₂₁ represents a direct bond, an ether bond (—O—), an ester bond (—COO—), an amide bond (—NHCO—), a urethane bond (—NHCOO—), a urea bond (—NHCONH—), a thioether bond (—S—) or a sulfonyl bond (—SO ₂ —). _{R 23} and R ₂₄ each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. m21 represents an integer of 0 to 3. n23 and n24 each independently represent an integer of 0 to 4. When there are multiple Z _{21 s} , the multiple Z ₂₁ s may be the same or different. When there are multiple n24 s, the multiple n24 s may be the same or different. When there are multiple R _{23 s} , the multiple R ₂₃ s may be the same or different. When there are multiple _{R 24 s} , the multiple R ₂₄ s may be the same or different. * represents a bond.
In formula (13-2), Z ₂₂ represents a divalent organic group represented by the following formula (14) or (15). _{R 25} and R ₂₆ each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. n25 and n26 each independently represent an integer of 0 to 4. When there are multiple R _25s , the multiple R _25s may be the same or different. When there are multiple R _26s , the multiple R _26s may be the same or different. * represents a bond.]

Specific examples of the optionally substituted hydrocarbon group having 1 to 6 carbon atoms for R ₂₃ , R ₂₄ , R ₂₅ , and R ₂₆ include the optionally substituted hydrocarbon groups having 1 to 6 carbon atoms exemplified in the description of R ₃ , R ₄ , R ₅ , and R ₆ .
The term "carbon atom number 1 to 6" in the "optionally substituted hydrocarbon group having carbon atoms 1 to 6" refers to the number of carbon atoms in the "hydrocarbon group" excluding substituents. The number of substituents is not particularly limited.

Specific examples of the optionally substituted alkyl group having 1 to 6 carbon atoms for R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ include the optionally substituted alkyl groups having 1 to 6 carbon atoms exemplified in the description of R ₁ and R ₂ .

In formula (14), R ₂₇ and R ₂₈ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom. * represents a bond.
In formula (15), R ₂₉ and R ₃₀ each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms. * represents a bond.

Specific examples of the hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom for R ₂₇ and R ₂₈ include the hydrocarbon groups having 1 to 6 carbon atoms which may be substituted with a halogen atom exemplified in the description of R ₇ and R ₈ .

Specific examples of the optionally substituted alkylene group having 1 to 6 carbon atoms for R ₂₉ and R ₃₀ include the optionally substituted alkylene groups having 1 to 6 carbon atoms exemplified in the description of R ₉ and R ₁₀ .
The "number of carbon atoms" in the "optionally substituted alkylene group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkylene group" excluding the substituents. The number of substituents is not particularly limited.

Specific examples of the optionally substituted arylene group having 6 to 10 carbon atoms for _R29 and _R30 include the optionally substituted arylene groups having 6 to 10 carbon atoms exemplified in the description of _R9 and _R10 .
The term "6 to 10 carbon atoms" in the "optionally substituted arylene group having 6 to 10 carbon atoms" refers to the number of carbon atoms in the "arylene group" excluding the substituents. The number of substituents is not particularly limited.

Examples of the divalent organic group represented by formula (14) include divalent organic groups represented by the following formulas:
In the formula, * represents a bond.

Examples of the divalent organic group represented by formula (15) include divalent organic groups represented by the following formulas:
In the formula, R ₃₃ to R ₃₅ each independently represent a halogen atom, an alkyl group of 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkoxy group of 1 to 6 carbon atoms which may be substituted with a halogen atom. n33 represents an integer of 0 to 5. n34 and n35 each independently represent an integer of 0 to 4. When there is a plurality of R _33s , the plurality of R _33s may be the same or different. When there is a plurality of R _34s , the plurality of R _34s may be the same or different. When there is a plurality of R _35s , the plurality of R _35s may be the same or different. * represents a bond.

Specific examples of the alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom in R ₃₃ to R ₃₅ include the alkyl groups having 1 to 6 carbon atoms which may be substituted with a halogen atom exemplified in the description of R ₁₃ to R ₁₅ .
Specific examples of the alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom for R ₃₃ to R ₃₅ include an alkoxy group formed from an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom.

Examples of Ar _1′ and Ar _3′ include divalent organic groups represented by the following formulas.
In the formula, * represents a bond.

Other examples of Ar _1′ and Ar _3′ include divalent organic groups represented by the following formulas.
In the formula, * represents a bond.

<<Ar _2′ and Ar _4′ >>
Examples of the tetravalent organic group having three or more aromatic rings in Ar _2′ and Ar _4′ include the tetravalent organic groups having three or more aromatic rings exemplified in the description of Ar ₂ and Ar ₄ .
Examples of the tetravalent organic group in Ar2 _' and Ar4 _' that does not have three or more aromatic rings include a tetravalent organic group having one or two aromatic rings and a tetravalent organic group that does not have an aromatic ring. The tetravalent organic group having one or two aromatic rings is derived, for example, from an aromatic tetracarboxylic dianhydride derivative. Furthermore, the tetravalent organic group that does not have an aromatic ring is derived, for example, from an aliphatic tetracarboxylic anhydride derivative. Such a tetravalent organic group is not particularly limited, but examples include the following tetravalent organic groups.
In the formula, * represents a bond.

The proportion of the structural unit represented by formula (1) in all structural units of the polyamic acid is not particularly limited, but from the viewpoint of obtaining sufficient photosensitivity, it is preferably 10 to 100 mol %, more preferably 50 to 100 mol %. Note that the structural unit is also a repeating unit.
When the polyamic acid has a structural unit represented by formula (1'), the proportion of the structural unit represented by formula (1') in all structural units of the polyamic acid is not particularly limited, but is preferably 1 to 90 mol %, more preferably 1 to 50 mol %.

When the imidization rate of the polyimide is not 100%, the polyimide may have a structural unit represented by formula (1) in addition to the structural unit represented by formula (2).
The total proportion of the structural units represented by formula (1) and the structural units represented by formula (2) in all structural units of the polyimide is not particularly limited, but from the viewpoint of obtaining sufficient photosensitivity, it is preferably 10 to 100 mol %, more preferably 50 to 100 mol %.
When the polyimide has at least one of the structural units represented by formula (1') and the structural units represented by formula (2'), the total proportion of the structural units represented by formula (1') and the structural units represented by formula (2') in all the structural units of the polyimide is not particularly limited, but is preferably 1 to 90 mol %, more preferably 1 to 50 mol %.

The weight-average molecular weight of the reaction product is not particularly limited, but the weight-average molecular weight measured in polystyrene equivalent terms by gel permeation chromatography (hereinafter abbreviated as GPC in this specification) is preferably 5,000 to 100,0000, more preferably 7,000 to 50,000, even more preferably 10,000 to 50,000, and particularly preferably 10,000 to 40,000.

<Method of producing reaction product>
The reaction product is obtained by reacting an aromatic diamine compound having a photopolymerizable group with a tetracarboxylic acid derivative having three or more aromatic rings, and, if necessary, other diamine compounds and other tetracarboxylic acid derivatives.

There are no particular limitations on the method for producing the reaction product, and examples include known methods for producing polyamic acid or polyimide by reacting a diamine compound with a tetracarboxylic acid derivative. Polyamic acid and polyimide can be synthesized by known methods, such as those described in WO 2013/157586.

The reaction product is produced, for example, by reacting (condensation polymerization) a diamine component containing an aromatic diamine compound having a photopolymerizable group with a tetracarboxylic acid derivative component having three or more aromatic rings in a solvent.

Specific examples of the solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyric acid amide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. When the polymer has high solubility in the solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or solvents represented by the following formulas [D-1] to [D-3] can be used.
(In formula [D-1], ^D1 represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], ^D2 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], ^D3 represents an alkyl group having 1 to 4 carbon atoms.)

