WO2022202098A1

WO2022202098A1 - Photosensitive resin composition

Info

Publication number: WO2022202098A1
Application number: PCT/JP2022/007899
Authority: WO
Inventors: 貴文遠藤; 秀則石井; 崇洋坂口; 浩司荻野; 有輝星野
Original assignee: 日産化学株式会社
Priority date: 2021-03-22
Filing date: 2022-02-25
Publication date: 2022-09-29
Also published as: KR20230160249A; CN116982003A; TW202244131A; JPWO2022202098A1

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

Photosensitive resin composition

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

Conventionally, polyimide resin, which has excellent heat resistance, electrical properties, and mechanical properties, has been used as an insulating material for electronic parts, and as a passivation film, surface protective film, interlayer insulating film, etc. for semiconductor devices. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor easily form a heat-resistant relief pattern film by thermal imidization treatment by applying, exposing, developing, and curing the precursor. be able to. Such a photosensitive polyimide precursor has the feature of enabling a significant process reduction compared to conventional non-photosensitive polyimide resins.

Patent Documents 1 and 2 propose a photosensitive resin composition containing polyamic acid or polyimide using a diamine having a (meth)acryloyloxy group.

JP-A-2000-347404 Japanese translation of PCT publication No. 2012-516927

2. Description of the Related Art In recent years, semiconductor devices are required to transmit and process a large amount of information at high speed, so the frequency of electrical signals is increasing. Since high-frequency electrical signals are easily attenuated, it is necessary to reduce transmission loss. Therefore, resins used in semiconductor devices are required to have a low dielectric loss tangent.
On the other hand, resins with a low dielectric loss tangent tend to be brittle, and cannot follow the thermal expansion of adjacent materials during a heat treatment process such as a solder reflow process, resulting in breakage or reduced interlayer adhesion. be. Therefore, resins used in semiconductor devices are required to have high tensile elongation.

In addition, when forming a cured relief pattern, development is performed with a developer, and generally an alkaline aqueous solution developer or an organic solvent developer is used. The photosensitive resin used to obtain the hardened relief pattern is divided into two types: the positive type, in which the photosensitive resin in the exposed areas is dissolved in the developer by exposure and development, leaving the photosensitive resin in the unexposed areas, and the photosensitive resin in the unexposed areas. is dissolved in the developer, and the photosensitive resin in the exposed areas remains. In particular, the negative type is inferior to the positive type in resolution, but is easy to form a thick film or a film, and is excellent in reliability. However, conventional negative photosensitive resins containing polyamic acids have a very high solubility in an alkaline aqueous solution developer, so that it is difficult to control the dissolution rate, and there is a concern that it is difficult to obtain a desired relief pattern. Furthermore, since the negative photosensitive resin containing polyamic acid has a high affinity with an alkaline aqueous solution developer, it tends to swell during development, and the relief pattern formed tends to peel off from the substrate due to the stress generated during drying. I had a problem. For this reason, organic solvent development is suitable for negative photosensitive resins containing polyamic acid because the dissolution rate can be controlled relatively easily and there is little concern about peeling of the substrate.

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

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

The present inventors have made intensive studies to solve the above problems, and found that a photosensitive resin composition contains an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid having three or more aromatic rings. By containing a reaction product with a derivative, organic solvent development is possible, and a photosensitive resin composition having a low dielectric loss tangent and a high tensile elongation in the resulting cured film can be obtained. The present invention has been completed.

[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 ring-closing a polyamic acid.
[3] The polyamic acid has at least a structural unit represented by the following formula (1),
The photosensitive resin composition according to [2], wherein the polyimide has at least a structural unit represented by the following formula (2).

[In formula (1), Ar ₁ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar ₂ represents a tetravalent organic group having three or more aromatic rings. ]

[In formula (2), 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. ]
[4] The photosensitive resin composition according to [3], wherein Ar ₂ in the formula (1) and Ar ₄ in the formula (2) are tetravalent organic groups represented by the following formula (3): thing.

[In Formula (3), X ₁ and X ₂ 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. R ₁ and R ₂ each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms. 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 R ₁ s, the multiple R _1s may be the same or different. When there are multiple R ₂ s, the multiple R _2s may be the same or different. * represents a bond. ]

[In formula (3-1), Z ₁ 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. R ₃ and R ₄ 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 Z ₁ is plural, the plural Z ₁ may be the same or different. When n4 is plural, the plural n4 may be the same or different. When R ₃ is plural, the plural R ₃ may be the same or different. When R ₄ is plural, the plural R ₄ may be the same or different. * represents a bond.
In formula (3-2), Z ₂ represents a divalent organic group represented by formula (4) or (5) below. R ₅ and R ₆ 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 R ₅ is plural, the plural R ₅ may be the same or different. When R ₆ is plural, the plural R ₆ may be the same or different. * represents a bond. ]

[In Formula (4), R ₇ and R ₈ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom. * represents a bond.
In formula (5), R ₉ and R ₁₀ each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms. * represents a bond. ]
[5] According to [3] or [4], wherein Ar ₁ in the formula (1) and Ar ₃ in the formula (2) are divalent organic groups represented by the following formula (6): A photosensitive resin composition.

[In formula (6), _Z3 represents an ether bond _, an ester bond, an amide bond, a urethane bond or a urea bond, and Z4 represents a direct bond, an ester bond or an amide bond. _Z5 represents a direct bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, or 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, and 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 formula ( ₆ ) are ester bonds.
[7] The photosensitive resin composition according to [5] or [6], wherein R ₁₁ in formula (6) is a 1,2-ethylene group.
[8] The photosensitive resin composition according to any one of [1] to [7], further comprising a photoradical polymerization initiator.
[9] The photosensitive resin composition according to any one of [1] to [8], further comprising a crosslinkable compound.
[10] The photosensitive resin composition according to any one of [1] to [9], which is used for forming an insulating film.
[11] The photosensitive resin composition according to any one of [1] to [10], which is a negative photosensitive resin composition.
[12] A resin film, which is a baked product of the 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 substrate 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;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a substrate with a cured relief pattern, comprising the step of heat-treating the relief pattern to form a cured relief pattern.
[16] The method for producing a cured relief patterned substrate according to [15], wherein the developer used for the development is an organic solvent.
[17] A substrate with 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 above or below the semiconductor element, wherein the cured film comprises the photosensitive resin composition according to any one of [1] to [11]. A semiconductor device that is a cured relief pattern formed from a material.

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

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

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

Photosensitivity is imparted to the resin composition containing the reaction product by including the aromatic diamine compound having a photopolymerizable group in 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 obtained cured film has a low dielectric loss tangent and a high tensile elongation. .

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

Examples of photopolymerizable groups include radically polymerizable groups, cationic polymerizable groups, and anionically polymerizable groups. Among these, a radically polymerizable group is preferred.
Examples of radically polymerizable groups include acryloyl groups, methacryloyl groups, propenyl ether groups, vinyl ether groups, and vinyl groups.

The reaction product contains 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 the resulting cured film. It is preferable in that dielectric loss tangent and higher tensile elongation can be obtained.

The number of aromatic rings in the aromatic diamine compound having 3 or more aromatic rings is not particularly limited as long as it is 3 or more, but may be 4 or more, for example. The upper limit of the number of aromatic rings is not particularly limited, but may be, for example, 8 or less, or 6 or less.

Regarding how to count aromatic rings in "3 or more aromatic rings", polycyclic aromatic rings formed by condensing two or more aromatic rings such as naphthalene ring and anthracene ring 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 and counts as two aromatic rings. A perylene ring is regarded as a structure formed by bonding two naphthalene rings and counted as two aromatic rings.
Aromatic rings include aromatic hydrocarbon rings, aromatic heterocycles, and the like.

Examples of the tetracarboxylic acid derivative in the "tetracarboxylic acid derivative" include tetracarboxylic dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, and tetracarboxylic acid dialkyl ester dihalide. Carboxylic dianhydrides are preferred.

