CN116982003A

CN116982003A - Photosensitive resin composition

Info

Publication number: CN116982003A
Application number: CN202280019418.XA
Authority: CN
Inventors: 远藤贵文; 石井秀则; 坂口崇洋; 荻野浩司; 星野有辉
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2021-03-22
Filing date: 2022-02-25
Publication date: 2023-10-31
Also published as: JPWO2022202098A1; TW202244131A; WO2022202098A1; KR20230160249A

Abstract

A photosensitive resin composition comprising a solvent and a reaction product of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having 3 or more aromatic rings.

Description

Photosensitive resin composition

Technical Field

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

Background

Polyimide resins having excellent heat resistance, electrical characteristics and mechanical characteristics have been used for insulating materials for electronic parts, passivation films, surface protective films, interlayer insulating films for semiconductor devices, and the like. In this polyimide resin, a polyimide resin supplied in the form of a photosensitive polyimide precursor can be easily formed into a heat-resistant uneven pattern coating by coating, exposing, developing, and thermal imidization treatment by curing the precursor. Such a photosensitive polyimide precursor has a feature that the process can be significantly shortened as compared with a conventional non-photosensitive polyimide resin.

Patent documents 1 and 2 propose photosensitive resin compositions containing polyamide acid or polyimide using diamine having (meth) acryloxy group.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2000-347404

Patent document 2: japanese patent application laid-open No. 2012-516927

Disclosure of Invention

Technical problem to be solved by the invention

In recent years, a semiconductor device is required to transmit and process information of a large capacity at a high speed, and thus, a high frequency of an electric signal is being developed. High frequency electrical signals are easily attenuated, and thus transmission loss needs to be reduced. Therefore, a low dielectric loss tangent is required for the resin used in the semiconductor device.

On the other hand, resins having a low dielectric loss tangent tend to be brittle, and for example, in a heat treatment step such as a solder reflow step, they may not be broken or interlayer adhesiveness may be lowered by following thermal expansion of adjacent materials. Therefore, a resin used in a semiconductor device is required to have a high tensile elongation.

In addition, when forming the cured uneven pattern, development is performed with a developer, and an aqueous alkali developer or an organic solvent developer is generally used. The photosensitive resin used to obtain the cured uneven pattern is divided into a positive type in which the photosensitive resin in the exposed portion is dissolved in a developer and the photosensitive resin in the unexposed portion remains, and a negative type in which the photosensitive resin in the unexposed portion is dissolved in the developer and the photosensitive resin in the exposed portion remains, by exposure and development. In particular, the negative type is inferior in resolution to the positive type, but is easy to make thick and thin and excellent in reliability, and is used for manufacturing a semiconductor device requiring such characteristics. However, in the conventional negative photosensitive resin containing polyamide acid, the solubility to an aqueous alkali developer is extremely high, and therefore, it is difficult to control the dissolution rate, and it is possible to obtain a desired uneven pattern. Further, since the negative photosensitive resin containing polyamide acid has high affinity with an aqueous alkali developer, there is a technical problem that the negative photosensitive resin is liable to swell during development and the uneven pattern formed by the stress generated during drying is liable to be peeled off from the substrate. Thus, in the negative photosensitive resin containing polyamide acid, the dissolution rate can be controlled relatively easily, and the organic solvent development is suitable with less concern for peeling the substrate.

Therefore, a photosensitive resin composition capable of organic solvent development, having a low dielectric loss tangent in the resulting cured film, and having a high tensile elongation is demanded.

However, the photosensitive resin compositions described in patent document 1 and patent document 2 do not satisfy all of these characteristics.

In view of the above, an object of the present invention is to provide a photosensitive resin composition which can be developed with an organic solvent, has a low dielectric tangent and has a high tensile elongation in the obtained 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, and a semiconductor device having a cured relief pattern.