These solvents may be used alone or in combination. Furthermore, even if a solvent does not dissolve the reaction product, it may be mixed with the above solvents to the extent that the reaction product does not precipitate.

When the diamine component and the tetracarboxylic acid derivative component are reacted in a solvent, the reaction can be carried out at any concentration, preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction can be carried out at a high concentration in the early stage, and then additional solvent can be added.
In the reaction, the ratio of the total number of moles of the diamine components to the total number of moles of the tetracarboxylic acid derivative components is preferably 0.8 to 1.2. As in a typical polycondensation reaction, the closer this molar ratio is to 1.0, the higher the molecular weight of the reaction product produced.

When the diamine component and the tetracarboxylic acid derivative component are reacted, a thermal polymerization inhibitor may be added to the reaction system to prevent polymerization of the photopolymerizable group.
Examples of the thermal polymerization inhibitor include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.
The amount of the thermal polymerization inhibitor used is not particularly limited.

Polyimide can be obtained by dehydrating and cyclizing the polyamic acid, which is the reaction product obtained in the above reaction.
Methods for obtaining polyimide include thermal imidization, in which a solution of polyamic acid, the reaction product obtained by the above reaction, is heated as is, or chemical imidization, in which a catalyst is added to a solution of polyamic acid. When thermal imidization is performed in a solution, the temperature is 100 to 400°C, preferably 120 to 250°C, and it is preferable to perform the imidization while removing water produced by the imidization reaction from the system.

The chemical imidization can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyamic acid obtained by the reaction and stirring at temperatures between -20 and 250°C, preferably between 0 and 180°C. The amount of the basic catalyst is 0.1 to 30 molar times, preferably 0.2 to 20 molar times, the amount of the amide acid groups. The amount of the acid anhydride is 1 to 50 molar times, preferably 1.5 to 30 molar times, the amount of the amide acid groups. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Of these, triethylamine is preferred because it is less likely to produce the by-product polyisoimide. Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, acetic anhydride is preferred because it facilitates purification after the reaction. The imidization rate (the ratio of ring-closed repeating units to all repeating units in the polyimide precursor, also known as the ring-closure rate) during chemical imidization can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

To recover the imidized product produced from the imidization reaction solution, the reaction solution can be poured into a solvent to cause precipitation. Examples of solvents that can be used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated by pouring into the solvent can be recovered by filtration and then dried at room temperature or by heating under atmospheric or reduced pressure.

In polyimides, some or all of the repeating units are ring-closed. The imidization rate in polyimides is preferably 20 to 99%, more preferably 30 to 99%, and even more preferably 50 to 99%.

The polyimide may be end-capped. The method for end-capping is not particularly limited, and conventional methods using, for example, monoamines or acid anhydrides can be used.

<Solvent>
As the solvent contained in the photosensitive resin composition, an organic solvent is preferably used from the viewpoint of solubility of the reaction product. Specific examples of the solvent include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyric acid amide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methyl 2-hydroxyisobutyrate, ethyl lactate, and solvents represented by the following formulas [D-1] to [D-3]. These may be used alone or in combination of two or more.
(In formula [D-1], ^D1 represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], ^D2 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], ^D3 represents an alkyl group having 1 to 4 carbon atoms.)

The solvent can be used in an amount ranging from 30 to 1,500 parts by weight, preferably from 100 to 1,000 parts by weight, per 100 parts by weight of the reaction product, depending on the desired coating film thickness and viscosity of the photosensitive resin composition.

<Other ingredients>
In an embodiment, the photosensitive resin composition may further contain other components in addition to the reaction product and the solvent, such as a photoradical polymerization initiator (also referred to as a "photoradical initiator"), a crosslinking compound (also referred to as a "crosslinking agent"), a thermosetting agent, other resin components, a filler, a sensitizer, an adhesion promoter, a thermal polymerization inhibitor, an azole compound, a hindered phenol compound, etc.

<<Photoradical polymerization initiator>>
The photoradical polymerization initiator is not particularly limited as long as it is a compound that has absorption in the light source used for photocuring, and examples thereof include tert-butylperoxy-iso-butylate, 2,5-dimethyl-2,5-bis(benzoyldioxy)hexane, 1,4-bis[α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butylperoxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexene hydroperoxide, α-(iso-propylphenyl)-iso-propyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy)valerate, cyclohexane ... Organic peroxides such as chlorohexanone peroxide, 2,2',5,5'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-amylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butyl peroxybenzoate, and di-tert-butyl diperoxyisophthalate; 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, and octamethylanthraquinone, Quinones such as 1,2-benzanthraquinone; benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin, and α-phenylbenzoin; 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propionyl)benzyl}-phenyl]-2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, Examples of suitable oxime ester compounds include alkylphenone compounds such as pan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; and oxime ester compounds such as 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone.

The photoradical polymerization initiator is commercially available, for example, IRGACURE [registered trademark] 651, 184, 2959, 127, 907, 369, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, OXE03, OXE04, 250, 1173, MBF, TPO, 4265, TPO (all manufactured by BASF), KAYACURE [registered trademark] DETX-S, MBP, DMBI, EPA, OA (all manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, VICURE-55 (all manufactured by Stauffer Co., Ltd.), ESACURE Examples of suitable acrylic resins include KIP150, TZT, 1001, KTO46, KB1, KL200, KS300, EB3, Triazine-PMS, Triazine A, and Triazine B (all manufactured by Nippon SiberHegner Co., Ltd.), ADEKA OPTOMER N-1717, N-1414, N-1606, ADEKA ARCLES N-1919T, NCI-831E, NCI-930, and NCI-730 (all manufactured by ADEKA Corporation).
These photoradical polymerization initiators may be used alone or in combination of two or more.

The amount of photoradical polymerization initiator contained is not particularly limited, but is preferably 0.1 to 20 parts by weight per 100 parts by weight of the reaction product, and more preferably 0.5 to 15 parts by weight from the perspective of photosensitivity characteristics. When 0.1 parts by weight or more of photoradical polymerization initiator is contained per 100 parts by weight of the reaction product, the photosensitivity of the photosensitive resin composition is likely to be improved, while when 20 parts by weight or less is contained, the thick-film curing properties of the photosensitive resin composition are likely to be improved.

<<Crosslinkable compound>>
In an embodiment, in order to improve the resolution of the relief pattern, a monomer (crosslinkable compound) having a photoradical polymerizable unsaturated bond can be optionally contained in the photosensitive resin composition.
Such a crosslinkable compound is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction with a photoradical polymerization initiator, and includes, but is not limited to, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol or polyethylene glycol mono- or di(meth)acrylate, propylene glycol or polypropylene glycol mono- or di(meth)acrylate, glycerol mono-, di- or tri(meth)acrylate, 1,4-butanediol, di(meth)acrylate of 1,6-hexanediol, di(meth)acrylate of 1,9-nonanediol, di(meth)acrylate of 1,10-decanediol, di(meth)acrylate of neopentyl glycol, cyclohexane di(meth)acrylate, di(meth)acrylate of cyclohexanedimethanol, di(meth)acrylate of tricyclodecanedimethanol, di(meth)acrylate of dioxane glycol, mono- or di(meth)acrylate of bisphenol A, bisphenol Di(meth)acrylate of bisphenol F, di(meth)acrylate of hydrogenated bisphenol A, benzene trimethacrylate, di(meth)acrylate of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, di(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, isobornyl (meth)acrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane tri(meth)acrylate, di- or tri(meth)acrylate of glycerol, pentaerythritol Examples of suitable compounds include di-, tri-, or tetra(meth)acrylates of teflon, as well as ethylene oxide or propylene oxide adducts of these compounds, 2-isocyanate ethyl (meth)acrylate or isocyanate-containing (meth)acrylates, and compounds obtained by adding a blocking agent such as methyl ethyl ketone oxime, ε-caprolactam, γ-caprolactam, 3,5-dimethylpyrazole, diethyl malonate, ethanol, isopropanol, n-butanol, or 1-methoxy-2-propanol to these compounds. These compounds may be used alone or in combination of two or more. In this specification, (meth)acrylate refers to acrylate and methacrylate.