As the tetracarboxylic derivative having three or more aromatic rings, an aromatic tetracarboxylic acid derivative having three or more aromatic rings is preferable. Aromatic tetracarboxylic acids refer to compounds having a total of four carboxy groups attached to the same or different aromatic rings.

The number of aromatic rings in the tetracarboxylic acid derivative having 3 or more aromatic rings is not particularly limited as long as it is 3 or more, but may be 4 or more, for example. The upper limit of the number of aromatic rings is not particularly limited, but may be, for example, 8 or less, or 6 or less.

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

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

Polyamic acid preferably has at least a structural unit represented by the following formula (1).
Polyimide preferably has at least a structural unit represented by the following formula (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. ]

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

Ar ₁ and Ar ₃ are preferably divalent organic groups represented by the following formula (6).

[In the formula (6), Z ₃ is an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-) or a urea bond (-NHCONH-). Z ₄ represents a direct bond, an ester bond (--COO--) or an amide bond (--NHCO--). Z ₅ is a direct bond, ether bond (-O-), ester bond (-COO-), amide bond (-NHCO-), urethane bond (-NHCOO-), urea bond (-NHCONH-), thioether bond (- S—) or a sulfonyl bond (—SO ₂ —). m2 represents an integer from 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. ]

Examples of the alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group include 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, alkylene in which at least part of these hydrogen atoms are substituted with hydroxyl groups groups (eg, 2-hydroxy-1,3-propylene group) and the like.

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

Examples of the divalent organic group represented by Formula (6) include the following divalent organic groups.

In the formula, * represents a bond. The two bonds are, for example, positioned meta to a substituent having a photopolymerizable group.

<<Ar ₂ and Ar ₄ >>
Ar ₂ in formula (1) and Ar ₄ in formula (2) are not particularly limited as long as they are tetravalent organic groups having three or more aromatic rings and exhibiting the effect of the present invention. , is preferably a divalent organic group represented by the following formula (3) from the viewpoint of suitably obtaining the effects of the present invention.

[In the formula (3), X ₁ and X ₂ are each independently a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-) , represents a urea bond (-NHCONH-), a thioether bond (-S-) or a sulfonyl bond (-SO ₂ -). R ₁ and R ₂ each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms. 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 R ₁ s, the multiple R _1s may be the same or different. When there are multiple R ₂ s, the multiple R _2s may be the same or different. * represents a bond. ]

Examples of the optionally substituted alkyl group having 1 to 6 carbon atoms for R ₁ and R ₂ include alkyl groups having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. In this specification, an alkyl group, unless otherwise specified for its structure, may be linear, branched, cyclic, or two or more of these. may be a combination of
Examples of substituents on 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, nitro group, nitroso group, oxo group, thioxy group, alkoxy group having 1 to 6 carbon atoms, and the like.
In addition, "1 to 6 carbon atoms" in "optionally substituted alkyl group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkyl group" excluding substituents. Also, the number of substituents is not particularly limited.

[In the formula (3-1), Z ₁ is a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), a urea bond ( -NHCONH-), a thioether bond (-S-) or a sulfonyl bond (-SO ₂ -). R ₃ and R ₄ 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 Z ₁ is plural, the plural Z ₁ may be the same or different. When n4 is plural, the plural n4 may be the same or different. When R ₃ is plural, the plural R ₃ may be the same or different. When R ₄ is plural, the plural R ₄ may be the same or different. * represents a bond.
In formula (3-2), Z ₂ represents a divalent organic group represented by formula (4) or (5) below. R ₅ and R ₆ 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 R ₅ is plural, the plural R ₅ may be the same or different. When R ₆ is plural, the plural R ₆ may be the same or different. * represents a bond. ]

Examples of the optionally substituted hydrocarbon group having 1 to 6 carbon atoms in R ₃ , R ₄ , R ₅ and R ₆ include an optionally substituted alkyl group having 1 to 6 carbon atoms, An optionally substituted phenyl group is included. Substituents include, for example, 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 1 carbon atom. alkoxy groups of 1 to 6, and the like.
The "1 to 6 carbon atoms" of the "optionally substituted hydrocarbon group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "hydrocarbon group" excluding substituents. Also, the number of substituents is not particularly limited.

Specific examples of the optionally substituted alkyl group having 1 to 6 carbon atoms for R ₃ , R ₄ , R ₅ and R ₆ include, for example, the substituted alkyl group exemplified in the description of R ₁ and R ₂ A good alkyl group having 1 to 6 carbon atoms is exemplified.

[In formula (4), R ₇ and R ₈ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom. * represents a bond.
In formula (5), R ₉ and R ₁₀ each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms. * represents a bond. ]

The hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom for R ₇ and R ₈ includes, for example, an alkyl group having 1 to 6 carbon atoms and a halogenated alkyl group having 1 to 6 carbon atoms. groups, phenyl groups, halogenated phenyl groups, and the like. Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include fluorine atom, chlorine atom, bromine atom and iodine atom. The halogenated alkyl group having 1 to 6 carbon atoms and the halogenated phenyl group may be partially or wholly halogenated.

Examples of substituents on the optionally substituted alkylene group having 1 to 6 carbon atoms in R ₉ and R ₁₀ include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, sulfo group, amino group, nitro group, nitroso group, oxo group, thioxy group, alkoxy group having 1 to 6 carbon atoms, and the like.
The optionally substituted alkylene group having 1 to 6 carbon atoms includes, for example, 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 methylene group, ethylene group, propylene group, and butylene group.
The "1 to 6 carbon atoms" of the "optionally substituted alkylene group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkylene group" excluding substituents. Also, the number of substituents is not particularly limited.

Examples of substituents on the optionally substituted arylene group having 6 to 10 carbon atoms in R ₉ and R ₁₀ include a halogen atom, an optionally halogenated C 1 to 6 alkyl group, halogen alkoxy groups having 1 to 6 carbon atoms which may be substituted, and the like. Halogenation may be partially or wholly.
The arylene group includes, for example, a phenylene group and a naphthylene group.
The "6 to 10 carbon atoms" of the "optionally substituted arylene group having 6 to 10 carbon atoms" refers to the number of carbon atoms in the "arylene group" excluding substituents. Also, the number of substituents is not particularly limited.

Examples of the divalent organic group represented by formula (4) include divalent organic groups represented by the following formulae.

In the formula, * represents a bond.

Examples of the divalent organic group represented by formula (5) include divalent organic groups represented by the following formulae.

In the formula, R ₁₃ to R ₁₅ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom represents an alkoxy group. n13 represents an integer of 0 to 5; n14 and n15 each independently represent an integer of 0 to 4; When R ₁₃ is plural, the plural R ₁₃ may be the same or different. When R ₁₄ is plural, the plural R ₁₄ may be the same or different. When R ₁₅ is plural, the plural R ₁₅ may be the same or different. * represents a bond.

Specific examples of alkyl groups having 1 to 6 carbon atoms which may be substituted with halogen atoms for R ₁₃ to R ₁₅ include alkyl groups having 1 to 6 carbon atoms and halogen having 1 to 6 carbon atoms. alkyl group. Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include fluorine atom, chlorine atom, bromine atom and iodine atom. A halogenated alkyl group having 1 to 6 carbon atoms may be partially or completely halogenated.
Specific examples of the alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom for R ₁₃ to R ₁₅ are an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom. based on.

Ar ₂ and Ar ₄ include, for example, tetravalent organic groups represented by the following formulas.

In the formula, * represents a bond.

<Other structural units>
The polyamic acid may have structural units other than the structural unit represented by formula (1). Other structural units include, for example, structural units represented by the following formula (1′).
Polyimide may have structural units other than the structural unit represented by formula (2). Other structural units include, for example, structural units represented by the following formula (2′).

