Photosensitive resin composition

Abstract

This photosensitive resin composition comprises: 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.

Description

[Technical Field]

[0001] 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 having a cured relief pattern, a substrate having a cured relief pattern, and a semiconductor device having a cured relief pattern. [Background technology]

[0002] Polyimide resins, which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic components and passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices. Among these polyimide resins, those provided 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 treatment through curing. Such photosensitive polyimide precursors have the advantage of enabling significant process reduction compared to conventional non-photosensitive polyimide resins.

[0003] Patent Documents 1 and 2 propose photosensitive resin compositions containing polyamic acid or polyimide using diamines having a (meth)acryloyloxy group. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-347404 [Patent Document 2] Special Publication No. 2012-516927 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, semiconductor devices have become required to transmit and process large amounts of information at high speeds, and as a result, electrical signals are becoming increasingly higher in frequency. Because high-frequency electrical signals are prone to attenuation, it is necessary to reduce transmission loss. For this reason, 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.

[0006] Furthermore, when forming a cured relief pattern, development is performed using a developer, and an alkaline aqueous developer or an organic solvent developer is generally used. Photosensitive resins for obtaining a cured relief pattern 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 have inferior resolution compared to positive-type resins, but are easily thickened and film-formed, and are highly reliable, making them suitable for the manufacture of semiconductor devices requiring such features. However, conventional negative-type photosensitive resins containing polyamic acid have extremely high solubility in alkaline aqueous developer, making it difficult to control the dissolution rate and potentially making it difficult to obtain a desired relief pattern. Furthermore, negative-type photosensitive resins containing polyamic acid have a high affinity for alkaline aqueous developer, which means they tend to swell during development, leading to problems such as the stress generated during drying that causes the formed relief pattern to peel off 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.

[0007] 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 tangent and high tensile elongation. However, the photosensitive resin compositions described in Patent Documents 1 and 2 do not satisfy all of these properties.

[0008] In view of the above circumstances, an 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 having a cured relief pattern; a substrate having a cured relief pattern; and a semiconductor device having a cured relief pattern. [Means for solving the problem]

[0009] As a result of extensive research to achieve the above object, the present inventors have found 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 having a low dielectric tangent and high tensile elongation, thereby completing the present invention.

[0010] [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): [ka] [In formula (1), Ar1 represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar2 represents a tetravalent organic group having three or more aromatic rings.] [ka] [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 Ar2 in the formula (1) and Ar4 in the formula (2) are tetravalent organic groups represented by the following formula (3): [ka] [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.] [ka] [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 more than one Z1, the multiple Z1s may be the same or different. When there is more than one n4, the multiple n4s may be the same or different. When there is more than one R3, the multiple R3s may be the same or different. When there is more than one R4, 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.] [ka] [In formula (4), R7 and R8 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 R 10 each independently represents 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 Ar1 in the formula (1) and Ar3 in the formula (2) are divalent organic groups represented by the following formula (6): [ka] [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 to 1. R 11 represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group, R 12 represents a hydrogen atom or a methyl group. * represents a bond.] [6] The photosensitive resin composition according to [5], wherein Z3 and Z4 in the formula (6) are ester bonds. [7] R in the formula (6) 11 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 which 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) heat-treating the relief pattern to form a hardened relief pattern; A method for producing a substrate with a cured relief pattern, comprising:

[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] . [Effects of the Invention]

[0011] According to the present invention, there are provided 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 having a cured relief pattern; a substrate having a cured relief pattern; and a semiconductor device having a cured relief pattern. DETAILED DESCRIPTION OF THE INVENTION

[0012] (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.

[0013] <Reaction products> The reaction product is a reaction product of 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.

[0014] 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.

[0015] 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.

[0016] 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.

[0017] The reaction product preferably 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, in that the resulting cured film has a lower dielectric tangent and a higher tensile elongation.

[0018] 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, and may be, for example, four or more. The upper limit of the number of aromatic rings is not particularly limited, and may be, for example, eight or less, or six or less.

[0019] Regarding the counting of aromatic rings in "three or more aromatic rings," polycyclic aromatic rings formed by the fusion 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 fused ring, so it is counted as two aromatic rings. And a perylene ring is considered to be a structure formed by the fusion 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.

[0020] Examples of the tetracarboxylic acid derivative 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.

[0021] The tetracarboxylic acid derivative having three or more aromatic rings is preferably an aromatic tetracarboxylic acid derivative having three or more aromatic rings. An aromatic tetracarboxylic acid refers to a compound having four carboxy groups bonded to the same or different aromatic rings.

[0022] 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, and may be, for example, four or more. The upper limit of the number of aromatic rings is not particularly limited, and may be, for example, eight or less, or six or less.

[0023] 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 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 %.

[0024] The reaction product is preferably a polyamic acid or a polyimide obtained by dehydrating and cyclizing a polyamic acid. From the viewpoint of obtaining a finer relief pattern, a polyimide obtained by dehydrating and cyclizing a 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.

[0025] 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). [ka] [In formula (1), Ar1 represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar2 represents a tetravalent organic group having three or more aromatic rings.] [Chemical formula] [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.]

[0026] [<Ar1 and Ar3>] Ar1 and Ar3 are divalent organic groups having a photopolymerizable group and an aromatic ring, and are not particularly limited as long as they exhibit 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 aforementioned photopolymerizable groups.

[0027] Ar1 and Ar3 are preferably divalent organic groups represented by the following formula (6). [Chemical formula] [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-), and 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 (-SO2-). m2 represents an integer of 0 to 1. R 11 represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group, and R 12 represents a hydrogen atom or a methyl group. * represents a bond.]

[0028] Examples of the alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group include, for example, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1,2-butylene group, 2,3-butylene group, 1,2-pentylene group, 2,4-pentylene group, 1,2-hexylene group, 1,2-cyclopropylene group, 1,2-cyclobutylene group, 1,3-cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, and alkylene groups in which at least a part of these hydrogen atoms are substituted with a hydroxyl group (for example, 2-hydroxy-1,3-propylene group).