The content of the crosslinking compound is not particularly limited, but is preferably 1 to 100 parts by mass, and more preferably 1 to 50 parts by mass, per 100 parts by mass of the reaction product.

<<Thermal curing agent>>
Examples of heat curing agents include hexamethoxymethylmelamine, tetramethoxymethylglycoluril, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.
The content of the heat curing agent in the photosensitive resin composition is not particularly limited.

<<Filler>>
Examples of the filler include inorganic fillers, and specific examples include sols of silica, aluminum nitride, boron nitride, zirconia, alumina, and the like.
The content of the filler in the photosensitive resin composition is not particularly limited.

<<Other resin components>>
In an embodiment, the photosensitive resin composition may further contain a resin component other than the reaction product, such as polyoxazole, a polyoxazole precursor, a phenolic resin, a polyamide, an epoxy resin, a siloxane resin, or an acrylic resin.
The content of these resin components is not particularly limited, but is preferably in the range of 0.01 to 20 parts by mass per 100 parts by mass of the reaction product.

<<Sensitizer>>
In embodiments, the photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity.
Examples of sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylideneindano. p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl [0039] Examples of the methylaminobenzoate include methylaminobenzoate, ...
These may be used alone or in combination.

The content of the sensitizer is not particularly limited, but it is preferable that it be 0.1 to 25 parts by weight per 100 parts by weight of the reaction product.

<<Adhesion aid>>
In an embodiment, an adhesion promoter may be optionally incorporated into the photosensitive resin composition to improve adhesion between the film formed using the photosensitive resin composition and the substrate.
Examples of the adhesion promoter include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-(meth)acryloxypropyldimethoxymethylsilane, 3-(meth)acryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]furan, Examples of the adhesive agent include silane coupling agents such as thalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride and N-phenylaminopropyltrimethoxysilane, and aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate) and ethylacetoacetate aluminum diisopropylate.

Of these adhesive aids, it is more preferable to use a silane coupling agent in terms of adhesive strength.

The content of the adhesive aid is not particularly limited, but a range of 0.5 to 25 parts by mass per 100 parts by mass of the reaction product is preferred.

<<Thermal polymerization inhibitor>>
In an embodiment, a thermal polymerization inhibitor may be optionally blended to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition during storage, particularly in the form of a solution containing a solvent.
Examples of the thermal polymerization inhibitor include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

The content of the thermal polymerization inhibitor is not particularly limited, but a range of 0.005 to 12 parts by mass per 100 parts by mass of the reaction product is preferred.

<<Azole compounds>>
For example, when a substrate made of copper or a copper alloy is used, an azole compound can be optionally blended into the photosensitive resin composition to suppress discoloration of the substrate.
Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, and the like. benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole.
These azole compounds may be used alone or in combination of two or more.

The amount of the azole compound is not particularly limited, but is preferably 0.1 to 20 parts by weight per 100 parts by weight of the reaction product, and more preferably 0.5 to 5 parts by weight from the viewpoint of photosensitivity characteristics. If the amount of the azole compound per 100 parts by weight of the reaction product is 0.1 parts by weight or more, discoloration of the copper or copper alloy surface is suppressed when the photosensitive resin composition is formed on copper or a copper alloy. On the other hand, if the amount is 20 parts by weight or less, excellent photosensitivity is achieved, which is preferable.

<<Hindered phenol compounds>>
In embodiments, a hindered phenol compound may optionally be incorporated into the photosensitive resin composition to inhibit discoloration on copper.
Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylamine, ethylene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydroxyphenyl)propionate rosinamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1 ,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6- (1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1, 3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy- 2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and the like, but are not limited thereto.
Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

The content of the hindered phenol compound is not particularly limited, but is preferably 0.1 to 20 parts by weight per 100 parts by weight of the reaction product, and more preferably 0.5 to 10 parts by weight from the viewpoint of photosensitivity characteristics. If the content of the hindered phenol compound per 100 parts by weight of the reaction product is 0.1 parts by weight or more, for example, when the photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented. On the other hand, if the content is 20 parts by weight or less, excellent photosensitivity is achieved, which is preferred.

The photosensitive resin composition can be suitably used as a negative-type photosensitive resin composition for producing the cured relief pattern described below.

(Resin film)
The resin film of the present invention is a fired product of a coating film of the photosensitive resin composition of the present invention.
As the application method, a method conventionally used for applying a photosensitive resin composition, such as a method of applying using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, or a method of spray application using a spray coater, can be used.
The firing method for obtaining the fired product can be selected from various methods, such as using a hot plate, an oven, or a temperature-programmable heating oven. The firing can be carried out, for example, at 130°C to 250°C for 30 minutes to 5 hours. The atmospheric gas during heat curing may be air, or an inert gas such as nitrogen or argon.
The thickness of the resin film is not particularly limited, but is preferably 1 μm to 100 μm, and more preferably 2 μm to 50 μm.
The resin film is, for example, an insulating film.

(Photosensitive resist film)
The photosensitive resin composition of the present invention can be used for a photosensitive resist film (so-called dry film resist).
The photosensitive resist film has a base film, a photosensitive resin layer (photosensitive resin film) formed from the photosensitive resin composition of the present invention, and a cover film.
Usually, a photosensitive resin layer and a cover film are laminated in this order on a substrate film.

The photosensitive resist film can be produced, for example, by applying a photosensitive resin composition onto a substrate film, drying it to form a photosensitive resin layer, and then laminating a cover film on the photosensitive resin layer.
As the application method, a method conventionally used for applying a photosensitive resin composition, such as a method of applying using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, or a method of spray application using a spray coater, can be used.
The drying method may be, for example, at 20° C. to 200° C. for 1 minute to 1 hour.
The thickness of the resulting photosensitive resin layer is not particularly limited, but is preferably 1 μm to 100 μm, and more preferably 2 μm to 50 μm.

The substrate film may be a known film, such as a thermoplastic resin film. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate. The thickness of the substrate film is preferably 2 μm to 150 μm.
The cover film may be a known film, such as a polyethylene film or a polypropylene film. The cover film preferably has a lower adhesive strength with the photosensitive resin layer than the base film. The thickness of the cover film is preferably 2 μm to 150 μm, more preferably 2 μm to 100 μm, and particularly preferably 5 μm to 50 μm.
The base film and the cover film may be made of the same film material, or different films may be used.

(Method for producing a substrate having a cured relief pattern)
The method for producing a substrate having a cured relief pattern of the present invention comprises the steps of:
(1) a step of applying the photosensitive resin composition according to the present invention onto a substrate to form a photosensitive resin layer (photosensitive resin film) on the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) heat-treating the relief pattern to form a hardened relief pattern.

Each process is explained below.

(1) Step of applying the photosensitive resin composition of the present invention onto a substrate to form a photosensitive resin layer on the substrate In this step, the photosensitive resin composition of the present invention is applied onto a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition can be used, such as a method of applying using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., or a method of spray application using a spray coater, etc.

If necessary, the coating film made from the photosensitive resin composition can be dried. Drying methods that can be used include air drying, heat drying in an oven or on a hot plate, and vacuum drying. Specifically, when air drying or heat drying is used, drying can be carried out at 20°C to 200°C for 1 minute to 1 hour. This allows a photosensitive resin layer to be formed on the substrate.

(2) Step of exposing the photosensitive resin layer In this step, the photosensitive resin layer formed in step (1) above is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, a mirror projection, or a stepper, either directly or through a photomask or reticle having a pattern.
Examples of light sources used for exposure include g-line, h-line, i-line, ghi-line broadband, and KrF excimer laser. The exposure dose is preferably 25 mJ/cm ² to 2000 mJ/cm ² .