[In the formula (1 '), Ar _{1 '} is a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring or a divalent organic group having a photopolymerizable group and an aromatic ring and Ar _2′ represents a tetravalent organic group having 3 or more aromatic rings or a tetravalent organic group having no 3 or more aromatic rings. However, the case where Ar _1' is a divalent organic group having a photopolymerizable group and an aromatic ring and Ar _2' is a tetravalent organic group having 3 or more aromatic rings is excluded. ]

[In formula (2′), Ar _3′ is a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring or a divalent organic group having a photopolymerizable group and an aromatic ring and Ar _4′ represents a tetravalent organic group having 3 or more aromatic rings or a tetravalent organic group having no 3 or more aromatic rings. However, the case where Ar _3' is a divalent organic group having a photopolymerizable group and an aromatic ring and Ar _4' is a tetravalent organic group having 3 or more aromatic rings is excluded. ]

Combinations of Ar _1′ and Ar _2′ include the following combinations (i) to (iii).
(i): A combination in which Ar _1′ represents a photopolymerizable group and a divalent organic group having an aromatic ring, and Ar _2′ represents a tetravalent organic group having no three or more aromatic rings (ii) ): Ar _1′ represents a divalent organic group other than a photopolymerizable group and a divalent organic group having an aromatic ring, and Ar _2′ is a tetravalent organic group having no three or more aromatic rings (iii): Ar _{1 '} represents a divalent organic group other than a photopolymerizable group and a divalent organic group having an aromatic ring, and Ar _{2 '} has three or more aromatic rings 4 a combination representing a valent organic group

Combinations of Ar _3′ and Ar _4′ include the following combinations (iv) to (vi).
(iv): A combination in which Ar _{3 '} represents a photopolymerizable group and a divalent organic group having an aromatic ring, and Ar _{4 '} represents a tetravalent organic group having no three or more aromatic rings (v ): Ar _3' represents a divalent organic group other than a photopolymerizable group and a divalent organic group having an aromatic ring, and Ar _4' is a tetravalent organic group having no three or more aromatic rings (vi): Ar _{3 '} represents a divalent organic group other than a photopolymerizable group and a divalent organic group having an aromatic ring, and Ar _{4 '} has three or more aromatic rings 4 a combination representing a valent organic group

<<Ar _1′ and Ar _3′ >>
As the divalent organic group having a photopolymerizable group and an aromatic ring in Ar _1' and Ar _3' , for example, the divalent organic group having a photopolymerizable group and an aromatic ring exemplified in the description of Ar ₁ and Ar ₃ organic group.
The divalent organic group other than the photopolymerizable group and the divalent organic group having an aromatic ring in Ar _1' and Ar _3' is not particularly limited, but the resulting cured film has a lower dielectric loss tangent and a higher A divalent organic group having three or more aromatic rings is preferred because it provides high tensile elongation.
Although the divalent organic group having three or more aromatic rings is not particularly limited, it is preferably a divalent organic group represented by the following formula (13).

[In the formula (13), X ₂₁ and X ₂₂ are each independently a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-) , represents a urea bond (-NHCONH-), a thioether bond (-S-) or a sulfonyl bond (-SO ₂ -). R ₂₁ and R ₂₂ each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms. Y 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; When R ₂₁ is plural, the plural R ₂₁ may be the same or different. When R ₂₂ is plural, the plural R ₂₂ may be the same or different. * represents a bond. ]

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

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

Specific examples of the optionally substituted hydrocarbon group having 1 to 6 carbon atoms in R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are those in the description of R ₃ , R ₄ , R ₅ and R ₆ Examples include optionally substituted hydrocarbon groups having 1 to 6 carbon atoms.
In addition, "1 to 6 carbon atoms" of "optionally substituted hydrocarbon group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "hydrocarbon group" excluding substituents. Also, the number of substituents is not particularly limited.

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

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

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

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

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

Examples of the divalent organic group represented by formula (14) include divalent organic groups represented by the following formulae.

In the formula, * represents a bond.

Examples of the divalent organic group represented by formula (15) include divalent organic groups represented by the following formulas.

In the formula, R ₃₃ to R ₃₅ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom represents an alkoxy group. n33 represents an integer of 0 to 5; n34 and n35 each independently represent an integer of 0 to 4; When R ₃₃ is plural, the plural R ₃₃ may be the same or different. When R ₃₄ is plural, the plural R ₃₄ may be the same or different. When R ₃₅ is plural, the plural R ₃₅ may be the same or different. * represents a bond.

Specific examples of alkyl groups having 1 to 6 carbon atoms which may be substituted with halogen atoms for R ₃₃ to R ₃₅ include the carbon atoms optionally substituted by halogen atoms exemplified in the description of R ₁₃ to R ₁₅ Examples include alkyl groups having 1 to 6 atoms.
Specific examples of the alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom for R ₃₃ to R ₃₅ are an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, based on.

Ar _1' and Ar _3' include, for example, divalent organic groups represented by the following formulas.

In the formula, * represents a bond.

Other Ar _1′ and Ar _3′ include, for example, divalent organic groups represented by the following formulas.

In the formula, * represents a bond.

<<Ar _2′ and Ar _4′ >>
Examples of the tetravalent organic group having 3 or more aromatic rings for Ar _2' and Ar _4' include the tetravalent organic groups having 3 or more aromatic rings exemplified in the description of Ar ₂ and Ar ₄ . groups.
The tetravalent organic group having no three or more aromatic rings in Ar _2' and Ar _4' is, for example, a tetravalent organic group having one or two aromatic rings or an aromatic ring. and a tetravalent organic group that does not have A tetravalent organic group having one or two aromatic rings is derived, for example, from an aromatic tetracarboxylic dianhydride derivative. Furthermore, the tetravalent organic group having no aromatic ring is derived from, for example, an aliphatic tetracarboxylic anhydride derivative. Examples of such a tetravalent organic group include, but are not particularly limited to, the following tetravalent organic groups.

In the formula, * represents a bond.

The ratio of the structural unit represented by formula (1) in the total 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%, and 50 to 100 mol%. more preferred. A structural unit is also a repeating unit.
When the polyamic acid has a structural unit represented by the formula (1′), the proportion of the structural unit represented by the formula (1′) in the total structural units of the polyamic acid is not particularly limited, but is 1 to 90 mol. %, more preferably 1 to 50 mol %.

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

The weight average molecular weight of the reaction product is not particularly limited. 0000 is preferred, 7,000 to 50,000 is more preferred, 10,000 to 50,000 is even more preferred, and 10,000 to 40,000 is particularly preferred.

<Method for producing reaction product>
The reaction product comprises an aromatic diamine compound having a photopolymerizable group, a tetracarboxylic acid derivative having three or more aromatic rings, and optionally other diamine compounds and other tetracarboxylic acid derivatives. Obtained by reaction.

The method for producing the reaction product is not particularly limited, and includes, for example, a known method for obtaining polyamic acid or polyimide by reacting a diamine compound and a tetracarboxylic acid derivative. Polyamic acid and polyimide can be synthesized by a known method as described in WO2013/157586, for example.

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

Specific examples of the above solvents 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, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone. Further, when the polymer has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3] Any of the indicated solvents can be used.

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

These solvents may be used alone or in combination. Furthermore, even a solvent that does not dissolve the reaction product may be used by mixing with the above solvent within the range that the reaction product does not precipitate.

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

When reacting the diamine component and the tetracarboxylic acid derivative component, a thermal polymerization inhibitor may be added to the reaction system in order to avoid polymerization of the photopolymerizable group.
Examples of thermal polymerization inhibitors include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, and 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, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt and the like.
The amount of the thermal polymerization inhibitor used is not particularly limited.

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

The chemical imidization can be carried out by adding a basic catalyst and an acid anhydride to the polyamic acid solution 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 mol times, preferably 0.2 to 20 mol times the amount of the amic acid groups, and the amount of the acid anhydride is 1 to 50 mol times the amount of the amic acid groups, preferably 1. 5 to 30 mol times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, triethylamine is preferred because it hardly produces polyisoimide as a by-product. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferable because purification after completion of the reaction is facilitated. The rate of imidization by chemical imidization (ratio of repeating units to be ring-closed to all repeating units of the polyimide precursor, also referred to as rate of ring closure) can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time. can.

In the case of recovering the produced imidized product from the imidization reaction solution, the reaction solution may be put into a solvent to precipitate. 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 putting it into a solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure.