[0029] As Z3, an ester bond is preferred. As Z4, an ester bond is preferred. R 11 As, a 1,2-ethylene group is preferred.

[0030] Examples of the divalent organic group represented by formula (6) include, for example, the following divalent organic groups.

Chemical formula

[0031] <<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. From the viewpoint of preferably obtaining the effects of the present invention, they are preferably divalent organic groups represented by the following formula (3).

Chemical formula

[0032] 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 "carbon atom number of 1 to 6" 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.

[0033] [ka] [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.]

[0034] 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 "hydrocarbon group having 1 to 6 carbon atoms which may be substituted" refers to the number of carbon atoms in the "hydrocarbon group" excluding the substituents. The number of substituents is not particularly limited.

[0035] 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.

[0036] [ka] [In formula (4), R7 and R8 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 R 10 each independently represents 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.]

[0037] 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.

[0038] R9 and R 10 Examples of the substituent in the optionally substituted alkylene group having 1 to 6 carbon atoms in the formula (I) 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 "carbon atom number of 1 to 6" 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.

[0039] R9 and R 10 Examples of the substituent in the optionally substituted arylene group having 6 to 10 carbon atoms in the formula (I) 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 "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.

[0040] Examples of the divalent organic group represented by formula (4) include divalent organic groups represented by the following formulas: [ka] In the formula, * represents a bond.

[0041] Examples of the divalent organic group represented by formula (5) include divalent organic groups represented by the following formulas: [ka] In the formula, R 13 ~R 15each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkoxy group having 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. R 13 If there are multiple, multiple R 13 may be the same or different. 14 If there are multiple, multiple R 14 may be the same or different. 15 If there are multiple, multiple R 15 may be the same or different. * represents a bond.

[0042] R 13 ~R 15 Specific examples of the alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom 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. R 13 ~R 15 Specific examples of the alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom in the formula (I) include an alkoxy group formed from an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom.

[0043] Examples of Ar2 and Ar4 include tetravalent organic groups represented by the following formulas. [ka] [ka] In the formula, * represents a bond.

[0044] <Other structural units> The polyamic acid may have structural units other than the structural unit represented by formula (1). Examples of the structural units other than the structural unit represented by formula (1') include the structural unit represented by the following formula (1'). The polyimide may have other structural units in addition to the structural unit represented by formula (2). Examples of other structural units include the structural unit represented by the following formula (2'). [ka] [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. 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.] [ka] [In formula (2'), Ar 3’ 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 4’ represents a tetravalent organic group having three or more aromatic rings or a tetravalent organic group not having three or more aromatic rings. 3’ is a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar 4’ is a tetravalent organic group having three or more aromatic rings.]

[0045] Ar 1’ and Ar 2’ Examples of the combination include the following combinations (i) to (iii). (i):Ar 1’represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar 2’ represents a tetravalent organic group that does not have three or more aromatic rings (ii):Ar 1’ represents a divalent organic group other than a divalent organic group having a photopolymerizable group or an aromatic ring, and Ar 2’ represents a tetravalent organic group that does not have three or more aromatic rings (iii):Ar 1’ represents a divalent organic group other than a divalent organic group having a photopolymerizable group or an aromatic ring, and Ar 2’ represents a tetravalent organic group having three or more aromatic rings

[0046] Ar 3’ and Ar 4’ Examples of the combinations include the following combinations (iv) to (vi). (iv):Ar 3’ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar 4’ represents a tetravalent organic group that does not have three or more aromatic rings (v):Ar 3’ represents a divalent organic group other than a divalent organic group having a photopolymerizable group or an aromatic ring, and Ar 4’ represents a tetravalent organic group that does not have three or more aromatic rings (vi):Ar 3’ represents a divalent organic group other than a divalent organic group having a photopolymerizable group or an aromatic ring, and Ar 4’ represents a tetravalent organic group having three or more aromatic rings

[0047] < <Ar 1’ and Ar 3’ >> Ar 1’ and Ar 3’ Examples of the divalent organic group having a photopolymerizable group and an aromatic ring in Ar include the divalent organic groups having a photopolymerizable group and an aromatic ring exemplified in the description of Ar1 and Ar3. Ar 1’ and Ar 3’The divalent organic group other than the photopolymerizable group and the divalent organic group having an aromatic ring in formula (I) is not particularly limited, but a divalent organic group having three or more aromatic rings is preferred because it allows the resulting cured film to have a lower dielectric tangent and a higher tensile elongation. 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). [ka] [In formula (13), X 21 and X 22 R each independently 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-). 21 and R 22 Y each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted. 20 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. R 21 If there are multiple, multiple R 21 may be the same or different. 22 If there are multiple, multiple R 22 may be the same or different. * represents a bond.]

[0048] R 21 and R 22 Specific examples of the optionally substituted alkyl group having 1 to 6 carbon atoms in the formula (I) include the optionally substituted alkyl groups having 1 to 6 carbon atoms exemplified in the description of R1 and R2. The "carbon atom number of 1 to 6" 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.

[0049] [ka] [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 (-SO2-). 23 and R 24 each independently represents an optionally substituted hydrocarbon group having 1 to 6 carbon atoms; m21 represents an integer of 0 to 3; n23 and n24 each independently represents an integer of 0 to 4; Z 21 If there are multiple, multiple Z 21 may be the same or different. When there are multiple n24s, the multiple n24s may be the same or different. R 23 If there are multiple, multiple R 23 may be the same or different. 24 If there are multiple, multiple R 24 may be the same or different. * represents a bond. In formula (13-2), Z 22 R represents a divalent organic group represented by the following formula (14) or (15). 25 and R 26 each independently represents an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. n25 and n26 each independently represent an integer of 0 to 4. R 25 If there are multiple, multiple R 25 may be the same or different. 26 If there are multiple, multiple R 26 may be the same or different. * represents a bond.]