After this, for purposes such as improving photosensitivity, post-exposure baking (PEB) and/or pre-development baking may be performed as needed using any combination of temperature and time. The baking conditions preferably range from 50°C to 200°C in temperature and from 10 to 600 seconds in time, but are not limited to these ranges as long as they do not impair the properties of the photosensitive resin composition.

(3) Step of developing the exposed photosensitive resin layer to form a relief pattern In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The development method for developing the exposed (irradiated) photosensitive resin layer can be any method selected from conventionally known photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment. After development, rinsing may be performed to remove the developer. Furthermore, post-development baking may be performed at any temperature and time combination, as necessary, for the purpose of adjusting the shape of the relief pattern, etc.
The developer used for development is preferably an organic solvent, such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. Two or more types of each solvent can also be used, for example, in combination.
The rinse solution used for rinsing is preferably an organic solvent that is miscible with the developer and has low solubility in the photosensitive resin composition. Examples of preferred rinse solutions include methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, toluene, and xylene. Two or more of each solvent, for example, a combination of several types, can also be used.

(4) Step of Heating the Relief Pattern to Form a Cured Relief Pattern In this step, the relief pattern obtained by the development described above is heated to convert it into a cured relief pattern. When the reaction product is a polyamic acid, this heating causes thermal imidization, resulting in a cured relief pattern containing polyimide. Various methods can be selected for heat curing, such as using a hot plate, an oven, or a temperature-programmable heating oven. Heating can be performed, for example, at 130°C to 250°C for 30 minutes to 5 hours. The atmospheric gas used during heat curing may be air, or an inert gas such as nitrogen or argon.

The thickness of the cured relief pattern is not particularly limited, but is preferably 1 μm to 100 μm, and more preferably 2 μm to 50 μm.

(Semiconductor device)
In an embodiment, a semiconductor device is provided that includes a semiconductor element and a cured film provided on or below the semiconductor element. The cured film is a cured relief pattern formed from the photosensitive resin composition of the present invention. The cured relief pattern can be obtained, for example, by steps (1) to (4) in the method for producing a substrate with a cured relief pattern described above.
The present invention can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-mentioned method for manufacturing a substrate having a cured relief pattern as part of its steps. The semiconductor device of the present invention can be manufactured by forming a cured relief pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and combining the method with a known method for manufacturing a semiconductor device.

(Display device)
In an embodiment, a display device is provided that includes a display element and a cured film provided on the display element, the cured film having the above-described cured relief pattern. The cured relief pattern may be laminated in direct contact with the display element, or may be laminated via another layer. Examples of the cured film include surface protection films, insulating films, and planarizing films for TFT (Thin Film Transistor) liquid crystal display elements and color filter elements, protrusions for MVA (Multi-Domain Vertical Alignment) liquid crystal display devices, and partition walls for cathodes of organic EL (Electro-Luminescence) elements.

In addition to being applicable to semiconductor devices as described above, the photosensitive resin composition of the present invention is also useful for applications such as interlayer insulating films in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

The following examples will explain the present invention in more detail, but the present invention is not limited to these examples.

The weight average molecular weights (Mw) shown in the following synthesis examples are the results of measurements by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). For the measurements, a GPC device (HLC-8320GPC (manufactured by Tosoh Corporation)) was used, and the measurement conditions were as follows:
Column: Shodex (registered trademark) KD-805/Shodex (registered trademark) KD-803 (manufactured by Showa Denko K.K.)
Column temperature: 50°C
Flow rate: 1 mL/min Eluent: N,N-dimethylformamide (DMF), lithium bromide monohydrate (30 mM)/phosphoric acid (30 mM)/tetrahydrofuran (1%)
・Standard sample: polyethylene oxide

The chemical imidization ratio shown in the following synthesis examples was calculated by the following method. 100 mg of polyimide powder was placed in an NMR sample tube (NMR Sampling Tube Standard, φ5 (Kusano Scientific Co., Ltd.)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) (0.53 ml) was added. Complete dissolution was achieved by applying ultrasound. This solution was subjected to 500 MHz proton NMR measurement using an NMR measurement device (JNM-ECA500) (JEOL Ltd.). The chemical imidization ratio was calculated by the following formula, using a proton derived from a structure that remains unchanged before and after imidization as the reference proton, and the integrated value of the peak of this proton and the integrated value of the proton peak derived from the NH group of the amic acid that appears around 9.5 ppm to 11.0 ppm:
Chemical imidization rate (%) = (1 - α x/y) x 100
In the above formula, x is the integrated value of the proton peak derived from the NH group of the amic acid, y is the integrated value of the peak of the reference proton, and α is the ratio of the number of reference protons to one NH group proton of the amic acid in the case of polyamic acid (imidization rate 0%).

Synthesis Example 1 Synthesis of Polyamic Acid (P-1) 11.00 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 0.05 g of 2,6-di-tert-butyl-p-cresol, and 33.14 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 21.45 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 42.68 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 1 hour and then at 60° C. for 93 hours. The resulting polyamic acid had a repeating unit structure represented by the following (P-1), and its weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 22,868.

Synthesis Example 2 Synthesis of Polyamic Acid (P-2) 9.85 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 12.84 g of 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene, 0.04 g of 2,6-di-tert-butyl-p-cresol, and 53.04 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 37.25 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride and 86.91 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 3 hours and then at 50° C. for 89 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-2), and had a weight average molecular weight (Mw) of 25,273 as measured by GPC in terms of polystyrene.

Synthesis Example 3 Synthesis of Polyamic Acid (P-3) 10.18 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 11.26 g of 1,4-bis(4-aminophenoxy)benzene, 0.04 g of 2,6-di-tert-butyl-p-cresol, and 50.13 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 38.49 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 89.82 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 3 hours and then at 50° C. for 89 hours. The resulting polyamic acid had a repeating unit structure represented by the following (P-3), and its weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 26,998.

Synthesis Example 4 Synthesis of Polyamic Acid (P-4) 13.73 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 9.14 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 0.06 g of 2,6-di-tert-butyl-p-cresol, and 53.50 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 37.08 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride and 86.53 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 2 hours and then at 50° C. for 88 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-4), and had a weight average molecular weight (Mw) of 24,973 as measured by GPC in terms of polystyrene.

Synthesis Example 5 Synthesis of Polyamic Acid (P-5) 9.47 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 14.70 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 0.04 g of 2,6-di-tert-butyl-p-cresol, and 56.49 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature in air, and then 35.79 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride and 83.51 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 3 hours and then at 50° C. for 89 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-5), and had a weight average molecular weight (Mw) of 27,852 as measured by GPC in terms of polystyrene.

Synthesis Example 6 Synthesis of Polyamic Acid (P-6) 3.59 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 13.01 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 0.01 g of 2,6-di-tert-butyl-p-cresol, and 66.47 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 23.33 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride and 93.33 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 3 hours and then at 50° C. for 95 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-6), and had a weight average molecular weight (Mw) of 56,737 as converted into polystyrene by GPC.

Synthesis Example 7 Synthesis of Polyamic Acid (P-7) 1.16 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 16.22 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 0.01 g of 2,6-di-tert-butyl-p-cresol, and 69.53 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature in air, and then 22.62 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride and 90.47 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 3 hours and then at 50° C. for 95 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-7), and had a weight average molecular weight (Mw) of 58,225 as measured by GPC in terms of polystyrene.

Synthesis Example 8 Synthesis of Polyamic Acid (P-8) 9.71 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 13.54 g of 4,4′-bis(4-aminophenoxy)biphenyl, 0.04 g of 2,6-di-tert-butyl-p-cresol, and 54.34 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 36.72 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride and 85.67 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 3 hours and then at 50° C. for 92 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-8), and had a weight average molecular weight (Mw) of 33,012 as measured by GPC in terms of polystyrene.