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

The polyimide may be end-sealed. A method for terminal blocking is not particularly limited, and for example, a conventionally known method using a monoamine or an acid anhydride can be used.

<Solvent>
As the solvent contained in the photosensitive resin composition, it is preferable to use an organic solvent from the viewpoint of the solubility of the reaction product. Specifically, 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 or the following formulas [D-1] to [D-3] ], and these can be used alone or in combination of two or more.

The solvent is in the range of, for example, 30 parts by mass to 1500 parts by mass, preferably 100 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the reaction product, depending on the desired coating thickness and viscosity of the photosensitive resin composition. can be used in the range of

<Other ingredients>
In embodiments, the photosensitive resin composition may further contain components other than the reaction product and the solvent. Other components include, for example, photoradical polymerization initiators (also referred to as “photoradical initiators”), crosslinkable compounds (also referred to as “crosslinkers”), thermosetting agents, other resin components, fillers, and sensitizers. , adhesion aids, thermal polymerization inhibitors, azole compounds, hindered phenol compounds, and the like.

<<Photo radical polymerization initiator>>
The photoradical polymerization initiator is not particularly limited as long as it is a compound that absorbs the light source used for photocuring. benzoyldioxy)hexane, 1,4-bis[α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butyl peroxide, 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, 2,2′,5,5′-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone , 3,3′,4,4′-tetra(tert-amylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3′-bis(tert- butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldiperoxyisophthalate and other organic peroxides; 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloro quinones such as anthraquinone, octamethylanthraquinone, and 1,2-benzanthraquinone; benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin, and α-phenylbenzoin; 2,2-dimethoxy-1,2-diphenylethane -1-one, 1-hydroxycyclohexylphenyl 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)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl) - alkylphenone compounds such as butan-1-one; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl )-9H-carbazol-3-yl]ethanone and other oxime ester compounds.

Radical photopolymerization initiators are commercially available, for example, IRGACURE [registered trademark] 651, 184, 2959, 127, 907, 369, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, OXE03, OXE04, 250, 1173, MBF, TPO, 4265, TPO (manufactured by BASF), KAYACURE [registered trademark] DETX-S, MBP, DMBI, EPA, OA (manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, 55 (manufactured by STAUFFER Co. LTD), ESACURE KIP150, TZT, the same 1001, KTO46, KB1, KL200, KS300, EB3, Triazine-PMS, Triazine A, Triazine B (manufactured by Nihon SiberHegner Co., Ltd.), Adeka Optomer N-1717, N-1414, N-1606, ADEKA Arkles N-1919T, ADEKA NCI-831E, ADEKA NCI-930, and ADEKA NCI-730 (manufactured by ADEKA Corporation).
These radical photopolymerization initiators may be used alone or in combination of two or more.

The content of the photoradical polymerization initiator is not particularly limited, but is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the reaction product, and from the viewpoint of photosensitivity characteristics, 0.5 parts by mass to 15 parts by mass. part is more preferred. If it contains 0.1 parts by mass or more of the photoradical polymerization initiator with respect to 100 parts by mass of the reaction product, the photosensitivity of the photosensitive resin composition is likely to be improved, on the other hand, if it contains 20 parts by mass or less is likely to improve the thick-film curability of the photosensitive resin composition.

<<crosslinkable compound>>
In the embodiment, in order to improve the resolution of the relief pattern, a monomer having a photoradical polymerizable unsaturated bond (a crosslinkable compound) can be arbitrarily included in the photosensitive resin composition.
As such a crosslinkable compound, a (meth)acrylic compound that undergoes a radical polymerization reaction with a photoradical polymerization initiator is preferable. ) 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, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di( meth)acrylate, cyclohexane di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, bisphenol A mono- or di(meth)acrylate ) acrylate, 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 , tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, isobornyl (meth) acrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane tri (meth) acrylate, glycerol di or tri (meth) ) acrylates, di-, tri-, or tetra-(meth)acrylates of pentaerythritol, and compounds such as ethylene oxide or propylene oxide adducts of these compounds, 2-isocyanatoethyl (meth)acrylate or isocyanate-containing (meth)acrylates, and these to methyl ethyl ketone oxime, ε-caprolactam, γ-caprolactam, 3,5-dimethylpyrazole, diethyl malonate, ethanol, isopropanol, n-butanol, 1-methoxy-2-propanol and other blocking agents. can. In addition, these compounds may be used individually or may be used in combination of 2 or more types. Moreover, in this specification, (meth)acrylate means acrylate and methacrylate.

Although the content of the crosslinkable compound is not particularly limited, it is preferably 1 to 100 parts by mass, more preferably 1 to 50 parts by mass, relative to 100 parts by mass of the reaction product.

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

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

<<Other resin components>>
In embodiments, the photosensitive resin composition may further contain a resin component other than the reaction product. Examples of resin components that can be contained in the photosensitive resin composition include polyoxazoles, polyoxazole precursors, phenol resins, polyamides, epoxy resins, siloxane resins, and acrylic resins.
The content of these resin components is not particularly limited, but is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the reaction product.

<<Sensitizer>>
In embodiments, the photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity.
Sensitizers include, for example, 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, p-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso naphthothiazole, 1,3-bis(4′-dimethylaminobenzal)acetone, 1,3-bis(4′-diethylaminobenzal)acetone, 3,3′-carbonyl-bis(7-diethylaminocoumarin), 3 -acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino Coumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercapto benzimidazole, 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 can be used singly or in multiple combinations.

Although the content of the sensitizer is not particularly limited, it is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the reaction product.

<<Adhesion Aid>>
In the embodiment, an adhesion promoter can optionally be added to the photosensitive resin composition in order to improve the adhesion between the film formed using the photosensitive resin composition and the substrate.
Examples of adhesion promoters 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]phthalamic acid, benzophenone-3,3′-bis(N-[3-triethoxysilyl]propylamide)-4,4′ -dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyl Silane coupling agents such as trimethoxysilane, and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like can be mentioned.

Among these adhesion aids, it is more preferable to use a silane coupling agent in terms of adhesion.

The content of the adhesion aid is not particularly limited, but is preferably in the range of 0.5 parts by mass to 25 parts by mass with respect to 100 parts by mass of the reaction product.

<<Thermal polymerization inhibitor>>
In the embodiment, a thermal polymerization inhibitor can be arbitrarily blended in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition, particularly during storage in the state of a solution containing a solvent.
Examples of thermal polymerization inhibitors include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, and 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, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt and the like are used.

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

<<Azole compound>>
For example, when using a substrate made of copper or a copper alloy, an azole compound can optionally be added to the photosensitive resin composition in order to suppress discoloration of the substrate.
Azole compounds include, for example, 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, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl -2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, Hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5- methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole.
In addition, these azole compounds may be used singly or as a mixture of two or more.

The content of the azole compound is not particularly limited, but it is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the reaction product, and from the viewpoint of photosensitivity characteristics, 0.5 to 5 parts by mass. Part is more preferred. When the content of the azole compound with respect to 100 parts by mass of the reaction product is 0.1 parts by mass or more, discoloration of the copper or copper alloy surface when the photosensitive resin composition is formed on copper or copper alloy is suppressed, and on the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent, which is preferable.

<<Hindered phenol compound>>
In embodiments, a hindered phenolic compound can optionally be incorporated into the photosensitive resin composition to inhibit discoloration on copper.
Hindered phenol compounds include, for example, 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-hydro cinnamamide), 2,2′-methylene-bis(4-methyl-6-t-butylphenol), 2,2′-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5- Trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6- dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethyl benzyl]-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-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2 -methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy -2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6 -diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl -3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3 -hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5 -ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like, but are not limited thereto. .
Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-trione is particularly preferred.