Technical scheme for solving technical problems

The present inventors have conducted intensive studies to achieve the above-mentioned object, and as a result, have found that a photosensitive resin composition having a low dielectric tangent and a high tensile elongation in a cured film, which can be developed with an organic solvent, can be obtained by adding a reaction product of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having 3 or more aromatic rings to a photosensitive resin composition, and have completed the present invention.

[1] A photosensitive resin composition comprising a solvent and a reaction product of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having 3 or more aromatic rings.

[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 photosensitive resin composition according to [2], wherein the polyamic acid has at least a structural unit represented by the following formula (1),

the polyimide has at least a structural unit represented by the following formula (2).

[ chemical 1]

[ in formula (1), ar ₁ Ar represents a 2-valent organic group having a photopolymerizable group and an aromatic ring ₂ Represents a 4-valent organic group having 3 or more aromatic rings.]

[ chemical 2]

[ in formula (2), ar ₃ Ar represents a 2-valent organic group having a photopolymerizable group and an aromatic ring ₄ Represents a 4-valent organic group having 3 or more aromatic rings.]

[4]According to [3]]The photosensitive resin composition, wherein Ar in the formula (1) ₂ And Ar in the formula (2) ₄ The organic group is a 4-valent organic group represented by the following formula (3).

[ chemical 3]

[ in formula (3), X ₁ X is X ₂ Each independently 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 is R ₁ R is R ₂ Each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted. Y represents a 2-valent organic group represented by the following formula (3-1) or (3-2). n1 and n2 each independently represent an integer of 0 to 3. At R ₁ In the case of a plurality of R ₁ May be the same or different. At R ₂ In the case of a plurality of R ₂ May be the same or different. * Representing a bond.]

[ chemical 4]

[ 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 is R ₃ R is R ₄ Each independently represents a hydrocarbon group having 1 to 6 carbon atoms which may be substituted. m1 represents an integer of 0 to 3. n3 and n4 each independently represent an integer of 0 to 4. At Z ₁ In the case of a plurality of Z' s ₁ May be the same or different. When n4 is plural, plural n4 may be the same or different. At R ₃ In the case of a plurality of R ₃ May be the same or different. At R ₄ In the case of a plurality of R ₄ May be the same or different. * Representing a bond.

In the formula (3-2), Z ₂ The 2-valent organic group represented by the following formula (4) or (5). R is R ₅ R is R ₆ Each independently represents a hydrocarbon group having 1 to 6 carbon atoms which may be substituted. n5 and n6 each independently represent an integer of 0 to 4. At R ₅ In the case of a plurality of R ₅ May be the same or different. At R ₆ In the case of a plurality of R ₆ May be the same or different. * Representing a bond.]

[ chemical 5]

[ in formula (4), R ₇ R is R ₈ Each independently represents a hydrogen atom, or a hydrocarbon group of 1 to 6 carbon atoms which may be substituted with a halogen atom. * Representing a bond.

In the formula (5), R ₉ R is R ₁₀ Each independently represents an alkylene group having 1 to 6 carbon atoms which may be substituted or an arylene group having 6 to 10 carbon atoms which may be substituted. * Representing a bond.]

[5]According to [3 ]]Or [4 ]]The photosensitive resin composition, wherein Ar in the formula (1) ₁ And Ar in the formula (2) ₃ Is a 2-valent organic group represented by the following formula (6).

[ chemical 6]

[ in formula (6), Z ₃ Represents an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, Z ₄ Represents a direct bond, an ester bond or an amide bond. Z is Z ₅ Represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a thioether bond or a sulfonyl bond. m2 represents an integer of 0 to 1. R is R ₁₁ Represents a directly bonded or hydroxy-substituted alkylene group having 2 to 6 carbon atoms, R ₁₂ Represents a hydrogen atom or a methyl group. * Representing a bond.]

[6]According to [ 5]]The photosensitive resin composition, wherein Z in the formula (6) ₃ And Z ₄ Is an ester bond.