Synthesis Example 9 Synthesis of Polyamic Acid (P-9) 6.22 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 10.18 g of bis[4-(4-aminophenoxy)phenyl]sulfone, 0.03 g of 2,6-di-tert-butyl-p-cresol, and 65.70 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature in air, and then 23.52 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride and 94.08 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 2 hours and then at 50° C. for 92 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-9), and had a weight average molecular weight (Mw) of 31,175 as measured by GPC in terms of polystyrene.

Synthesis Example 10 Synthesis of Polyamic Acid (P-10) 6.62 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 13.34 g of 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene (BPF-AN, manufactured by JFE Chemical Corporation), and 79.86 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 25.04 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride and 25.14 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 3 hours and then at 40° C. for 42 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-10), and had a weight average molecular weight (Mw) of 25,249 as measured by GPC in terms of polystyrene.

Synthesis Example 11 Synthesis of Polyamic Acid (P-11) 7.94 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 10.46 g of bis(4-aminophenyl) terephthalate, 0.05 g of 4-methoxyphenol, and 87.05 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 29.98 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 58.04 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 3 hours and then at 50° C. for 74 hours. The resulting polyamic acid had a repeating unit structure represented by the following (P-11), and had a weight average molecular weight (Mw) of 29,792 as measured by GPC in terms of polystyrene.

Synthesis Example 12 Synthesis of Polyamic Acid (P-12) 7.94 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 10.46 g of 1,4-phenylenebis(4-aminobenzoate), 0.05 g of 4-methoxyphenol, and 87.05 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 29.98 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 58.04 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 3 hours and then at 50° C. for 74 hours. The resulting polyamic acid had a repeating unit structure represented by the following (P-12), and had a weight average molecular weight (Mw) of 24,660 as measured by GPC relative to polystyrene standards.

Synthesis Example 13 Synthesis of Polyamic Acid (P-13) 10.95 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 17.01 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 0.05 g of 2,6-di-tert-butyl-p-cresol, and 112.00 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 32.00 g of hydroquinone diphthalic anhydride (HQDA, manufactured by Air Water Inc.) and 28.00 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 2 hours and then at 40° C. for 39 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-13), and had a weight average molecular weight (Mw) of 21,092 as measured by GPC in terms of polystyrene.

Synthesis Example 14 Synthesis of Polyamic Acid (P-14) 8.63 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 13.41 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 0.04 g of 2,6-di-tert-butyl-p-cresol, and 88.32 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature in air, and then 37.92 g of bis-(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)propane-2,2-diylbis(2-methyl-4,1-phenylene) and 51.68 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 2 hours and then at 40° C. for 39 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-14), and had a weight average molecular weight (Mw) of 16,379 as measured by GPC in terms of polystyrene.

Synthesis Example 15 Synthesis of Polyamic Acid (P-15) 6.23 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 9.68 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 63.64 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 29.09 g of 9,9-bis[4-(3,4-dicarboxyphenoxy)phenylfluorenedioic anhydride (BPF-PA, manufactured by JFE Chemical Corporation) and 41.36 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 3 hours and then at 40° C. for 42 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-15), and had a weight average molecular weight (Mw) of 24,559 as measured by GPC in terms of polystyrene.

Synthesis Example 16 Synthesis of Polyamic Acid (P-16) 5.29 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 10.36 g of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 0.04 g of 4-methoxyphenol, and 65.87 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 24.68 g of 9,9-bis[4-(3,4-dicarboxyphenoxy)phenylfluorenedioic anhydride (BPF-PA, manufactured by JFE Chemical Corporation) and 28.23 g of N-ethyl-2-pyrrolidone were added to the system, and the mixture was stirred at room temperature for 4 hours and then at 50° C. for 26.5 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-16), and had a weight average molecular weight (Mw) of 28,330 as measured by GPC in terms of polystyrene.

Synthesis Example 17 Synthesis of Polyamic Acid (P-17) 6.181 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 9.60 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 0.04 g of 4-methoxyphenol, and 79.65 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature in air, and then 24.0 g of 5-isobenzofurancarboxylic acid, 1,3-dihydro-1,3-dioxo-cyclohexylidene-4,1-phenylene ester (BPZ-TME, manufactured by Honshu Chemical Industry Co., Ltd.) and 39.82 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 1 hour and then at 50° C. for 63 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-17), and had a weight average molecular weight (Mw) of 13,550 as measured by GPC in terms of polystyrene.

Synthesis Example 18 Synthesis of Polyamic Acid (P-18) 8.65 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 13.44 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 0.053 g of 4-methoxyphenol, and 105.62 g of N-ethyl-2-pyrrolidone were dissolved by stirring under air at room temperature, and then 15.0 g of p-phenylenebis(trimellitate anhydride) (TAHQ, manufactured by Manac Corporation), 15.67 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride, and 52.81 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 1 hour and then at 50° C. for 40 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-18), and had a weight average molecular weight (Mw) of 36,287 as converted into polystyrene by GPC.

Synthesis Example 19 Synthesis of Polyamic Acid (P-19) 8.65 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 13.44 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 0.054 g of 4-methoxyphenol, and 107.24 g of N-ethyl-2-pyrrolidone were dissolved by stirring under air at room temperature, and then 9.0 g of p-phenylenebis(trimellitate anhydride) (TAHQ, manufactured by Manac Corporation), 22.49 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride, and 53.62 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 1 hour and then at 50° C. for 40 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-19), and had a weight average molecular weight (Mw) of 34,006 as converted into polystyrene by GPC.

Synthesis Example 20 Synthesis of Polyamic Acid (P-20) 7.418 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 11.52 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 0.047 g of 4-methoxyphenol, and 126.47 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 15.0 g of p-biphenylenebis(trimellitic acid monoester anhydride) (BP-TME, manufactured by Honshu Chemical Co., Ltd.), 13.44 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride, and 63.23 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 1 hour and then at 50° C. for 40 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-20), and had a weight average molecular weight (Mw) of 28,962 as measured by GPC in terms of polystyrene.

Synthesis Example 21 Synthesis of Polyamic Acid (P-21) 7.418 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 11.52 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 0.047 g of 4-methoxyphenol, and 126.47 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature in air, and then 9.0 g of p-biphenylenebis(trimellitic acid monoester anhydride) (BP-TME, manufactured by Honshu Chemical Co., Ltd.), 19.28 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride, and 63.23 g of N-ethyl-2-pyrrolidone were added to the system, and the mixture was stirred at room temperature for 1 hour and then at 50° C. for 40 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-21), and had a weight average molecular weight (Mw) of 26,182 as measured by GPC in terms of polystyrene.

Synthesis Example 22: Synthesis of Solvent-Soluble Polyimide (P-22) 80.42 g of N-ethyl-2-pyrrolidone, 3.66 g of acetic anhydride, and 0.61 g of triethylamine were added to 40.21 g of the polyamic acid (P-16) obtained in Synthesis Example 16. The mixture was stirred in air at room temperature for 30 minutes, followed by stirring at 60°C for 3 hours. This solution was slowly added to 437.15 g of stirring methanol, and the mixture was stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 874.30 g of methanol and then dried under reduced pressure at 80°C to obtain a solvent-soluble polyimide powder having the repeating unit structure represented by the following formula (P-22). The chemical imidization rate was 95.3%.