The content of the hindered phenol compound is not particularly limited, but it is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the reaction product, and from the viewpoint of photosensitivity characteristics, 0.5 to 20 parts by mass It is more preferably 10 parts by mass. When the content of the hindered phenol compound with respect to 100 parts by mass of the reaction product is 0.1 parts by mass or more, for example, when a photosensitive resin composition is formed on copper or a copper alloy, discoloration of copper or copper alloy - Corrosion is prevented, and on the other hand, when it is 20 parts by mass or less, it is preferable because it is excellent in photosensitivity.

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.

(resin film)
The resin film of the present invention is a baked product of the coating film of the photosensitive resin composition of the present invention.
As the coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a method of spray coating with a spray coater. method etc. can be used.
As a baking method for obtaining a baked product, various methods can be selected such as, for example, using a hot plate, using an oven, and using a heating oven in which a temperature program can be set. Firing can be performed, for example, at 130° C. to 250° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.
The thickness of the resin film is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm.
The resin film is, for example, an insulating film.

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

A photosensitive resist film is produced, for example, by coating a base film with a photosensitive resin composition, drying it to form a photosensitive resin layer, and then laminating a cover film on the photosensitive resin layer. can.
As the coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a method of spray coating with a spray coater. method etc. can be used.
The drying method includes, for example, conditions of 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, more preferably 2 μm to 50 μm.

A known base film can be used, and for example, a thermoplastic resin film or the like is used. Examples of the thermoplastic resin include polyester such as polyethylene terephthalate. The thickness of the base film is preferably 2 μm to 150 μm.
A known cover film can be used, for example, a polyethylene film, a polypropylene film, or the like. As the cover film, a film having adhesive strength to the photosensitive resin layer smaller than that of the base film is preferable. The thickness of the cover film is preferably 2 μm to 150 μm, more preferably 2 μm to 100 μm, particularly preferably 5 μm to 50 μm.
The base film and the cover film may be made of the same film material, or may be made of different films.

(Manufacturing method of substrate with cured relief pattern)
The method for producing a cured relief patterned substrate of the present invention comprises:
(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;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) heat-treating the relief pattern to form a cured relief pattern.

Each step will be explained below.

(1) A step of applying the photosensitive resin composition according to 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 the substrate. Then, if necessary, it is dried to form a photosensitive resin layer. As the coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a method of spray coating with a spray coater. method etc. can be used.

If necessary, the coating film made of the photosensitive resin composition can be dried, and drying methods include, for example, air drying, heat drying using an oven or hot plate, vacuum drying, and the like. Specifically, when air drying or heat drying is performed, drying can be performed at 20° C. to 200° C. for 1 minute to 1 hour. As described above, a photosensitive resin layer can be formed on the substrate.

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

After that, for the purpose of improving photosensitivity, etc., post-exposure baking (PEB) and/or pre-development baking may be performed at any combination of temperature and time, if necessary. As for the baking conditions, the temperature is preferably 50° C. to 200° C., and the time is preferably 10 seconds to 600 seconds. is not limited to

(3) Step of developing the exposed photosensitive resin layer to form a relief pattern In this step, an unexposed portion of the exposed photosensitive resin layer is removed by development. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any of conventionally known photoresist developing methods such as a rotary spray method, a paddle method, an immersion method accompanied by ultrasonic treatment, and the like can be used. method can be selected and used. After development, rinsing may be performed for the purpose of removing the developer. Furthermore, for the purpose of adjusting the shape of the relief pattern, etc., post-development baking may be performed at any combination of temperature and time, if necessary.
Organic solvents are preferred as the developer used for development. Examples of organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α- Acetyl-γ-butyrolactone and the like are preferred. Moreover, two or more kinds of each solvent can be used, for example, several kinds can be used in combination.
As the rinsing liquid used for rinsing, an organic solvent that is miscible with the developer and has low solubility in the photosensitive resin composition is preferable. Preferred examples of the rinse liquid include methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, toluene, and xylene. Moreover, two or more kinds of each solvent can be used, for example, several kinds can be used in combination.

(4) Step of Heating the Relief Pattern to Form a Hardened Relief Pattern In this step, the relief pattern obtained by the development is heated and converted into a hardened relief pattern. When the reaction product is a polyamic acid, this heating results in thermal imidization resulting in a cured relief pattern comprising polyimide. As the heat curing method, various methods can be selected, for example, a method using a hot plate, a method using an oven, and a method using a heating oven capable of setting a temperature program. Heating can be performed, for example, at 130° C. to 250° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.

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

(semiconductor device)
Embodiments also provide a semiconductor device comprising a semiconductor element and a cured film provided over or under the semiconductor element. A 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 of manufacturing a semiconductor device using a semiconductor element as a substrate and including the above-described method of manufacturing a substrate with a cured relief pattern as part of the steps. The semiconductor device of the present invention forms a cured relief pattern as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, a protective film for a semiconductor device having a bump structure, or the like. It can be manufactured by combining with a manufacturing method of a semiconductor device.

(Display device)
In an embodiment, there is provided a display device comprising a display element and a cured film provided on top of the display element, wherein the cured film is the cured relief pattern described above. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer interposed therebetween. For example, the cured film includes a surface protective film, an insulating film, and a flattening film for TFT (Thin Film Transistor) liquid crystal display elements and color filter elements, projections for MVA (Multi-domain Vertical Alignment) type liquid crystal display devices, and A partition wall for an organic EL (Electro-Luminescence) device cathode can be mentioned.

The photosensitive resin composition of the present invention, in addition to application to the semiconductor device as described above, is also used for applications such as interlayer insulating films of multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. Useful.

Next, the contents of the present invention will be specifically described with reference to Examples, but the present invention is not limited to these.

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

The chemical imidization rates shown in the Synthesis Examples below were calculated by the following method. Put 100 mg of polyimide powder in an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku Co., Ltd.)), deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) ( 0.53 ml) was added and sonicated to completely dissolve. This solution was subjected to proton NMR at 500 MHz using an NMR spectrometer (JNM-ECA500) (manufactured by JEOL Ltd.). For the chemical imidization rate, a proton derived from a structure that does not change before and after imidization is determined as a reference proton, and the peak integrated value of this proton and the proton derived from the NH group of amic acid appearing around 9.5 ppm to 11.0 ppm. It was calculated by the following formula using the peak integrated value.
Chemical imidization rate (%) = (1-α x/y) x 100
In the above formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is one NH group proton of the amic acid in the case of polyamic acid (imidization rate is 0%). is the number ratio of reference protons to

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

<Synthesis Example 2> Synthesis of polyamic acid (P-2) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 9.85 g, 1,4- 12.84 g of 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 stirred in air. Then, after stirring at room temperature to dissolve, 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, and then stirred at 50° C. for 89 hours. The resulting polyamic acid had a repeating unit structure represented by (P-2) below, and had a weight average molecular weight (Mw) of 25,273 as measured by GPC in terms of polystyrene.

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

<Synthesis Example 4> Synthesis of polyamic acid (P-4) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 13.73 g, 2,2- 9.14 g of 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 placed in air at room temperature. After dissolving with stirring, 37.08 g of 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride and 86.53 g of N-ethyl-2-pyrrolidone were added to the system, After stirring at room temperature for 2 hours, the mixture was stirred at 50°C for 88 hours. The resulting polyamic acid had a repeating unit structure represented by (P-4) below, and had a weight average molecular weight (Mw) of 24,973 as measured by GPC in terms of polystyrene.

<Synthesis Example 5> Synthesis of polyamic acid (P-5) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 9.47 g, 2,2- 14.70 g of 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 placed in air at room temperature. After dissolving with stirring, 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, After stirring at room temperature for 3 hours, the mixture was stirred at 50° C. for 89 hours. The resulting polyamic acid had a repeating unit structure represented by (P-5) below, and had a weight average molecular weight (Mw) of 27,852 as measured by GPC in terms of polystyrene.

<Synthesis Example 6> Synthesis of polyamic acid (P-6) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 3.59 g, 2,2- 13.01 g of 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 placed in air at room temperature. After dissolving with stirring, 23.33 g of 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride and 93.33 g of N-ethyl-2-pyrrolidone were added to the system, After stirring at room temperature for 3 hours, the mixture was stirred at 50° C. for 95 hours. The resulting polyamic acid had a repeating unit structure represented by (P-6) below, and had a weight average molecular weight (Mw) of 56,737 as measured by GPC in terms of polystyrene.