[0050] R 23 , R 24 , R 25 , and R 26 Specific examples of the optionally substituted hydrocarbon group having 1 to 6 carbon atoms in the formula (I) include the optionally substituted hydrocarbon groups having 1 to 6 carbon atoms exemplified in the description of R3, R4, R5, and R6. The term "carbon atom number 1 to 6" in the "hydrocarbon group having 1 to 6 carbon atoms which may be substituted" refers to the number of carbon atoms in the "hydrocarbon group" excluding the substituents. The number of substituents is not particularly limited.

[0051] R 23 , R 24 , R 25 and R 26 Specific examples of the optionally substituted alkyl group having 1 to 6 carbon atoms in the formula (I) include the optionally substituted alkyl groups having 1 to 6 carbon atoms exemplified in the description of R1 and R2.

[0052] [ka] [In formula (14), R 27 and R 28 each independently represents 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 represents 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.]

[0053] R 27 and R 28 Specific examples of the hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom in the formula (I) include the hydrocarbon groups having 1 to 6 carbon atoms which may be substituted with a halogen atom exemplified in the description of R7 and R8.

[0054] R 29 and R 30 Specific examples of the optionally substituted alkylene group having 1 to 6 carbon atoms in the formula (I) include R and R 10 Examples include the alkylene groups having 1 to 6 carbon atoms which may be substituted as exemplified in the description of the above. The "carbon atom number of 1 to 6" 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.

[0055] R 29 and R 30 Specific examples of the optionally substituted arylene group having 6 to 10 carbon atoms in the formula (I) include R and R 10 Examples thereof include the optionally substituted arylene groups having 6 to 10 carbon atoms exemplified in the description of the above. The "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.

[0056] Examples of the divalent organic group represented by formula (14) include divalent organic groups represented by the following formulas: [ka] In the formula, * represents a bond.

[0057] Examples of the divalent organic group represented by formula (15) include divalent organic groups represented by the following formulas: [ka] In the formula, R 33 ~R 35 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkoxy group having 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. R 33 If there are multiple, multiple R 33 may be the same or different. 34 If there are multiple, multiple R 34 may be the same or different. 35 If there are multiple, multiple R 35may be the same or different. * represents a bond.

[0058] R 33 ~R 35 Specific examples of the alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom in R 13 ~R 15 Examples include alkyl groups having 1 to 6 carbon atoms which may be substituted with a halogen atom as exemplified in the description of (1). R 33 ~R 35 Specific examples of the alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom in the formula (I) include an alkoxy group formed from an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom.

[0059] Ar 1’ and Ar 3’ Examples of the group include divalent organic groups represented by the following formula: [ka] [ka] In the formula, * represents a bond.

[0060] Other Ar 1’ and Ar 3’ Examples of the group include divalent organic groups represented by the following formula: [ka] In the formula, * represents a bond.

[0061] < <Ar 2’ and Ar 4’ >> Ar 2’ and Ar 4’ Examples of the tetravalent organic group having three or more aromatic rings in the formula (I) include the tetravalent organic groups having three or more aromatic rings exemplified in the description of Ar2 and Ar4. Ar2’ and Ar 4’ In the above, examples of the tetravalent organic group not having three or more aromatic rings include a tetravalent organic group having one or two aromatic rings and a tetravalent organic group not having 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 not having an aromatic ring is derived, for example, from an aliphatic tetracarboxylic anhydride derivative. Such a tetravalent organic group is not particularly limited, but examples thereof include the following tetravalent organic groups. [ka] [ka] In the formula, * represents a bond.

[0062] 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 %.

[0063] 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 %.

[0064] The weight-average molecular weight of the reaction product is not particularly limited, but the weight-average molecular weight measured in terms of polystyrene 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, still more preferably 10,000 to 50,000, and particularly preferably 10,000 to 40,000.

[0065] <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.

[0066] The method for producing the reaction product is not particularly limited, and examples thereof 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 WO2013 / 157586.

[0067] The reaction product is produced, for example, by reacting 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 (condensation polymerization).

[0068] 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. [ka] (In formula [D-1], D 1 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-2], D 2 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D 3 represents an alkyl group having 1 to 4 carbon atoms).

[0069] 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-mentioned solvent to the extent that the reaction product does not precipitate.

[0070] 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 mass %, more preferably 5 to 30 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.

[0071] 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.

[0072] 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 the polyamic acid, which is 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.

[0073] 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 -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is 0.1 to 30 times, preferably 0.2 to 20 times, the molar ratio of the amic acid groups, and the amount of the acid anhydride is 1 to 50 times, preferably 1.5 to 30 times, the molar ratio of the amic 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 polyisoimide as a by-product. 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) of chemical imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0074] When recovering the produced imidized product from the imidization reaction solution, the reaction solution may be poured into a solvent to cause precipitation. Examples of solvents 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 normal or reduced pressure.

[0075] In the polyimide, the repeating units are partially or entirely ring-closed, and the imidization rate in the polyimide is preferably 20 to 99%, more preferably 30 to 99%, and even more preferably 50 to 99%.

[0076] The polyimide may be end-capped. The method for end-capping is not particularly limited, and for example, a conventionally known method using a monoamine or an acid anhydride can be used.

[0077] <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. [ka] (In formula [D-1], D 1 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-2], D 2 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D 3 represents an alkyl group having 1 to 4 carbon atoms).

[0078] The solvent can be used in an amount of, for example, 30 to 1500 parts by mass, preferably 100 to 1000 parts by mass, per 100 parts by mass of the reaction product, depending on the desired coating film thickness and viscosity of the photosensitive resin composition.

[0079] <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.