Synthesis Example 23 Synthesis of Solvent-Soluble Polyimide (P-23) 9.51 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 18.66 g of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 0.06 g of 4-methoxyphenol, and 98.06 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 23.99 g of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, 7.87 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride, and 42.03 g of N-ethyl-2-pyrrolidone were added to the system, and the mixture was stirred at room temperature for 2 hours and then at 50° C. for 24 hours. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 29,468. To 50.00 g of the resulting polyamic acid, 100.00 g of N-ethyl-2-pyrrolidone, 5.51 g of acetic anhydride, and 0.91 g of triethylamine were added, and the mixture was stirred in air at room temperature for 30 minutes, followed by stirring at 60°C for 3 hours. This solution was slowly added to 547.47 g of stirring methanol, and the mixture was stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 1094.94 g of methanol and then dried under reduced pressure at 80°C to obtain a solvent-soluble polyimide powder having the repeating unit structure represented by the following (P-23). The chemical imidization rate was 95.3%.

Synthesis Example 24 Synthesis of Solvent-Soluble Polyimide (P-24) 9.25 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 18.15 g of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 0.06 g of 4-methoxyphenol, and 97.52 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 15.55 g of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, 16.76 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride, and 41.79 g of N-ethyl-2-pyrrolidone were added to the system, and the mixture was stirred at room temperature for 2 hours and then at 50° C. for 24 hours. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 30,055. To 50.00 g of the resulting polyamic acid, 100.00 g of N-ethyl-2-pyrrolidone, 5.39 g of acetic anhydride, and 0.89 g of triethylamine were added, and the mixture was stirred in air at room temperature for 30 minutes, followed by stirring at 60°C for 3 hours. This solution was slowly added to 546.97 g of stirring methanol, and the mixture was stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 1093.94 g of methanol and then dried under reduced pressure at 80°C to obtain a solvent-soluble polyimide powder having the repeating unit structure represented by the following (P-24). The chemical imidization rate was 95.3%.

Comparative Synthesis Example 1 Synthesis of Polyamic Acid (P-25) 30.00 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 0.13 g of 2,6-di-tert-butyl-p-cresol, and 90.38 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 24.51 g of pyromellitic anhydride and 37.11 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 13 hours and then at 80° C. for 51 hours. The resulting polyamic acid had a repeating unit structure represented by the following (P-25), and had a weight average molecular weight (Mw) of 10,579 as measured by GPC in terms of polystyrene.

Comparative Synthesis Example 2 Synthesis of Polyamic Acid (P-26) 42.28 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 0.09 g of 4-methoxyphenol, and 144.42 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature in air, and then 46.13 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 61.89 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 1 hour and then at 80° C. for 75 hours. A polyamic acid having the repeating unit structure represented by the following (P-26) was obtained.

Comparative Synthesis Example 3 Synthesis of Polyamic Acid (P-27) 31.71 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 0.09 g of 4-methoxyphenol, and 137.13 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 52.24 g of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 58.77 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 3 hours and then at 80°C for 75 hours. A polyamic acid having the repeating unit structure represented by the following (P-27) was obtained.

Comparative Synthesis Example 4 Synthesis of Polyamic Acid (P-28) 18.00 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 0.08 g of 2,6-di-tert-butyl-p-cresol, and 54.23 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 13.22 g of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 30.40 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 62 hours and then at 40° C. for 34 hours. The resulting polyamic acid had a repeating unit structure represented by the following (P-28), and had a weight average molecular weight (Mw) of 42,930 as measured by GPC relative to polystyrene standards.

Comparative Synthesis Example 5 Synthesis of Polyamic Acid (P-29) 15.00 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 0.06 g of 2,6-di-tert-butyl-p-cresol, and 45.19 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 17.21 g of 1,1′-bicyclohexane-3,3′,4,4′-tetracarboxylic acid-3,3′,4,4′-dianhydride (BPDA-H, manufactured by Iwatani Industrial Gases Corporation) and 30.12 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 62 hours and then at 40° C. for 34 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-29), and had a weight average molecular weight (Mw) of 45,136 as converted into polystyrene by GPC.

Comparative Synthesis Example 6 Synthesis of Solvent-Soluble Polyimide (P-30) 8.60 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 16.85 g of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 0.05 g of 4-methoxyphenol, and 148.85 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 27.72 g of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 63.79 g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 1 hour and then at 50°C for 87 hours. The weight average molecular weight (Mw) of the resulting polyamic acid, measured in terms of polystyrene by GPC, was 27,335.
To 60.00 g of the resulting polyamic acid, 60.00 g of N-ethyl-2-pyrrolidone, 4.49 g of acetic anhydride, and 0.58 g of pyridine were added, and the mixture was stirred in air at room temperature for 30 minutes, followed by stirring at 50°C for 3 hours. This solution was slowly added to 437.76 g of stirring methanol, and the mixture was stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 875.52 g of methanol and then dried under reduced pressure at 60°C to obtain a solvent-soluble polyimide powder having the repeating unit structure represented by the following formula (P-30). The chemical imidization rate was 93.2%.

Example 1
27.75 g of a solution (solids concentration: 30 wt %) containing the polyamic acid (P-1) obtained in Synthesis Example 1, 1.67 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.42 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and 0.17 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the mixture was filtered using a polypropylene filter with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

Example 2
32.24 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-2) obtained in Synthesis Example 2, 1.93 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.48 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert- 0.15 g of (butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Ltd., and 0.19 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 3
33.16 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-2) obtained in Synthesis Example 2, 1.93 g of NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.48 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert 0.15 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.19 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 4
22.08 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-3) obtained in Synthesis Example 3, 1.32 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.33 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzoyl)) were used. A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 0.10 g of (dibenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.), 0.13 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 11.04 g of N-ethyl-2-pyrrolidone, and then filtering the solution using a polypropylene filter having a pore size of 5 μm.

Example 5
32.49 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-3) obtained in Synthesis Example 3, 0.97 g of NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.49 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and 0.49 g of IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzoyl)methyl) as a photopolymerizable copolymer were used. A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 0.15 g of (acryloxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Ltd., 0.19 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), and 0.71 g of N-ethyl-2-pyrrolidone, and then filtering the solution using a polypropylene filter having a pore size of 5 μm.

Example 6
33.16 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-4) obtained in Synthesis Example 4, 0.99 g of NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.50 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert 0.15 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.20 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 7
29.96 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-5) obtained in Synthesis Example 5, 1.80 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.45 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzoyl)) were used. A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 0.13 g of (dibenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.), 0.18 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 2.48 g of N-ethyl-2-pyrrolidone, and then filtering the solution using a polypropylene filter having a pore size of 5 μm.

Example 8
23.89 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-5) obtained in Synthesis Example 5, 0.72 g of NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.36 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzoyl)) as a photopolymerizable copolymer were used. A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 0.11 g of (acryloxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.), 0.14 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 4.78 g of N-ethyl-2-pyrrolidone, and then filtering the solution using a polypropylene filter having a pore size of 5 μm.

Example 9
37.84 g of a solution (solid content: 20% by weight) containing the polyamic acid (P-6) obtained in Synthesis Example 6, 1.51 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.38 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl)propanol) as a photopolymerizable copolymer were added. A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 0.11 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.15 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and then filtering the solution using a polypropylene filter having a pore size of 5 μm.

Example 10
37.84 g of a solution (solid content: 20% by weight) containing the polyamic acid (P-7) obtained in Synthesis Example 7, 1.51 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.38 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert- 0.11 g of (butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Ltd., and 0.15 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 11
22.08 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-8) obtained in Synthesis Example 8, 1.32 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.33 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzoyl)) were used. A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 0.10 g of (dibenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.), 0.13 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 11.04 g of N-ethyl-2-pyrrolidone, and then filtering the solution using a polypropylene filter having a pore size of 5 μm.

Example 12
31.50 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-8) obtained in Synthesis Example 8, 0.95 g of NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.47 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzoyl)) as a photopolymerizable copolymer were used. A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 0.14 g of (acryloxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Ltd., 0.19 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), and 1.75 g of N-ethyl-2-pyrrolidone, and then filtering the solution using a polypropylene filter having a pore size of 5 μm.