[7]According to [5 ]]Or [6 ]]The photosensitive resin composition, wherein R in the formula (6) ₁₁ Is 1, 2-ethylene.

[8] The photosensitive resin composition according to any one of [1] to [7], wherein the photosensitive resin composition further comprises a photo radical polymerization initiator.

[9] The photosensitive resin composition according to any one of [1] to [8], wherein the photosensitive resin composition further comprises a crosslinkable compound.

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the photosensitive resin composition is used for forming an insulating film.

[11] The photosensitive resin composition according to any one of [1] to [10], wherein the photosensitive resin composition is a negative photosensitive resin composition.

[12] A resin film which is a fired product of a coating film of the photosensitive resin composition described in any one of [1] to [11 ].

[13] The resin film according to [12], wherein the resin film is an insulating film.

[14] A photosensitive resist film comprising a base film, a photosensitive resin layer formed from the photosensitive resin composition of any one of [1] to [11], and a cover film.

[15] A method for manufacturing a substrate with a cured relief pattern, comprising the steps of:

(1) Coating a photosensitive resin composition substrate according to any one of [1] to [11], forming a photosensitive resin layer on the substrate,

(2) The photosensitive resin layer is subjected to exposure to light,

(3) Developing the exposed photosensitive resin layer to form a concave-convex pattern, and

(4) The relief pattern is subjected to a heat treatment to form a cured relief pattern.

[16] The method of producing a substrate with a cured relief pattern according to [15], wherein the developer used in the development is an organic solvent.

[17] A substrate with a cured relief pattern produced by the method of [15] or [16 ].

[18] A semiconductor device comprising a semiconductor element and a cured film provided on an upper or lower portion of the semiconductor element, wherein the cured film is a cured uneven pattern formed of the photosensitive resin composition according to any one of [1] to [11 ].

Effects of the invention

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

Detailed Description

(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 of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having 3 or more aromatic rings.

The reaction product contains an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having 3 or more aromatic rings as constituent components, and may contain other diamine compounds and other tetracarboxylic acid derivatives as constituent components, as required.

The reaction product is, for example, a polyamic acid or a polyimide obtained by dehydrating and ring-closing a polyamic acid.

The reaction product contains an aromatic diamine compound having a photopolymerizable group in a constituent component, and thus imparts photosensitivity to a resin composition containing the reaction product.

The reaction product contains an aromatic diamine compound and a tetracarboxylic acid derivative having 3 or more aromatic rings as constituent components, whereby a low dielectric loss tangent and a high tensile elongation can be obtained in the obtained cured film.

In the aromatic diamine compound having a photopolymerizable group, 2 amino groups may be bonded to 1 aromatic ring or may be bonded to 2 aromatic rings, respectively. Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

The aromatic diamine compound may have an aromatic ring to which an amino group is not bonded.

Examples of the photopolymerizable group include a radical polymerizable group, a cation polymerizable group, and an anion polymerizable group. Among them, radical polymerizable groups are preferable.

Examples of the radical polymerizable group include an acryl group, a methacryl group, an acryl ether group, a vinyl ether group, and a vinyl group.

From the viewpoint of obtaining a lower dielectric loss tangent and a higher tensile elongation in the obtained cured film, the reaction product preferably contains an aromatic diamine compound having 3 or more aromatic rings as a diamine compound other than the aromatic diamine compound having a photopolymerizable group in the constituent components.

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, and may be, for example, 4 or more. The upper limit of the number of aromatic rings is not particularly limited, and may be 8 or less, or 6 or less, for example.

In the method for counting aromatic rings in "3 or more aromatic rings", a polycyclic aromatic ring in which 2 or more aromatic rings such as a naphthalene ring and an anthracene ring are condensed is counted as 1 aromatic ring. Therefore, naphthalene rings are counted as 1 aromatic ring. On the other hand, the biphenyl ring is not a condensed ring, and is thus counted as 2 aromatic rings. The perylene ring is considered to have a structure in which 2 naphthalene rings are bonded, and is counted as 2 aromatic rings.

Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

Examples of the tetracarboxylic acid derivative in the "tetracarboxylic acid derivative" include: tetracarboxylic dianhydride, tetracarboxylic dihalide, tetracarboxylic dialkyl ester, and tetracarboxylic dialkyl ester dihalide are particularly preferable.

As the tetracarboxylic acid derivative having 3 or more aromatic rings, an aromatic tetracarboxylic acid derivative having 3 or more aromatic rings is preferable. The aromatic tetracarboxylic acid is a compound in which 4 carboxyl groups are bonded in total 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, and may be, for example, 4 or more. The upper limit of the number of aromatic rings is not particularly limited, and may be 8 or less, or 6 or less, for example.

The proportion of the aromatic diamine compound having a photopolymerizable group to the entire diamine compound constituting the reaction product is not particularly limited, but is preferably 10 to 100 mol%, more preferably 50 to 100 mol%, from the viewpoint of obtaining sufficient photosensitivity.

The proportion of the aromatic tetracarboxylic acid derivative having 3 or more aromatic rings to the total tetracarboxylic acid derivatives constituting the reaction product is not particularly limited, but is preferably 20 to 100 mol%, more preferably 50 to 100 mol%, from the viewpoint of suitably obtaining the effect of the present invention.

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 uneven pattern, polyimide obtained by dehydrating and ring-closing a polyamic acid is more preferable. Here, the imidization rate of polyimide is not necessarily 100%. The imidization ratio may be, for example, 90% or more, 95% or more, or 98% or more.

The polyamic acid preferably has at least a structural unit represented by the following formula (1).

The polyimide preferably has at least a structural unit represented by the following formula (2).

[ chemical 7]

[ chemical 8]

[ in formula (2), ar ₃ Ar represents a 2-valent organic group having a photopolymerizable group and an aromatic ring ₄ Represents a 4-valent organic group having 3 or more aromatic rings. ]

<<Ar ₁ Ar and Ar ₃ >>

Ar ₁ Ar and Ar ₃ The 2-valent organic group having a photopolymerizable group and an aromatic ring is not particularly limited as long as the effect of the present invention is exhibited. The 2-valent organic group having a photopolymerizable group and an aromatic ring is a residue obtained by removing 2 amino groups from an aromatic diamine compound having a photopolymerizable group.

Examples of the photopolymerizable group include the above-mentioned photopolymerizable group.

Ar ₁ Ar and Ar ₃ The organic group having a valence of 2 represented by the following formula (6) is preferable.

[ chemical 9]

[ in formula (6), Z ₃ Represents an ether bond (-O-), an ester bond (-COO-); amide bond (-NHCO-); a urethane bond (-NHCOO-) or a urea bond (-NHCONH-), Z is Z ₄ Represents a direct bond, an ester bond (-COO-) or an amide bond (-NHCO-). Z is Z ₅ Represents a direct bond, an ether bond (-O-), an ether bond ester bond (-COO-), amide bond (-NHCO-), urethane bond (-NHCOO-), urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO-) ₂ -). m2 represents an integer of 0 to 1. R is R ₁₁ Represents a directly bonded or hydroxy-substituted alkylene group having 2 to 6 carbon atoms, R ₁₂ Represents a hydrogen atom or a methyl group. * Representing 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, 1, 2-propylene, 1, 3-propylene, 1, 4-butylene, 1, 2-butylene, 2, 3-butylene, 1, 2-pentylene, 2, 4-pentylene, 1, 2-hexylene, 1, 2-cyclopropyl, 1, 2-cyclobutylene, 1, 3-cyclobutylene, 1, 2-cyclopentylene, 1, 2-hexylene, alkylene groups in which at least a part of these hydrogen atoms is replaced with a hydroxyl group (e.g., 2-hydroxy-1, 3-propylene), and the like.

As Z ₃ Ester bonds are preferred.

As Z ₄ Ester bonds are preferred.