[0080] <<Photoradical polymerization initiator>> The photoradical polymerization initiator is not particularly limited as long as it is a compound that absorbs the light of the light source used for photocuring. Examples of the photoradical polymerization initiator 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, cyclohexanone peroxide, and 2,2',5,5'-tetra(tert-butylperoxy)- ... Organic peroxides such as 3,3'-bis(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; quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 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, 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl) alkylphenone compounds such as 2-dimethylamino-2-(4-methylbenzyl)-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-diphenylphosphine oxide; 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;

[0081] The photoradical polymerization initiator is commercially available, and examples thereof include IRGACURE [registered trademark] 651, 184, 2959, 127, 907, 369, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, OXE03, OXE04, 250, 1173, MBF, TPO, 4265, and TPO (all manufactured by BASF), KAYACURE [registered trademark] DETX-S, MBP, DMBI, EPA, and OA (all manufactured by Nippon Kayaku Co., Ltd.), VICURE-10 and 55 (all manufactured by Stauffer Co., Ltd.), and ESACURE Examples of such anti-aging agents 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.

[0082] The content of the photoradical polymerization initiator is not particularly limited, but is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the reaction product, and more preferably 0.5 to 15 parts by mass from the viewpoint of photosensitivity characteristics. When the content of the photoradical polymerization initiator is 0.1 part by mass or more relative to 100 parts by mass of the reaction product, the photosensitivity of the photosensitive resin composition tends to improve, while when the content is 20 parts by mass or less, the thick-film curability of the photosensitive resin composition tends to improve.

[0083] <<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 such compounds include di-, tri-, or tetra(meth)acrylates of tungsten, ethylene oxide or propylene oxide adducts of these compounds, 2-isocyanateethyl(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 addition, in this specification, (meth)acrylate means acrylate and methacrylate.

[0084] The content of the crosslinkable compound is not particularly limited, but is preferably 1 to 100 parts by mass, and more preferably 1 to 50 parts by mass, relative to 100 parts by mass of the reaction product.

[0085] <<Thermal hardener>> 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.

[0086] <<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.

[0087] <<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 relative to 100 parts by mass of the reaction product.

[0088] <<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-Dimethylaminobenzylideneindanone, 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-acetone methyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These may be used alone or in combination.

[0089] The content of the sensitizer is not particularly limited, but is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the reaction product.

[0090] <<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 suitable adhesives 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.

[0091] Among these adhesion aids, it is more preferable to use a silane coupling agent in terms of adhesive strength.

[0092] The content of the adhesion promoter is not particularly limited, but is preferably in the range of 0.5 to 25 parts by mass per 100 parts by mass of the reaction product.

[0093] <<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 that can be used 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.

[0094] The content of the thermal polymerization inhibitor is not particularly limited, but is preferably in the range of 0.005 to 12 parts by mass per 100 parts by mass of the reaction product.

[0095] <<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 2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole. Examples of suitable benzotriazoles include 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, and 1-methyl-1H-tetrazole. 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.

[0096] The content of the azole compound is not particularly limited, but is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the reaction product, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the content of the azole compound relative to 100 parts by mass of the reaction product is 0.1 part by mass 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, while when the content is 20 parts by mass or less, excellent photosensitivity is achieved, which is preferable.

[0097] <<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 hindered phenol compounds 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'-butylidene-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-hydrocinnamamide), 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-hydroxybenzyl) 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-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, etc., 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.

[0098] The content of the hindered phenol compound is not particularly limited, but is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the reaction product, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. When the content of the hindered phenol compound relative to 100 parts by mass of the reaction product is 0.1 part by mass 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, while when the content is 20 parts by mass or less, excellent photosensitivity is achieved, which is preferable.

[0099] The photosensitive resin composition can be suitably used as a negative photosensitive resin composition for producing a cured relief pattern, which will be described later.

[0100] (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. Firing can be carried out, 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 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.

[0101] (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 comprises 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.

[0102] 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 onto 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.

[0103] 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.

[0104] (Method for manufacturing 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; Includes:

[0105] Each step will be described below.

[0106] (1) A 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 according to 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, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or the like, or spray application using a spray coater, can be used.

[0107] If necessary, the coating film made of the photosensitive resin composition can be dried, and examples of the drying method include air drying, heat drying using an oven or a hot plate, vacuum drying, etc. Specifically, when air drying or heat drying is performed, drying can be carried out under conditions of 20°C to 200°C for 1 minute to 1 hour. In this way, a photosensitive resin layer can be formed on the substrate.

[0108] (2) A step of exposing the photosensitive resin layer to light In this process, the photosensitive resin layer formed in the above process (1) is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, mirror projection, or 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 25 mJ / cm. 2 ~2000mJ / cm 2 is desirable.

[0109] Thereafter, post-exposure baking (PEB) and / or pre-development baking may be performed at any temperature and time combination as necessary for the purpose of improving photosensitivity, etc. The baking conditions are preferably in the range of a temperature of 50°C to 200°C and a time of 10 seconds to 600 seconds, but are not limited to these ranges as long as they do not impair the properties of the photosensitive resin composition.

[0110] (3) A 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 needed, for the purpose of adjusting the shape of the relief pattern, etc. The developer used for development is preferably an organic solvent. Examples of the organic solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. 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 types of each solvent, for example, a combination of several types, can also be used.

[0111] (4) A step of heat-treating the relief pattern to form a hardened relief pattern. In this step, the relief pattern obtained by the development 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.

[0112] 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.

[0113] (Semiconductor Devices) 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.

[0114] (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. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched therebetween. 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.

[0115] The photosensitive resin composition of the present invention is useful not only for application to the semiconductor devices described above, but also for applications such as an interlayer insulating film for a multilayer circuit, a cover coat for a flexible copper-clad board, a solder resist film, and a liquid crystal alignment film. [Example]

[0116] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0117] 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 (Showa Denko K.K.) Column temperature: 50℃ ·Flow rate: 1mL / min Eluent: N,N-dimethylformamide (DMF), lithium bromide monohydrate (30 mM) / phosphoric acid (30 mM) / tetrahydrofuran (1%) Standard sample: Polyethylene oxide

[0118] The chemical imidization ratio shown in the following synthesis examples was calculated as follows. 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 ultrasonic irradiation. This solution was measured by proton NMR at 500 MHz using an NMR measurement system (JNM-ECA500) (JEOL Ltd.). The proton derived from the structure that remains unchanged before and after imidization was determined as the reference proton. The chemical imidization ratio was calculated using the integrated peak value of this proton and the integrated peak value of the proton derived from the NH group of the amic acid that appears around 9.5 ppm to 11.0 ppm according to the following formula: Chemical imidization rate (%) = (1 - α x / y) × 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%).