Example 13
33.11 g of a solution (solid content: 20% by weight) containing the polyamic acid (P-9) obtained in Synthesis Example 9, 1.32 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.33 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert- 0.10 g of (butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Ltd., and 0.13 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 14
20.75 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-10) obtained in Synthesis Example 10, 1.25 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.31 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzoyl)methyl) as a photopolymerizable copolymer were used. A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 0.09 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.), 0.12 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 2.47 g of N-ethyl-2-pyrrolidone, and then filtering the solution using a polypropylene filter having a pore size of 5 μm.

Example 15
23.66 g of a solution (solid content: 25% by weight) containing the polyamic acid (P-11) obtained in Synthesis Example 11, 0.99 g of N-ethyl-2-pyrrolidone, 0.59 g of NK ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.30 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert 0.09 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.12 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 16
24.78 g of a solution (solid content: 25% by weight) containing the polyamic acid (P-12) obtained in Synthesis Example 12, 0.62 g of NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.31 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert 0.09 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.12 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 17
27.64 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-13) obtained in Synthesis Example 13, 1.66 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.41 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert- 0.12 g of (butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Ltd., and 0.17 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 18
28.42 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-13) obtained in Synthesis Example 13, 0.85 g of NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.43 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert 0.13 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.17 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 19
27.64 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-14) obtained in Synthesis Example 14, 1.66 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.41 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert- 0.12 g of (butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Ltd., and 0.17 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 20
28.42 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-14) obtained in Synthesis Example 14, 0.85 g of NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.43 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert 0.13 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.17 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 21
21.40 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-15) obtained in Synthesis Example 15, 1.28 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.32 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzoyl)) were used. A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 0.10 g of (dibenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.), 0.13 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 1.77 g of N-ethyl-2-pyrrolidone, and then filtering the solution using a polypropylene filter having a pore size of 5 μm.

Example 22
37.81 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-16) obtained in Synthesis Example 16, 2.27 g of NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.57 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert 0.17 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.23 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 23
65.34 g of a solution (solid content: 25% by weight) containing the polyamic acid (P-17) obtained in Synthesis Example 17, 3.27 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.82 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert- 0.25 g of (butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Ltd., and 0.33 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 24
38.23 g of a solution (solid content: 25 wt %) containing the polyamic acid (P-18) obtained in Synthesis Example 18, 0.96 g of NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.48 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and 0.48 g of IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert 0.14 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.19 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 25
38.23 g of a solution (solid content: 25% by weight) containing the polyamic acid (P-19) obtained in Synthesis Example 19, 0.96 g of NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.48 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert 0.14 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.19 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 26
38.57 g of a solution (solid content: 20 wt %) containing the polyamic acid (P-20) obtained in Synthesis Example 20, 0.77 g of NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.39 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert 0.12 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.15 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 27
38.57 g of a solution (solid content: 20% by weight) containing the polyamic acid (P-21) obtained in Synthesis Example 21, 0.77 g of NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.39 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert 0.12 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.15 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 28
The solvent-soluble polyimide (P-22) powder (11.02 g) obtained in Synthesis Example 22, N-ethyl-2-pyrrolidone (25.71 g), NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) (2.20 g) as a crosslinking agent, IRGACURE® OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) (0.55 g) as a photoradical initiator, IRGANOX® 3114 (1,3,5-tris(3,5-di-tert-butyl)phenyl) (0.55 g) as a photopolymerizable copolymer, and the like were then mixed together. 0.17 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.22 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

Example 29
The solvent-soluble polyimide (P-23) powder (10.89 g) obtained in Synthesis Example 23, N-ethyl-2-pyrrolidone (26.00 g), NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) (2.18 g) as a crosslinking agent, IRGACURE® OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) (0.54 g) as a photoradical initiator, IRGANOX® 3114 (1,3,5-tris(3,5-di-tert-butyl)phenyl) (0.54 g) as a photopolymerizable copolymer, and 1,3,5-tris(3,5-di-tert-butyl)phenyl) (0.54 g) as a photopolymerizable copolymer. 0.16 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.22 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

<Example 30>
The solvent-soluble polyimide (P-24) powder (10.89 g) obtained in Synthesis Example 24, N-ethyl-2-pyrrolidone (26.00 g), NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) (2.18 g) as a crosslinking agent, IRGACURE® OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) (0.54 g) as a photoradical initiator, IRGANOX® 3114 (1,3,5-tris(3,5-di-tert-butyl)phenyl) (0.54 g) as a photopolymerizable copolymer, and 1,3,5-tris(3,5-di-tert-butyl)phenyl) (0.54 g) as a photopolymerizable copolymer. 0.16 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.22 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

<Comparative Example 1>
27.75 g of a solution (solids concentration: 30 wt %) containing the polyamic acid (P-25) obtained in Comparative Synthesis Example 1, 1.67 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.42 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and 0.17 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the mixture was filtered using a polypropylene filter with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Comparative Example 2>
26.17 g of a solution (solids concentration: 30 wt %) containing the polyamic acid (P-26) obtained in Comparative Synthesis Example 2, 1.57 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.39 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and 0.16 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the mixture was filtered using a polypropylene filter with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Comparative Example 3>
25.08 g of a solution (solids concentration: 30 wt %) containing the polyamic acid (P-27) obtained in Comparative Synthesis Example 3, 1.50 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.38 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and 0.15 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the mixture was filtered using a polypropylene filter with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Comparative Example 4>
27.96 g of a solution (solids concentration: 27 wt %) containing the polyamic acid (P-28) obtained in Comparative Synthesis Example 4, 1.51 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.38 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and 0.15 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the mixture was filtered using a polypropylene filter with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Comparative Example 5>
27.75 g of a solution (solids concentration: 30 wt %) containing the polyamic acid (P-29) obtained in Comparative Synthesis Example 5, 1.67 g of NK Ester A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.42 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and 0.17 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the mixture was filtered using a polypropylene filter with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Comparative Example 6>
9.14 g of the powder of the solvent-soluble polyimide (P-30) obtained in Comparative Synthesis Example 6, 16.98 g of N-ethyl-2-pyrrolidone, 1.83 g of NK Ester A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, 0.46 g of IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, and IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl)methyl) 0.14 g of (1H,3H,5H)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.18 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a solution of a negative photosensitive resin composition.

[Photosensitivity Evaluation]
The negative photosensitive resin compositions prepared in Examples 1 to 30 and Comparative Examples 1 to 6 were applied to 8-inch silicon wafers using a spin coater (CLEAN TRACK ACT-8, manufactured by Tokyo Electron Limited) and baked at 115°C for 180 seconds or 270 seconds to form photosensitive resin films with thicknesses of 5 to 15 μm on the wafers. Next, the wafers were exposed to light using an i-line stepper (NSR-2205i12D, manufactured by Nikon Corporation). Furthermore, using an automatic developing apparatus (AD-1200, manufactured by Mikasa Co., Ltd.), the wafers were spray-developed for 20 to 240 seconds using cyclopentanone as the developer, followed by spray rinsing with propylene glycol monomethyl ether acetate (PGMEA) for 10 seconds. The film thickness immediately after film formation and the film thickness after development at 0 mJ/cm ² (unexposed area) and 300 mJ/cm ² (exposed area) were measured using an interference film thickness meter (Lambda Ace VM-2110, manufactured by SCREEN Co., Ltd.) to compare the film thicknesses of the unexposed and exposed areas. The film thickness measurement results are shown in Table 1.