<Synthesis Example 7> Synthesis of polyamic acid (P-7) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 1.16 g, 2,2- 16.22 g of 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 placed in air at room temperature. After dissolving with stirring, 22.62 g of 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride and 90.47 g of N-ethyl-2-pyrrolidone were added to the system, After stirring at room temperature for 3 hours, the mixture was stirred at 50° C. for 95 hours. The resulting polyamic acid had a repeating unit structure represented by (P-7) below, and had a weight average molecular weight (Mw) of 58,225 as measured by GPC in terms of polystyrene.

<Synthesis Example 8> Synthesis of polyamic acid (P-8) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 9.71 g, 4,4′ -Bis(4-aminophenoxy)biphenyl 13.54 g, 2,6-di-tert-butyl-p-cresol 0.04 g, and N-ethyl-2-pyrrolidone 54.34 g were stirred under air at room temperature. After dissolution, 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 allowed to stand at room temperature for 3 hours. After stirring, the mixture was stirred at 50°C for 92 hours. The resulting polyamic acid had a repeating unit structure represented by (P-8) below, and had a weight average molecular weight (Mw) of 33,012 as measured by GPC in terms of polystyrene.

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

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

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

<Synthesis Example 12> Synthesis of polyamic acid (P-12) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 7.94 g, 1,4- After dissolving 10.46 g of phenylene bis(4-aminobenzoate), 0.05 g of 4-methoxyphenol, and 87.05 g of N-ethyl-2-pyrrolidone under air at room temperature, 4,4'- (4,4′-Isopropylidenediphenoxy)diphthalic anhydride 29.98 g and N-ethyl-2-pyrrolidone 58.04 g were added to the system, stirred at room temperature for 3 hours, and then stirred at 50° C. for 74 hours. did. The resulting polyamic acid had a repeating unit structure represented by (P-12) below, and had a weight average molecular weight (Mw) of 24,660 as measured by GPC in terms of polystyrene.

<Synthesis Example 13> Synthesis of polyamic acid (P-13) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 10.95 g, 2,2- 17.01 g of 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 placed in air at room temperature. 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. After stirring for 1 hour, the mixture was stirred at 40°C for 39 hours. The resulting polyamic acid had a repeating unit structure represented by (P-13) below, and had a weight average molecular weight (Mw) of 21,092 as measured by GPC in terms of polystyrene.

<Synthesis Example 14> Synthesis of polyamic acid (P-14) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 8.63 g, 2,2- 13.41 g of 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 placed in air at room temperature. bis-(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)propane-2,2-diylbis(2-methyl-4,1-phenylene) 37 .92 g and 51.68 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 2 hours, and then stirred at 40° C. for 39 hours. The resulting polyamic acid had a repeating unit structure represented by (P-14) below, and had a weight average molecular weight (Mw) of 16,379 as measured by GPC in terms of polystyrene.

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

<Synthesis Example 16> Synthesis of polyamic acid (P-16) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 5.29 g, 2,2- 10.36 g of bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 0.04 g of 4-methoxyphenol, and 65.87 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air. After that, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenylfluorene dianhydride (BPF-PA, manufactured by JFE Chemical Co., Ltd.) 24.68 g, and N-ethyl-2-pyrrolidone 28 0.23 g was added to the system, and the mixture was stirred at room temperature for 4 hours, and then stirred at 50° C. for 26.5 hours. The resulting polyamic acid had a repeating unit structure represented by (P-16) below, and had a weight average molecular weight (Mw) of 28,330 as measured by GPC in terms of polystyrene.

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

<Synthesis Example 18> Synthesis of polyamic acid (P-18) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 8.65 g, 2,2- After dissolving 13.44 g of bis[4-(4-aminophenoxy)phenyl]propane, 0.053 g of 4-methoxyphenol, and 105.62 g of N-ethyl-2-pyrrolidone under air at room temperature, P-phenylene bis(trimellitate anhydride) (TAHQ, manufactured by Manac Co., Ltd.) 15.0 g, 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride 15.67 g and N-ethyl- 52.81 g of 2-pyrrolidone was added to the system, stirred at room temperature for 1 hour, and then stirred at 50° C. for 40 hours. The resulting polyamic acid had a repeating unit structure represented by (P-18) below, and had a weight average molecular weight (Mw) of 36,287 as measured by GPC in terms of polystyrene.

<Synthesis Example 19> Synthesis of polyamic acid (P-19) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 8.65 g, 2,2- After dissolving 13.44 g of bis[4-(4-aminophenoxy)phenyl]propane, 0.054 g of 4-methoxyphenol, and 107.24 g of N-ethyl-2-pyrrolidone under air at room temperature, P-phenylene bis(trimellitate anhydride) (TAHQ, manufactured by Manac Co., Ltd.) 9.0 g, 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride 22.49 g and N-ethyl- 53.62 g of 2-pyrrolidone was added to the system, stirred at room temperature for 1 hour, and then stirred at 50° C. for 40 hours. The resulting polyamic acid had a repeating unit structure represented by (P-19) below, and had a weight average molecular weight (Mw) of 34,006 as measured by GPC in terms of polystyrene.

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

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

<Synthesis Example 22> Synthesis of solvent-soluble polyimide (P-22) Polyamic acid (P-16) 40.21 g obtained in Synthesis Example 16, N-ethyl-2-pyrrolidone 80.42 g, acetic anhydride 3 0.66 g and 0.61 g of triethylamine were added, and the mixture was stirred under air at room temperature for 30 minutes, and then stirred at 60° C. for 3 hours. This solution was slowly added to 437.15 g of stirring methanol and then stirred for 10 minutes, and the resulting precipitate was filtered off. After washing the precipitate with 874.30 g of methanol, it was dried under reduced pressure at 80° C. to obtain a solvent-soluble polyimide powder having a repeating unit structure represented by (P-22) below. The chemical imidization rate was 95.3%.

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

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

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

<Comparative Synthesis Example 2> Synthesis of polyamic acid (P-26) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 42.28 g, 4-methoxy After dissolving 0.09 g of phenol and 144.42 g of N-ethyl-2-pyrrolidone under air at room temperature with stirring, 46.13 g of 3,3′,4,4′-biphenyltetracarboxylic dianhydride was added. , and 61.89 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 1 hour, and then stirred at 80° C. for 75 hours. A polyamic acid having a repeating unit structure represented by (P-26) below was obtained.

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

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

<Comparative Synthesis Example 5> Synthesis of polyamic acid (P-29) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 15.00 g, 2,6 0.06 g of di-tert-butyl-p-cresol and 45.19 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 1,1'-bicyclohexane-3,3 was added. 17.21 g of ',4,4'-tetracarboxylic acid-3,3',4,4'-dianhydride (BPDA-H, manufactured by Iwatani Gas Co., Ltd.), and 30 g of N-ethyl-2-pyrrolidone. 12 g was added to the system and stirred at room temperature for 62 hours, and then stirred at 40° C. for 34 hours. The resulting polyamic acid had a repeating unit structure represented by (P-29) below, and had a weight average molecular weight (Mw) of 45,136 as measured by GPC in terms of polystyrene.

<Comparative Synthesis Example 6> Synthesis of solvent-soluble polyimide (P-30) 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 8.60 g, 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 stirred under air at room temperature. 27.72 g of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride and 63.79 g of N-ethyl-2-pyrrolidone were added to the system and stirred at room temperature for 1 hour. Stir at 50° C. for 87 hours. The weight average molecular weight (Mw) of the obtained polyamic acid measured by GPC in terms of polystyrene was 27,335.
60.00 g of N-ethyl-2-pyrrolidone, 4.49 g of acetic anhydride, and 0.58 g of pyridine were added to 60.00 g of the obtained polyamic acid, and the mixture was stirred at room temperature for 30 minutes in air, and then stirred at 50°C for 3 hours. Stirred for an hour. This solution was slowly added to 437.76 g of stirring methanol and then stirred for 10 minutes, and the resulting precipitate was filtered off. After washing the precipitate with 875.52 g of methanol, it was dried at 60° C. under reduced pressure to obtain a solvent-soluble polyimide powder having a repeating unit structure represented by (P-30) below. The chemical imidization rate was 93.2%.