[0119] <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 under air at room temperature, 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. The mixture was stirred at room temperature for 1 hour and then at 60°C for 93 hours. The resulting polyamic acid had the repeating unit structure shown below (P-1), and its weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 22,868. [ka]

[0120] <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 under air at room temperature. 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 and stirred at room temperature for 3 hours, followed by stirring at 50°C for 89 hours. The resulting polyamic acid had the repeating unit structure shown below (P-2), and its weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 25,273. [ka]

[0121] <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 under air at room temperature. 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 and stirred at room temperature for 3 hours, followed by stirring at 50°C for 89 hours. The resulting polyamic acid had the repeating unit structure shown below (P-3), and its weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 26,998. [ka]

[0122] <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 under air at room temperature. 37.08 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 86.53 g of N-ethyl-2-pyrrolidone were then added to the system and stirred at room temperature for 2 hours, followed by stirring at 50°C for 88 hours. The resulting polyamic acid had the repeating unit structure shown below (P-4), and its weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 24,973. [ka]

[0123] <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 under air at room temperature. 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 and stirred at room temperature for 3 hours, followed by stirring at 50°C for 89 hours. The resulting polyamic acid had the repeating unit structure shown below (P-5), and its weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 27,852. [ka]

[0124] <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 under air at room temperature. 23.33 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 93.33 g of N-ethyl-2-pyrrolidone were then added to the system and stirred at room temperature for 3 hours, followed by stirring at 50°C for 95 hours. The resulting polyamic acid had the repeating unit structure shown below (P-6), and its weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 56,737. [ka]

[0125] <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 under air at room temperature. 22.62 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 90.47 g of N-ethyl-2-pyrrolidone were then added to the system and stirred at room temperature for 3 hours, followed by stirring at 50°C for 95 hours. The resulting polyamic acid had the repeating unit structure shown below (P-7), and its weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 58,225. [ka]

[0126] <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 under air at room temperature. 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 and stirred at room temperature for 3 hours, followed by stirring at 50°C for 92 hours. The resulting polyamic acid had the repeating unit structure shown below (P-8), and its weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 33,012. [ka]

[0127] <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 under air at room temperature. 23.52 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 94.08 g of N-ethyl-2-pyrrolidone were then added to the system and stirred at room temperature for 2 hours, followed by stirring at 50°C for 92 hours. The resulting polyamic acid had the repeating unit structure shown below (P-9), and its weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 31,175. [ka]

[0128] <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. 25.04 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 25.14 g of N-ethyl-2-pyrrolidone were then added to the system and stirred at room temperature for 3 hours, followed by stirring at 40°C for 42 hours. The resulting polyamic acid had the repeating unit structure shown below (P-10), and its weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 25,249. [ka]

[0129] 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 under air at room temperature. 29.98 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 58.04 g of N-ethyl-2-pyrrolidone were then added to the system and stirred at room temperature for 3 hours, followed by stirring at 50°C for 74 hours. The resulting polyamic acid had the repeating unit structure shown below (P-11), and its weight-average molecular weight (Mw) measured by GPC relative to polystyrene standards was 29,792. [ka]

[0130] <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 under air at room temperature. 29.98 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 58.04 g of N-ethyl-2-pyrrolidone were then added to the system and stirred at room temperature for 3 hours, followed by stirring at 50°C for 74 hours. The resulting polyamic acid had the repeating unit structure shown below (P-12), and its weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 24,660. [ka]

[0131] <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. 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 and stirred at room temperature for 2 hours, followed by stirring at 40°C for 39 hours. The resulting polyamic acid had the repeating unit structure shown below (P-13). Its weight-average molecular weight (Mw) measured by GPC relative to polystyrene standards was 21,092. [ka]

[0132] 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 under 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 obtained polyamic acid had a repeating unit structure represented by the following (P-14), and had a weight average molecular weight (Mw) of 16,379 as measured by GPC in terms of polystyrene. [ka]

[0133] <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 under air at room temperature. Then, 29.09 g of 9,9-bis[4-(3,4-dicarboxyphenoxy)phenylfluorene dianhydride (BPF-PA, manufactured by JFE Chemical Corporation) and 41.36 g of N-ethyl-2-pyrrolidone were added to the system and stirred at room temperature for 3 hours, followed by stirring at 40°C for 42 hours. The resulting polyamic acid had a repeating unit structure represented by the following formula (P-15). Its weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 24,559. [ka]

[0134] <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 under air at room temperature. Then, 24.68 g of 9,9-bis[4-(3,4-dicarboxyphenoxy)phenylfluorene dianhydride (BPF-PA, manufactured by JFE Chemical Corporation) and 28.23 g of N-ethyl-2-pyrrolidone were added to the system and stirred at room temperature for 4 hours, followed by stirring at 50°C for 26.5 hours. The resulting polyamic acid had the repeating unit structure shown below (P-16). Its weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 28,330. [ka]

[0135] <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 under 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 obtained polyamic acid had a repeating unit structure represented by the following (P-17), and had a weight average molecular weight (Mw) of 13,550 as measured by GPC in terms of polystyrene. [ka]

[0136] <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 at room temperature under air, 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 obtained polyamic acid had a repeating unit structure represented by the following (P-18), and had a weight average molecular weight (Mw) of 36,287 as converted into polystyrene by GPC. [ka]