From the results in Table 1, in the negative-type photosensitive resin compositions of Examples 1 to 30, the photosensitive resin film in the unexposed areas (0 mJ/cm ² ) was sufficiently dissolved (developed) after development, while the photosensitive resin film in the exposed areas (300 mJ/cm ² ) remained undissolved (developed). That is, a clear difference in solubility (dissolution contrast) between the exposed and unexposed areas of the photosensitive resin film was obtained, and therefore these compositions can be suitably used as negative-type photosensitive resin compositions for a relief pattern creation process in which development is carried out using a general-purpose organic solvent such as cyclopentanone. On the other hand, in the photosensitive resin compositions of Comparative Examples 1, 2, 4, and 5, the photosensitive resin film in the unexposed areas (0 mJ/cm ² ) was not sufficiently dissolved (developed) after development. That is, a clear dissolution contrast was not obtained between the exposed and unexposed areas, and these compositions are unsuitable as negative-type photosensitive resin compositions for a relief pattern creation process in which development is carried out using a general-purpose organic solvent such as cyclopentanone.

[Electrical property evaluation]
The negative photosensitive resin compositions prepared in Examples 1 to 30 and Comparative Examples 1 to 6 were spin-coated onto a 4-inch silicon wafer coated with 20 μm-thick aluminum foil and baked on a hot plate at 115°C for 180 seconds or 270 seconds to form a photosensitive resin film on the aluminum foil. Next, using an i-line aligner (PLA-501, manufactured by Canon Inc.), the entire surface of the wafer was exposed to 500 mJ/ ^cm² , followed by baking in a nitrogen atmosphere at 160°C for 1 hour and then at 230°C for 1 hour. The baked aluminum foil was then immersed in 6N hydrochloric acid to dissolve the aluminum foil, yielding a film. The resulting film was then dried under reduced pressure at 80°C for 2 hours and left for 24 hours in an environment at a temperature of approximately 25°C and a humidity of approximately 42%, after which the dielectric loss tangent at 1 GHz was measured using a cavity resonator (TMR-1A, manufactured by Keycom Co., Ltd.). The dielectric loss tangent measurement conditions were as follows:
Measurement method: Perturbation cavity resonator method Vector network analyzer: FieldFox N9926A (Keysight Technologies, Inc.)
Cavity resonator: TMR-1A (manufactured by Keycom Co., Ltd.)
Cavity volume: 1,192,822 ^mm3
Measurement frequency: approximately 1 GHz
Sample tube: PTFE, inner diameter: 3 mm, length: approximately 30 mm (manufactured by Keycom Co., Ltd.)

[Mechanical property evaluation]
The negative photosensitive resin compositions prepared in Examples 1 to 30 and Comparative Examples 1 to 6 were spin-coated onto 100 nm-thick aluminum wafers and baked on a hot plate at 115°C for 180 seconds or 270 seconds to form photosensitive resin films on the aluminum wafers. Next, using an i-line aligner (PLA-501, manufactured by Canon Inc.), the entire surface of the wafer was exposed to 500 mJ/ ^cm² , followed by baking at 160°C for 1 hour and then at 230°C for 1 hour in a nitrogen atmosphere. The photosensitive resin film was then cut at 5 mm intervals using a dicing saw (DAD323, manufactured by Disco Corporation). The aluminum wafer was then immersed in 6N hydrochloric acid to dissolve the aluminum, yielding 5 mm-wide films. The tensile elongation of the resulting films was then measured using a desktop precision universal testing machine (Autograph AGS-10kNX, manufactured by Shimadzu Corporation). The conditions for measuring the tensile elongation are as follows.
・Desktop precision universal testing machine: Autograph AGS-10kNX (Shimadzu Corporation)
・Film width: 5mm
Distance between grippers: 25 mm
Here, a tensile elongation of 50% means that the film can be stretched up to 1.5 times its original length, in other words, the film breaks when the distance between the grippers is 1.5 times (37.5 mm).

The measurement results for dielectric tangent and tensile elongation are shown in Table 2.

From the results in Table 2, the films obtained from the negative-type photosensitive resin compositions of Examples 1 to 30 had dielectric loss tangent values at 1 GHz that were smaller than those of Comparative Examples 1 to 5. Furthermore, the films obtained from the negative-type photosensitive resin compositions of Examples 1 to 30 had improved tensile elongation values than those of Comparative Examples 1 to 6.
That is, the negative-type photosensitive resin compositions of Examples 1 to 30 are capable of forming relief patterns, and simultaneously have the features of a low dielectric tangent and high tensile elongation, and therefore can be suitably used for producing electronic materials that require excellent electrical and mechanical properties.

Claims (14)

A photosensitive resin composition comprising a reaction product of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings, and a solvent,
the reaction product is a polyamic acid or a polyimide obtained by dehydrating and cyclizing a polyamic acid,
The polyamic acid has at least a structural unit represented by the following formula (1):
The polyimide has at least a structural unit represented by the following formula (2):
Ar ₂ in the formula (1) and Ar ₄ in the formula (2) are tetravalent organic groups represented by the following formula (3):
Ar ₁ in the formula (1) and Ar ₃ in the formula (2) are divalent organic groups represented by the following formula (6):
Photosensitive resin composition.
[In formula (1), Ar ₁ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar ₂ represents a tetravalent organic group having three or more aromatic rings.]
[In formula (2), _Ar3 represents a divalent organic group having a photopolymerizable group and an aromatic ring, and _Ar4 represents a tetravalent organic group having three or more aromatic rings.]
[In formula (3), _X1 and _X2 each independently represent an ether bond or an ester bond . _R1 and _R2 each independently represent an alkyl group having 1 to 6 carbon atoms which may be substituted. Y represents a divalent organic group represented by the following formula ( 3-2). n1 and n2 each independently represent an integer of 0 to 3. When there are multiple _R1s , the multiple _R1s may be the same or different. When there are multiple _R2s , the multiple _R2s may be the same or different. * represents a bond.]
[In formula (3-2), _Z2 represents a divalent organic group represented by the following formula (4) or (5). _R5 and _R6 each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. n5 and n6 each independently represent an integer of 0 to 4. When there are multiple _R5s , the multiple _R5s may be the same or different. When there are multiple _R6s , the multiple _R6s may be the same or different. * represents a bond.]

In formula (4), R ₇ and R ₈ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom. * represents a bond.
In formula (5), _R9 and _R10 each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms. * represents a bond.
[In formula (6), _Z3 represents an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond; _Z4 represents a direct bond, an ester bond, or an amide bond; _Z5 represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a thioether bond, or a sulfonyl bond; m2 represents an integer of 0 or 1; _R11 represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group; _R12 represents a hydrogen atom or a methyl group; and * represents a bond.] The photosensitive resin composition according to claim 1, wherein _Z3 and _Z4 in the formula (6) are ester bonds. 3. The photosensitive resin composition according to claim 1, wherein R ₁₁ in the formula (6) is a 1,2-ethylene group. The photosensitive resin composition according to any one of claims 1 to 3, further comprising a photoradical polymerization initiator. The photosensitive resin composition according to any one of claims 1 to 4, further comprising a crosslinkable compound. The photosensitive resin composition according to any one of claims 1 to 5, which is used to form an insulating film. The photosensitive resin composition according to any one of claims 1 to 6, which is a negative-type photosensitive resin composition. A resin film formed by firing a coating film of the photosensitive resin composition described in any one of claims 1 to 7. The resin film according to claim 8, which is an insulating film. A photosensitive resist film comprising a substrate film, a photosensitive resin layer formed from the photosensitive resin composition described in any one of claims 1 to 7, and a cover film. (1) applying the photosensitive resin composition according to any one of claims 1 to 7 onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a substrate having a cured relief pattern, comprising the step of: heat-treating the relief pattern to form a cured relief pattern. The method for producing a substrate with a cured relief pattern according to claim 11, wherein the developer used for the development is an organic solvent. A substrate with a cured relief pattern produced by the method of claim 11 or 12. A semiconductor device comprising a semiconductor element and a cured film provided above or below the semiconductor element, wherein the cured film is a cured relief pattern formed from the photosensitive resin composition described in any one of claims 1 to 7.