As R ₁₁ 1, 2-ethylene is preferred.

Examples of the 2-valent organic group represented by the formula (6) include the following 2-valent organic groups.

[ chemical 10]

Wherein, represents a bond. The 2 bonding bonds are located, for example, in meta positions with respect to the substituents having the photopolymerizable group.

<<Ar ₂ Ar and Ar ₄ >>

Ar as in formula (1) ₂ Ar in formula (2) ₄ The organic group having 3 or more aromatic rings and exhibiting the effect of the present invention is not particularly limited as long as it is a 4-valent organic group, and from the viewpoint of properly obtaining the effect of the present invention, a 2-valent organic group represented by the following formula (3) is preferable.

[ chemical 11]

[ in formula (3), X ₁ X is X ₂ Each independently represents a direct bond, an ether bond (-O-), an ether bond ester bond (-COO-), amide bond (-NHCO-), urethane bond (-NHCOO-), urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO-) ₂ -)。R ₁ R is R ₂ Each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted. Y represents a 2-valent organic group represented by the following formula (3-1) or (3-2). n1 and n2 are independently of each otherStanding represents an integer of 0 to 3. At R ₁ In the case of a plurality of R ₁ May be the same or different. At R ₂ In the case of a plurality of R ₂ May be the same or different. * Representing a bond.]

As R ₁ R is R ₂ Examples of the alkyl group having 1 to 6 carbon atoms which may be substituted include alkyl groups having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include: methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like. In the present specification, the alkyl group may be linear, branched, cyclic, or a combination of 2 or more thereof unless the structure is specifically mentioned.

Examples of the substituent in the alkyl group having 1 to 6 carbon atoms which may be substituted include: halogen atom, hydroxyl group, mercapto group, carboxyl group, cyano group, formyl group, 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 "carbon number 1 to 6" of the "alkyl group having 1 to 6 carbon atoms which may be substituted" means the carbon number of the "alkyl group" other than the substituent. The number of substituents is not particularly limited.

[ chemical 12]

[ in formula (3-1), Z ₁ Represents a direct bond, an ether bond (-O-), an ether bond ester bond (-COO-), amide bond (-NHCO-), urethane bond (-NHCOO-), urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO-) ₂ -)。R ₃ R is R ₄ Each independently represents a hydrocarbon group having 1 to 6 carbon atoms which may be substituted. m1 represents an integer of 0 to 3. n3 and n4 each independently represent an integer of 0 to 4. At Z ₁ In the case of a plurality of Z' s ₁ May be the same or different. When n4 is plural, plural n4 may be the same or different. At R ₃ In the case of a plurality of R ₃ May be the same or different. At R ₄ In the case of a plurality of R ₄ May be the same or different. * Representing a bond.

As R ₃ 、R ₄ 、R ₅ R is R ₆ Examples of the hydrocarbon group having 1 to 6 carbon atoms which may be substituted include an alkyl group having 1 to 6 carbon atoms which may be substituted and a phenyl group which may be substituted. Examples of the substituent include: halogen atom, hydroxyl group, mercapto group, carboxyl group, cyano group, formyl group, 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 "carbon number 1 to 6" of the "hydrocarbon group having 1 to 6 carbon atoms which may be substituted" means the carbon number of the "hydrocarbon group" other than the substituent. The number of substituents is not particularly limited.

As R ₃ 、R ₄ 、R ₅ R is R ₆ Specific examples of the alkyl group having 1 to 6 carbon atoms which may be substituted include R ₁ R is R ₂ Alkyl groups having 1 to 6 carbon atoms which may be substituted are exemplified in the description of (a).

[ chemical 13]

As R ₇ R is R ₈ Examples of the hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom include an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a phenyl group, a halophenyl group and the like. Examples of the alkyl group having 1 to 6 carbon atoms include: methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like. Examples of the halogen atom in the haloalkyl group having 1 to 6 carbon atoms include: fluorine atom, chlorine atom, bromine atom, iodine atom. The halogeno group in the halogenoalkyl group having 1 to 6 carbon atoms and the halogenophenyl group may be a part or all of them.