[0137] 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 at room temperature under air, 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, and the mixture was stirred at room temperature for 1 hour and then at 50°C for 40 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-19), and had a weight average molecular weight (Mw) of 34,006 as converted into polystyrene by GPC. [ka]

[0138] <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, and the mixture was stirred at room temperature for 1 hour and then at 50°C for 40 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-20), and had a weight average molecular weight (Mw) of 28,962 as measured by GPC in terms of polystyrene. [ka]

[0139] 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 under 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 obtained polyamic acid had a repeating unit structure represented by the following (P-21), and had a weight average molecular weight (Mw) of 26,182 as measured by GPC in terms of polystyrene. [ka]

[0140] Synthesis Example 22: Synthesis of solvent-soluble polyimide (P-22) To 40.21 g of the polyamic acid (P-16) obtained in Synthesis Example 16, 80.42 g of N-ethyl-2-pyrrolidone, 3.66 g of acetic anhydride, and 0.61 g of triethylamine were added and 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 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 shown below (P-22). The chemical imidization rate was 95.3%. [ka]

[0141] Synthesis Example 23: Synthesis of solvent-soluble polyimide (P-23) 9.51 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, 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 under air at room temperature. 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 stirred at room temperature for 2 hours, followed by stirring 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 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 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 shown below (P-23). ​​The chemical imidization rate was 95.3%. [ka]

[0142] Synthesis Example 24: Synthesis of solvent-soluble polyimide (P-24) 9.25 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, 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 under air at room temperature. 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 stirred at room temperature for 2 hours, followed by stirring 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 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 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 shown below (P-24). The chemical imidization rate was 95.3%. [ka]

[0143] 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 under air at room temperature, and then 24.51 g of pyromellitic anhydride and 37.11 g of N-ethyl-2-pyrrolidone were added to the system. The mixture was stirred 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 (P-25) below, and its weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 10,579. [ka]

[0144] 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 under 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. The mixture was stirred at room temperature for 1 hour and then at 80°C for 75 hours. A polyamic acid having the repeating unit structure shown below (P-26) was obtained. [ka]

[0145] 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. The mixture was stirred at room temperature for 3 hours and then at 80°C for 75 hours. A polyamic acid having the repeating unit structure shown below (P-27) was obtained. [ka]

[0146] 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 under air at room temperature, and then 13.22 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 30.40 g of N-ethyl-2-pyrrolidone were added to the system. The mixture was stirred at room temperature for 62 hours and then at 40°C for 34 hours. The resulting polyamic acid had the repeating unit structure shown below (P-28), and its weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 42,930. [ka]

[0147] 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 under air at room temperature. 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 and stirred at room temperature for 62 hours, followed by 34 hours at 40°C. The resulting polyamic acid had the repeating unit structure shown below (P-29), and its weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 45,136. [ka]

[0148] Comparative Synthesis Example 6: Synthesis of solvent-soluble polyimide (P-30) 8.60 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, 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. 27.72 g of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 63.79 g of N-ethyl-2-pyrrolidone were then added to the system, and the mixture was stirred at room temperature for 1 hour, followed by stirring at 50°C for 87 hours. The weight-average molecular weight (Mw) of the resulting polyamic acid measured by GPC in terms of polystyrene 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 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 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 shown below (P-30). The chemical imidization rate was 93.2%. [ka]

[0149] 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 crosslinker, 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 then filtered using a polypropylene filter with a pore size of 5 μm to prepare a solution of a negative-tone photosensitive resin composition.

[0150] <Example 2> 32.24 g of a solution (solid concentration: 30% by weight) containing the polyamic acid (P-2) obtained in Synthesis Example 2, and NK ester as a crosslinker A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 1.93 g of A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.48 g of IRGACURE® OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, 0.15 g of IRGANOX® 3114 (1,3,5-tris(3,5-di-tert-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.). The solution was then filtered using a polypropylene filter with a pore size of 5 μm.

[0151] Example 3 The mixture consisted of 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 crosslinker, 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-butyl) methyl acrylate, manufactured by BASF Japan Ltd.) as a photopolymerizable copolymer. 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 with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

[0152] Example 4 22.08 g of a solution (solid content: 30 wt%) 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 crosslinker, 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 with a pore size of 5 μm.

[0153] <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 crosslinker, 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 with a pore size of 5 μm.

[0154] Example 6 The mixture was diluted with 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 crosslinker, 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 0.50 g of IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl) methyl acrylate, manufactured by BASF Japan Ltd.) as a photopolymerizable copolymer. 0.15 g of (-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.20 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 with a pore size of 5 μm to prepare a solution of a negative-type photosensitive resin composition.

[0155] 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 with a pore size of 5 μm.

[0156] 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 crosslinker, 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)methyl) 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 with a pore size of 5 μm.

[0157] Example 9 37.84 g of a solution (solid concentration: 20% by weight) containing the polyamic acid (P-6) obtained in Synthesis Example 6, and NK ester as a crosslinker A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 1.51 g of A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.38 g of IRGACURE® OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, 0.11 g of IRGANOX® 3114 (1,3,5-tris(3,5-di-tert-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.). The solution was then filtered using a polypropylene filter with a pore size of 5 μm.

[0158] Example 10 37.84 g of a solution (solid content: 20% by weight) containing the polyamic acid (P-7) obtained in Synthesis Example 7, and NK ester as a crosslinker A solution of a negative-tone photosensitive resin composition was prepared by mixing and dissolving 1.51 g of A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.38 g of IRGACURE® OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, 0.11 g of IRGANOX® 3114 (1,3,5-tris(3,5-di-tert-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.). The solution was then filtered using a polypropylene filter with a pore size of 5 μm.

[0159] 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 with a pore size of 5 μm.

[0160] 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 crosslinker, 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 0.47 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 0.14 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 with a pore size of 5 μm.