<Example 1>
27.75 g of the solution containing the polyamic acid (P-1) obtained in Synthesis Example 1 (solid content concentration: 30% by weight), NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.67 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.42 g and KBM-5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) 0.17 g were mixed and dissolved. A solution of a negative photosensitive resin composition was prepared by filtering with a filter.

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

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

<Example 4>
22.08 g of the solution (solid content concentration: 30% by weight) containing the polyamic acid (P-3) obtained in Synthesis Example 3, NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.32 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.33 g, IRGANOX [registered trademark] 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 Co., Ltd.) 0.10 g, KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.13 g, and N After mixing and dissolving 11.04 g of ethyl-2-pyrrolidone, 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.

<Example 5>
32.49 g of a solution containing the polyamic acid (P-3) obtained in Synthesis Example 3 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.97 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.49 g, IRGANOX [registered trademark] 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 Co., Ltd.) 0.15 g, KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) After mixing and dissolving 0.19 g of N-ethyl-2-pyrrolidone and 0.71 g of N-ethyl-2-pyrrolidone, a solution of a negative photosensitive resin composition was prepared by filtering using a polypropylene filter with a pore size of 5 μm. .

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

<Example 7>
29.96 g of the solution containing the polyamic acid (P-5) obtained in Synthesis Example 5 (solid content concentration: 30% by weight), NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.80 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.45 g, IRGANOX [registered trademark] 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 Co., Ltd.) 0.13 g, KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.18 g, and N After mixing and dissolving 2.48 g of ethyl-2-pyrrolidone, 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.

<Example 8>
23.89 g of a solution containing the polyamic acid (P-5) obtained in Synthesis Example 5 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.72 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.36 g, IRGANOX [registered trademark] 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 Co., Ltd.) 0.11 g, KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) After mixing and dissolving 0.14 g and 4.78 g of N-ethyl-2-pyrrolidone, a solution of a negative photosensitive resin composition was prepared by filtering using a polypropylene filter with a pore size of 5 μm. .

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

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

<Example 11>
22.08 g of the solution (solid content concentration: 30% by weight) containing the polyamic acid (P-8) obtained in Synthesis Example 8, NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.32 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.33 g, IRGANOX [registered trademark] 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 Co., Ltd.) 0.10 g, KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.13 g, and N After mixing and dissolving 11.04 g of ethyl-2-pyrrolidone, the solution was filtered using a polypropylene filter having a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Example 12>
31.50 g of a solution containing the polyamic acid (P-8) obtained in Synthesis Example 8 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.95 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.47 g, IRGANOX [registered trademark] 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 Co., Ltd.) 0.14 g, KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) After mixing and dissolving 0.19 g and 1.75 g of N-ethyl-2-pyrrolidone, a solution of a negative photosensitive resin composition was prepared by filtering using a polypropylene filter with a pore size of 5 μm. .

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

<Example 14>
20.75 g of the solution (solid content concentration: 30% by weight) containing the polyamic acid (P-10) obtained in Synthesis Example 10, NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.25 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.31 g, IRGANOX [registered trademark] 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 Co., Ltd.) 0.09 g, KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.12 g, and N -Ethyl-2-pyrrolidone 2.47 was mixed and dissolved, and filtered through a polypropylene filter having a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Example 15>
Solution containing polyamic acid (P-11) obtained in Synthesis Example 11 (solid concentration: 25% by weight) 23.66 g, N-ethyl-2-pyrrolidone 0.99 g, NK ester A-DOD- as a cross-linking agent N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.59 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) Phenyl-,2-(O-benzoyloxime)], manufactured by BASF Japan Ltd.) 0.30 g, IRGANOX [registered trademark] 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.) 0.09 g, and KBM-5103 (3-acryloxypropyl After mixing and dissolving 0.12 g of trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), the solution was filtered using a polypropylene filter having a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition. .

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

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

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

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

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

<Example 21>
21.40 g of a solution containing the polyamic acid (P-15) obtained in Synthesis Example 15 (solid content concentration: 30% by weight), NK Ester A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent )) 1.28 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio) phenyl-, 2-(O-benzoyloxime)] as a photoradical initiator, BASF Japan ( Co., Ltd.) 0.32 g, IRGANOX [registered trademark] 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 Co., Ltd.) 0.10 g, KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.13 g, and N After mixing and dissolving 1.77 g of ethyl-2-pyrrolidone, 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.

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

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

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

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

<Example 26>
38.57 g of a solution (solid concentration: 20% by weight) containing the polyamic acid (P-20) obtained in Synthesis Example 20, NK ester A-DOD-N (1,10-decanediol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 0.77 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime) as a photoradical initiator )], manufactured by BASF Japan Ltd.) 0.39 g, IRGANOX [registered trademark] 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 Co., Ltd.) 0.12 g, and KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) ) was mixed and dissolved, and filtered through a polypropylene filter having a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

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

<Example 28>
Powder 11.02 g of the solvent-soluble polyimide (P-22) obtained in Synthesis Example 22, N-ethyl-2-pyrrolidone 25.71 g, NK ester A-DOD-N (1,10-decane Diol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 2.20 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-( O-benzoyloxime)], manufactured by BASF Japan Ltd.) 0.55 g, IRGANOX [registered trademark] 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 Co., Ltd.) 0.17 g, and KBM-5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. Co., Ltd.) was mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Example 29>
Powder 10.89 g of solvent-soluble polyimide (P-23) obtained in Synthesis Example 23, N-ethyl-2-pyrrolidone 26.00 g, NK ester A-DOD-N (1,10-decane Diol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 2.18 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-( O-benzoyloxime)], manufactured by BASF Japan Ltd.) 0.54 g, IRGANOX [registered trademark] 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 Co., Ltd.) 0.16 g, and KBM-5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. Co., Ltd.) was mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Example 30>
Powder 10.89 g of the solvent-soluble polyimide (P-24) obtained in Synthesis Example 24, N-ethyl-2-pyrrolidone 26.00 g, NK ester A-DOD-N (1,10-decane Diol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 2.18 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-( O-benzoyloxime)], manufactured by BASF Japan Ltd.) 0.54 g, IRGANOX [registered trademark] 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 Co., Ltd.) 0.16 g, and KBM-5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. Co., Ltd.) was mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

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

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

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

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

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

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

[Photosensitivity evaluation]
The negative photosensitive resin compositions prepared in Examples 1 to 30 and Comparative Examples 1 to 6 were coated on an 8-inch silicon wafer using a spin coater (CLEAN TRACK ACT-8, manufactured by Tokyo Electron Ltd.). and baked at 115° C. for 180 seconds or 270 seconds to form a photosensitive resin film having a thickness of 5 to 15 μm on the wafer. Next, exposure was performed using an i-line stepper (NSR-2205i12D, manufactured by Nikon Corporation). Furthermore, using an automatic developing device (AD-1200, manufactured by Mikasa Co., Ltd.), spray development was performed using cyclopentanone as a developer for 20 to 240 seconds, and then propylene glycol monomethyl ether acetate (PGMEA) was added as a rinse. Spray rinse for 10 seconds. The film thickness immediately after film formation and the film thickness after development at 0 mJ/cm ² (unexposed area) and 300 mJ/cm ² (exposed area) were measured using an interference film thickness meter (Lambda Ace VM-2110, manufactured by SCREEN Co., Ltd.). The film thicknesses of the unexposed area and the exposed area were compared by measuring using . Table 1 shows the measurement results of the film thickness.