As R ₉ R is R ₁₀ Examples of the substituent in the alkylene group having 1 to 6 carbon atoms which may be substituted include: halogen atom, hydroxyl group, mercapto group, carboxyl group, cyano group, formyl group, 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.

Examples of the alkylene group having 1 to 6 carbon atoms which may be substituted include an alkylene group having 1 to 6 carbon atoms, a halogenated alkylene group having 1 to 6 carbon atoms, and the like. Examples of the alkylene group having 1 to 6 carbon atoms include methylene, ethylene, propylene, and butylene.

The "carbon number 1 to 6" of the "alkylene group having 1 to 6 carbon atoms which may be substituted" means the carbon number of the "alkylene group" other than the substituent. The number of substituents is not particularly limited.

As R ₉ R is R ₁₀ Examples of the substituent in the arylene group having 6 to 10 carbon atoms which may be substituted include a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be halogenated, an alkoxy group having 1 to 6 carbon atoms which may be halogenated, and the like. The halogenation may be a part or all of the above.

Examples of the arylene group include phenylene and naphthylene.

The "carbon number 6 to 10" of the "arylene group having 6 to 10 carbon atoms which may be substituted" means the carbon number of the "arylene group" other than the substituent. The number of substituents is not particularly limited.

Examples of the 2-valent organic group represented by the formula (4) include 2-valent organic groups represented by the following formulas.

[ chemical 14]

Wherein, represents a bond.

Examples of the 2-valent organic group represented by the formula (5) include 2-valent organic groups represented by the following formulas.

[ 15]

Wherein R is ₁₃ ～R ₁₅ Each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom. n13 represents an integer of 0 to 5. n14 and n15 each independently represent an integer of 0 to 4. At R ₁₃ In the case of a plurality of R ₁₃ May be the same or different. At R ₁₄ In the case of a plurality of R ₁₄ May be the same or different. At R ₁₅ In the case of a plurality of R ₁₅ May be the same or different. * Representing a bond.

As R ₁₃ ～R ₁₅ Specific examples of the alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom include an alkyl group having 1 to 6 carbon atoms and a haloalkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include: methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like. Examples of the halogen atom in the haloalkyl group having 1 to 6 carbon atoms include: fluorine atom, chlorine atom, bromine atom, iodine atom. Halogen with 1 to 6 carbon atoms The halo in the alkyl group may be a part or all.

As R ₁₃ ～R ₁₅ Specific examples of the alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom include an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom as an alkoxy group.

As Ar ₂ Ar and Ar ₄ Examples thereof include a 4-valent organic group represented by the following formula.

[ 16]

[ chemical 17]

Wherein, represents a bond.

< other structural units >)

The polyamic acid may have a structural unit other than the structural unit represented by the formula (1). Examples of the other structural unit include a structural unit represented by the following formula (1').

The polyimide may have other structural units than the structural unit represented by the formula (2). Examples of the other structural unit include a structural unit represented by the following formula (2').

[ chemical 18]

[ in formula (1'), ar _1′ Ar represents a 2-valent organic group having a photopolymerizable group and an aromatic ring or a 2-valent organic group other than a 2-valent organic group having a photopolymerizable group and an aromatic ring _2′ Represents a 4-valent organic group having 3 or more aromatic rings or a 4-valent organic group having no 3 or more aromatic rings. Wherein Ar is _1′ Is 2-valent with a photopolymerisable group and an aromatic ringA radical Ar _2′ Except for the case of a 4-valent organic group having 3 or more aromatic rings.]