[0161] Example 13 33.11 g of a solution (solid concentration: 20% by weight) containing the polyamic acid (P-9) obtained in Synthesis Example 9, and NK ester as a crosslinker A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 1.32 g of A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.33 g of IRGACURE® OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, 0.10 g of IRGANOX® 3114 (1,3,5-tris(3,5-di-tert-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.). The solution was then filtered using a polypropylene filter with a pore size of 5 μm.

[0162] Example 14 20.75 g of a solution (solid content: 30 wt%) 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 crosslinker, 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 added. 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 (BASF Japan Ltd.), 0.12 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.), and 2.47 g of N-ethyl-2-pyrrolidone, and then filtering the solution using a polypropylene filter with a pore size of 5 μm.

[0163] 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-butyl) methyl acrylate) were used. 0.09 g of (1H,3H,5H)-butyl-4-hydroxybenzyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (BASF Japan Ltd.) and 0.12 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

[0164] Example 16 24.78 g of a solution (solid content: 25 wt%) 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 crosslinker, 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 0.31 g of IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl) methyl acrylate) as a photopolymerizable copolymer were added. 0.09 g of (1H,3H,5H)-butyl-4-hydroxybenzyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (BASF Japan Ltd.) and 0.12 g of KBM-5103 (3-acryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved, and the solution was filtered using a polypropylene filter with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

[0165] Example 17 27.64 g of a solution (solid concentration: 30% by weight) containing the polyamic acid (P-13) obtained in Synthesis Example 13, and NK ester as a crosslinker A solution of a negative-tone photosensitive resin composition was prepared by mixing and dissolving 1.66 g of A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.41 g of IRGACURE® OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, 0.12 g of IRGANOX® 3114 (1,3,5-tris(3,5-di-tert-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.). The solution was then filtered using a polypropylene filter with a pore size of 5 μm.

[0166] Example 18 28.42 g of a solution (solid content: 30 wt%) 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 crosslinker, 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 0.43 g of IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl) methyl acrylate) as a photopolymerizable copolymer were added. 0.13 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 with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

[0167] Example 19 27.64 g of a solution (solid content: 30% by weight) containing the polyamic acid (P-14) obtained in Synthesis Example 14, and NK ester as a crosslinker A solution of a negative-tone photosensitive resin composition was prepared by mixing and dissolving 1.66 g of A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.41 g of IRGACURE® OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, 0.12 g of IRGANOX® 3114 (1,3,5-tris(3,5-di-tert-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.). The solution was then filtered using a polypropylene filter with a pore size of 5 μm.

[0168] Example 20 28.42 g of a solution (solid content: 30 wt%) 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 crosslinker, 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 0.43 g of IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl) methyl acrylate) as a photopolymerizable copolymer were added. 0.13 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 with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

[0169] 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 with a pore size of 5 μm.

[0170] Example 22 37.81 g of a solution (solid content: 30 wt%) 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 crosslinker, 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-butyl) methyl acrylate) were used. 0.17 g of (-butyl-4-hydroxybenzyl)-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 with a pore size of 5 μm to prepare a solution of a negative-type photosensitive resin composition.

[0171] Example 23 65.34 g of a solution (solid concentration: 25% by weight) containing the polyamic acid (P-17) obtained in Synthesis Example 17, and NK ester as a crosslinker A solution of a negative-tone photosensitive resin composition was prepared by mixing and dissolving 3.27 g of A-200 (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.82 g of IRGACURE® OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photoradical initiator, 0.25 g of IRGANOX® 3114 (1,3,5-tris(3,5-di-tert-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.). The solution was then filtered using a polypropylene filter with a pore size of 5 μm.

[0172] 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 crosslinker, 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-butyl) methyl acrylate) as a photopolymerizable copolymer were added. 0.14 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 with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

[0173] Example 25 38.23 g of a solution (solid content: 25 wt%) 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 crosslinker, 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-butyl) methyl acrylate) were used. 0.14 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 with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

[0174] <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 crosslinker, 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 0.39 g of IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl) methyl acrylate) as a photopolymerizable copolymer were added. 0.12 g of (-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.15 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 with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

[0175] Example 27 38.57 g of a solution (solid content: 20 wt%) 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 crosslinker, 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 0.39 g of IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl) methyl acrylate) as a photopolymerizable copolymer were added. 0.12 g of (-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.) and 0.15 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 with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

[0176] 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) methyl acrylate), and 1,3,5-tris(3,5-di-tert-butyl) methyl acrylate were mixed together. 0.17 g of (-butyl-4-hydroxybenzyl)-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 with a pore size of 5 μm to prepare a solution of a negative-type photosensitive resin composition.

[0177] 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) methyl acrylate), and 1,3,5-tris(3,5-di-tert-butyl) methyl acrylate were mixed together. 0.16 g of (-butyl-4-hydroxybenzyl)-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 with a pore size of 5 μm to prepare a solution of a negative-type photosensitive resin composition.

[0178] 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) methyl acrylate), and 1,3,5-tris(3,5-di-tert-butyl) methyl acrylate were mixed together. 0.16 g of (-butyl-4-hydroxybenzyl)-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 with a pore size of 5 μm to prepare a solution of a negative-type photosensitive resin composition.

[0179] <Comparative Example 1> A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 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 crosslinker, 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.). The solution was then filtered using a polypropylene filter with a pore size of 5 μm.

[0180] <Comparative Example 2> A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 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.). The solution was then filtered using a polypropylene filter with a pore size of 5 μm.

[0181] <Comparative Example 3> A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 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 crosslinker, 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.). The solution was then filtered using a polypropylene filter with a pore size of 5 μm.

[0182] <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-tone photosensitive resin composition.

[0183] <Comparative Example 5> A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 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 crosslinker, 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.). The solution was then filtered using a polypropylene filter with a pore size of 5 μm.

[0184] <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 acrylate) were used. 0.14 g of (-butyl-4-hydroxybenzyl)-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 with a pore size of 5 μm to prepare a solution of a negative-type photosensitive resin composition.