From the results in Table 1, the negative photosensitive resin compositions of Examples 1 to 30 fully dissolved (developed) the photosensitive resin film in the unexposed area (0 mJ/cm ² ) after development, and the exposed area (300 mJ/cm ² ) of the photosensitive resin film remained without being dissolved (developed). That is, since a clear dissolution difference (dissolution contrast) of the photosensitive resin film was obtained in the exposed and unexposed areas, the relief pattern creation process using general-purpose organic solvents such as cyclopentanone for development It can be suitably used as a negative photosensitive resin composition for. On the other hand, in the photosensitive resin compositions of Comparative Examples 1, 2, 4 and 5, the photosensitive resin film in the unexposed area (0 mJ/cm ² ) was not sufficiently dissolved (developed) after development. remained. That is, a negative photosensitive resin composition for a relief pattern forming process in which a clear dissolution contrast is not obtained in an exposed area and an unexposed area and development is performed using a general-purpose organic solvent such as cyclopentanone. is inappropriate as

[Evaluation of electrical characteristics]
The negative photosensitive resin compositions prepared in Examples 1 to 30 and Comparative Examples 1 to 6 were spin-coated onto a 4-inch silicon wafer coated with an aluminum foil having a thickness of 20 μm, and heated at 115 degrees on a hot plate. C. for 180 seconds or 270 seconds to form a photosensitive resin film on the aluminum foil. Next, using an i-line aligner (PLA-501, manufactured by Canon Inc.), the entire surface of the wafer was exposed at 500 mJ/cm ² , then in a nitrogen atmosphere at 160° C. for 1 hour, then at 230° C. for 1 hour. Baked. Furthermore, the film was obtained by immersing the baked aluminum foil in 6N hydrochloric acid to dissolve the aluminum foil. Next, the obtained film was dried under reduced pressure at 80° C. for 2 hours, left for 24 hours in an environment with a temperature of about 25° C. and a humidity of about 42%. (manufactured by Co., Ltd.). The dielectric loss tangent measurement conditions are as follows.
・Measurement method: Perturbation cavity resonator method ・Vector network analyzer: FieldFox N9926A (manufactured by Keysight Technologies Inc.)
・Cavity resonator: TMR-1A (manufactured by Keycom Co., Ltd.)
・Cavity volume: 1192822 mm ³
・Measurement frequency: about 1 GHz
・Sample tube: made of PTFE, inner diameter: 3 mm, length of about 30 mm (manufactured by Keycom Co., Ltd.)

[Mechanical property evaluation]
The negative photosensitive resin compositions prepared in Examples 1 to 30 and Comparative Examples 1 to 6 are spin-coated on a 100 nm thick aluminum wafer and baked on a hot plate at 115 ° C. for 180 seconds or 270 seconds. By doing so, a photosensitive resin film was formed on the aluminum wafer. Next, using an i-line aligner (PLA-501, manufactured by Canon Inc.), the entire surface of the wafer was exposed at 500 mJ/cm ² , then in a nitrogen atmosphere at 160° C. for 1 hour, then at 230° C. for 1 hour. Baked. Furthermore, after cutting the photosensitive resin film at intervals of 5 mm in width with a dicing saw (DAD323, manufactured by Disco Co., Ltd.), the aluminum wafer was immersed in 6N hydrochloric acid to dissolve the aluminum, thereby obtaining a film with a width of 5 mm. rice field. Next, the tensile elongation of the obtained film was measured using a desktop precision universal testing machine (Autograph AGS-10kNX, manufactured by Shimadzu Corporation). The conditions for measuring the tensile elongation are as follows.
・Desktop precision universal testing machine: Autograph AGS-10kNX (manufactured by Shimadzu Corporation)
・Film width: 5mm
・Distance between grips: 25mm
Here, the tensile elongation of 50% means that the film is stretched up to 1.5 times, in other words, the film breaks when the distance between the grips is 1.5 times (37.5 mm).

Table 2 shows the measurement results of dielectric loss tangent and tensile elongation.

From the results in Table 2, the dielectric loss tangent values at 1 GHz of the films obtained from the negative photosensitive resin compositions of Examples 1 to 30 were lower than those of Comparative Examples 1 to 5. In addition, the films obtained from the negative photosensitive resin compositions of Examples 1 to 30 had higher tensile elongation values than those of Comparative Examples 1 to 6.
That is, the negative photosensitive resin compositions of Examples 1 to 30 can form a relief pattern, have a low dielectric loss tangent, and have a high tensile elongation at the same time. It can be suitably used for the production of electronic materials that require properties.

Claims

A photosensitive resin composition containing 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 photosensitive resin composition according to claim 1, wherein the reaction product is a polyamic acid or a polyimide obtained by dehydrating and ring-closing a polyamic acid.
The polyamic acid has at least a structural unit represented by the following formula (1),
The photosensitive resin composition according to claim 2, wherein the polyimide has at least a structural unit represented by the following formula (2).

[In formula (1), Ar 1 represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar 2 represents a tetravalent organic group having three or more aromatic rings. ]

[In formula (2), 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. ]
4. The photosensitive resin composition according to claim 3, wherein Ar 2 in the formula (1) and Ar 4 in the formula (2) are tetravalent organic groups represented by the following formula (3).

[In Formula (3), X 1 and X 2 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. R 1 and R 2 each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms. 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 R 1 s, the multiple R 1s may be the same or different. When there are multiple R 2 s, the multiple R 2s may be the same or different. * represents a bond. ]

[In formula (3-1), Z 1 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. R 3 and R 4 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 Z 1 is plural, the plural Z 1 may be the same or different. When n4 is plural, the plural n4 may be the same or different. When R 3 is plural, the plural R 3 may be the same or different. When R 4 is plural, the plural R 4 may be the same or different. * represents a bond.
In formula (3-2), Z 2 represents a divalent organic group represented by formula (4) or (5) below. R 5 and R 6 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 R 5 is plural, the plural R 5 may be the same or different. When R 6 is plural, the plural R 6 may be the same or different. * represents a bond. ]

[In Formula (4), R 7 and R 8 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom. * represents a bond.
In formula (5), R 9 and R 10 each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms. * represents a bond. ]
The photosensitive resin composition according to claim 3 or 4, wherein Ar 1 in the formula (1) and Ar 3 in the formula (2) are divalent organic groups represented by the following formula (6). .

[In formula (6), Z3 represents an ether bond , an ester bond, an amide bond, a urethane bond or a urea bond, and Z4 represents a direct bond, an ester bond or an amide bond. Z5 represents a direct bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, or 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, and R 12 represents a hydrogen atom or a methyl group. * represents a bond. ]
The photosensitive resin composition according to claim 5 , wherein Z3 and Z4 in formula ( 6 ) are ester bonds.
7. The photosensitive resin composition according to claim 5, wherein R 11 in formula (6) is a 1,2-ethylene group.
The photosensitive resin composition according to any one of claims 1 to 7, further comprising a photoradical polymerization initiator.
The photosensitive resin composition according to any one of claims 1 to 8, further comprising a crosslinkable compound.
The photosensitive resin composition according to any one of claims 1 to 9, which is used for forming an insulating film.
The photosensitive resin composition according to any one of claims 1 to 10, which is a negative photosensitive resin composition.
A resin film that is a baked product of the coating film of the photosensitive resin composition according to any one of claims 1 to 11.
The resin film according to claim 12, which is an insulating film.
A photosensitive resist film comprising a base film, a photosensitive resin layer formed from the photosensitive resin composition according to any one of claims 1 to 11, and a cover film.
(1) a step of applying the photosensitive resin composition according to any one of claims 1 to 11 onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a substrate with a hardened relief pattern, comprising the step of heat-treating the relief pattern to form a hardened relief pattern.
The method for manufacturing a cured relief patterned substrate according to claim 15, wherein the developer used for the development is an organic solvent.
A substrate with a cured relief pattern, manufactured by the method according to claim 15 or 16.
A semiconductor device comprising a semiconductor element and a cured film provided above or below the semiconductor element, wherein the cured film is formed from the photosensitive resin composition according to any one of claims 1 to 11. A semiconductor device that is a cured relief pattern.