[ chemical 19]

[ in formula (2'), ar _3′ Ar represents a 2-valent organic group having a photopolymerizable group and an aromatic ring or a 2-valent organic group other than a 2-valent organic group having a photopolymerizable group and an aromatic ring _4′ Represents a 4-valent organic group having 3 or more aromatic rings or a 4-valent organic group having no 3 or more aromatic rings. Wherein Ar is _3′ Is a 2-valent organic group having a photopolymerizable group and an aromatic ring, and Ar _4′ Except for the case of a 4-valent organic group having 3 or more aromatic rings.]

As Ar _1′ Ar and Ar _2′ The following combinations (i) to (iii) are given as examples of the combinations (a) and (b).

(i)：Ar _1′ Ar represents a 2-valent organic group having a photopolymerizable group and an aromatic ring _2′ Represents a combination of 4-valent organic groups having no aromatic rings of 3 or more

(ii)：Ar _1′ Represents a 2-valent organic group other than a 2-valent organic group having a photopolymerizable group and an aromatic ring, ar _2′ Represents a combination of 4-valent organic groups having no aromatic rings of 3 or more

(iii)：Ar _1′ Represents a 2-valent organic group other than a 2-valent organic group having a photopolymerizable group and an aromatic ring, ar _2′ Represents a combination of 4-valent organic groups having 3 or more aromatic rings

As Ar _3′ Ar and Ar _4′ The following combinations (iv) to (vi) are given as examples of the combinations (i).

(iv)：Ar _3′ Ar represents a 2-valent organic group having a photopolymerizable group and an aromatic ring _4′ Represents a combination of 4-valent organic groups having no aromatic rings of 3 or more

(v)：Ar _3′ The representation has light2-valent organic groups other than 2-valent organic groups of the polymerizable group and aromatic ring, ar _4′ Represents a combination of 4-valent organic groups having no aromatic rings of 3 or more

(vi)：Ar _3′ Represents a 2-valent organic group other than a 2-valent organic group having a photopolymerizable group and an aromatic ring, ar _4′ Represents a combination of 4-valent organic groups having 3 or more aromatic rings

<<Ar _1′ Ar and Ar _3′ >>

As Ar _1′ Ar and Ar _3′ Examples of the 2-valent organic group having a photopolymerizable group and an aromatic ring in (B) include Ar ₁ Ar and Ar ₃ A 2-valent organic group having a photopolymerizable group and an aromatic ring, which are exemplified in the description of (a).

As Ar _1′ Ar and Ar _3′ The 2-valent organic group other than the 2-valent organic group having a photopolymerizable group and an aromatic ring is not particularly limited, and a 2-valent organic group having 3 or more aromatic rings is preferable in that a lower dielectric loss tangent and a higher tensile elongation can be obtained in the obtained cured film.

The 2-valent organic group having 3 or more aromatic rings is not particularly limited, and is preferably a 2-valent organic group represented by the following formula (13).

[ chemical 20]

[ in formula (13), X ₂₁ X is X ₂₂ Each independently represents a direct bond, an ether bond (-O-), an ether bond ester bond (-COO-), amide bond (-NHCO-), urethane bond (-NHCOO-), urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO-) ₂ -)。R ₂₁ R is R ₂₂ Each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted. Y is Y ₂₀ The 2-valent organic group represented by the following formula (13-1) or (13-2). n21 and n22 each independently represent an integer of 0 to 4. At R ₂₁ In the case of a plurality of R ₂₁ May be the same or different. At R ₂₂ In the case of a plurality of R ₂₂ May be the same or different. * Representing a bond.]

As R ₂₁ R is R ₂₂ Specific examples of the alkyl group having 1 to 6 carbon atoms which may be substituted include R ₁ R is R ₂ Alkyl groups having 1 to 6 carbon atoms which may be substituted are exemplified in the description of (a).