[0185] [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 a thickness 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 deposition and the 0 mJ / cm 2 (unexposed area) and 300mJ / cm 2 The film thickness of the exposed area after development was measured using an interference film thickness meter (Lambda Ace VM-2110, manufactured by SCREEN Co., Ltd.) to compare the film thickness of the exposed area with that of the unexposed area. The film thickness measurement results are shown in Table 1.

[0186] [Table 1]

[0187] From the results in Table 1, the negative photosensitive resin compositions of Examples 1 to 30 had a low photoirradiation rate in the unexposed area (0 mJ / cm ) after development. 2 ) photosensitive resin film is fully dissolved (developed) and the exposed area (300 mJ / cm 2 ) remained without dissolving (development). In other words, a clear difference in dissolution (dissolution contrast) of the photosensitive resin film was obtained between the exposed and unexposed areas, and therefore the composition can be suitably used as a negative photosensitive resin composition 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, the photosensitive resin compositions of Comparative Examples 1, 2, 4, and 5 remained without dissolving (development) in the unexposed areas (0 mJ / cm 2 ) remained without being sufficiently dissolved (developed). In other words, no clear dissolution contrast was obtained between the exposed and unexposed areas, and the composition is unsuitable as a negative-tone photosensitive resin composition for a relief pattern creation process in which development is performed using a general-purpose organic solvent such as cyclopentanone.

[0188] [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 covered 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, an i-line aligner (PLA-501, manufactured by Canon Inc.) was used to apply 500 mJ / cm to the wafer. 2 After the entire surface was exposed to light, the foil was baked 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 to stand 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 Corporation). The dielectric loss tangent measurement conditions were as follows: ·Measurement method: perturbation method cavity resonator method Vector network analyzer: FieldFox N9926A (Keysight Technologies) Cavity resonator: TMR-1A (Keycom Co., Ltd.) Cavity volume: 1192822mm 3 Measurement frequency: approx. 1 GHz Sample tube: PTFE, inner diameter: 3 mm, length: approximately 30 mm (Keycom Co., Ltd.)

[0189] [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, an i-line aligner (PLA-501, manufactured by Canon Inc.) was used to apply 500 mJ / cm2 of radiation onto the wafers. 2 After the entire surface was exposed to UV light, the wafer was baked in a nitrogen atmosphere at 160°C for 1 hour and then at 230°C for 1 hour. The photosensitive resin film was then cut into 5mm-wide 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 a 5mm-wide film. The tensile elongation of the resulting film was then measured using a desktop precision universal testing machine (Autograph AGS-10kNX, manufactured by Shimadzu Corporation). The tensile elongation measurement conditions were as follows: Desktop precision universal testing machine: Autograph AGS-10kNX (Shimadzu Corporation) Film width: 5mm Grip distance: 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).

[0190] The measurement results of the dielectric loss tangent and tensile elongation are shown in Table 2.

[0191] [Table 2]

[0192] The results in Table 2 show that the films obtained from the negative photosensitive resin compositions of Examples 1 to 30 had lower dielectric loss tangent values ​​at 1 GHz than those of Comparative Examples 1 to 5. Furthermore, the films obtained from the negative 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 have the features of 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

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, 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 in the formula (1) ２ and Ar in the formula (2) ４ is a tetravalent organic group represented by the following formula (3): Ar in the formula (1) １ and Ar in the formula (2) ３ is a divalent organic group represented by the following formula (6): Photosensitive resin composition. 【Chemistry 1】 [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. 【Chemistry 2】 [In formula (2), Ar ３ represents 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. 【Transformation 3】 [In formula (3), X １ and X ２ R each independently represents an ether bond or an ester bond. １ and R ２ each independently represents an optionally substituted alkyl group having 1 to 6 carbon atoms; 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. R １ If there are multiple R １ may be the same or different. ２ If there are multiple R ２ may be the same or different. * represents a bond.] 【Chemistry 4】 [In formula (3-2), Z ２ R represents a divalent organic group represented by the following formula (4) or (5): ５ and R ６ each independently represents an optionally substituted hydrocarbon group having 1 to 6 carbon atoms; n5 and n6 each independently represent an integer of 0 to 4. R ５ If there are multiple R ５ may be the same or different. ６ If there are multiple R ６ may be the same or different. * represents a bond.] 【Transformation 5】 [In formula (4), R ７ and R ８ each independently represents 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), R ９ and R １０ each independently represents 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.] 【Transformation 6】 [In formula (6), Z ３ represents an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond; Z ４ represents a direct bond, an ester bond or an amide bond. ５ 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. R １１ represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group; R １２ represents a hydrogen atom or a methyl group. * represents a bond.]

2. Z in the formula (6) ３ and Z ４ The photosensitive resin composition according to claim 1 , wherein is an ester bond.

3. R in the formula (6) １１ The photosensitive resin composition according to claim 1 or 2, wherein is a 1,2-ethylene group.

4. The photosensitive resin composition according to any one of claims 1 to 3, further comprising a photoradical polymerization initiator.

5. The photosensitive resin composition according to any one of claims 1 to 4, further comprising a crosslinkable compound.

6. The photosensitive resin composition according to any one of claims 1 to 5, which is used for forming an insulating film.

7. The photosensitive resin composition according to any one of claims 1 to 6, which is a negative photosensitive resin composition.

8. A resin film which is a fired product of a coating film of the photosensitive resin composition according to any one of claims 1 to 7.

9. The resin film according to claim 8, which is an insulating film.

10. A photosensitive resist film comprising a substrate film, a photosensitive resin layer formed from the photosensitive resin composition according to any one of claims 1 to 7, and a cover film.

11. (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) heat-treating the relief pattern to form a hardened relief pattern; A method for producing a substrate with a cured relief pattern, comprising:

12. The method for producing a substrate having a cured relief pattern according to claim 11 , wherein the developer used for the development is an organic solvent.

13. A substrate with a cured relief pattern produced by the method of claim 11 or 12.

14. 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 claims 1 to 7.

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