[ chemical 21]

[ in formula (13-1), Z ₂₁ Represents a direct bond, an ether bond (-O-), an ether bond ester bond (-COO-), amide bond (-NHCO-), urethane bond (-NHCOO-), urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO-) ₂ -)。R ₂₃ R is R ₂₄ Each independently represents a hydrocarbon group having 1 to 6 carbon atoms which may be substituted. m21 represents an integer of 0 to 3. n23 and n24 each independently represent an integer of 0 to 4. At Z ₂₁ In the case of a plurality of Z' s ₂₁ May be the same or different. When n24 is plural, plural n24 may be the same or different. At R ₂₃ In the case of a plurality of R ₂₃ May be the same or different. At R ₂₄ In the case of a plurality of R ₂₄ May be the same or different. * Representing a bond.

In the formula (13-2), Z ₂₂ The 2-valent organic group represented by the following formula (14) or (15). R is R ₂₅ R is R ₂₆ Each independently represents a hydrocarbon group having 1 to 6 carbon atoms which may be substituted. n25 and n26 each independently represent an integer of 0 to 4. At R ₂₅ In the case of a plurality of R ₂₅ May be the same or different. At R ₂₆ In the case of a plurality of R ₂₆ May be the same or different. * Representing a bond.]

As R ₂₃ 、R ₂₄ 、R ₂₅ R is R ₂₆ Specific examples of the hydrocarbon group having 1 to 6 carbon atoms which may be substituted include R ₃ 、R ₄ 、R ₅ R is R ₆ The hydrocarbon group having 1 to 6 carbon atoms which may be substituted is exemplified in the description of (a).

As R ₂₃ 、R ₂₄ 、R ₂₅ R is R ₂₆ Specific examples of the alkyl group having 1 to 6 carbon atoms which may be substituted include R ₁ R is R ₂ Alkyl groups having 1 to 6 carbon atoms which may be substituted are exemplified in the description of (a).

[ chemical 22]

[ in formula (14), R ₂₇ R is R ₂₈ Each independently represents a hydrogen atom, or a hydrocarbon group of 1 to 6 carbon atoms which may be substituted with a halogen atom. * Representing a bond.

In the formula (15), R ₂₉ R is R ₃₀ Each independently represents an alkylene group having 1 to 6 carbon atoms which may be substituted or an arylene group having 6 to 10 carbon atoms which may be substituted. * Representing a bond.]

As R ₂₇ R is R ₂₈ Specific examples of the hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom include R ₇ R is R ₈ The hydrocarbon group of 1 to 6 carbon atoms which may be substituted with a halogen atom is exemplified in the description of (a).

As R ₂₉ R is R ₃₀ Specific examples of the alkylene group having 1 to 6 carbon atoms which may be substituted include R ₉ R is R ₁₀ An alkylene group having 1 to 6 carbon atoms which may be substituted is exemplified in the description of (a).

As R ₂₉ R is R ₃₀ Specific examples of the optionally substituted arylene group having 6 to 10 carbon atoms include R ₉ R is R ₁₀ Arylene groups having 6 to 10 carbon atoms which may be substituted are exemplified in the description of (a).

Examples of the 2-valent organic group represented by the formula (14) include 2-valent organic groups represented by the following formulas.

[ chemical 23]

Wherein, represents a bond.

Examples of the 2-valent organic group represented by the formula (15) include 2-valent organic groups represented by the following formulas.

[ chemical 24]

Wherein R is ₃₃ ～R ₃₅ Each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom. n33 represents an integer of 0 to 5. n34 and n35 each independently represent an integer of 0 to 4. At R ₃₃ In the case of a plurality of R ₃₃ May be the same or different. At R ₃₄ In the case of a plurality of R ₃₄ May be the same or different. At R ₃₅ In the case of a plurality of R ₃₅ May be the same or different. * Representing a bond.

As R ₃₃ ～R ₃₅ Specific examples of the alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom include R ₁₃ ～R ₁₅ Alkyl groups having 1 to 6 carbon atoms which may be substituted with halogen atoms are exemplified in the description of (a).

As R ₃₃ ～R ₃₅ Specific examples of the alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom include an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom as an alkoxy group.

As Ar _1′ Ar and Ar _3′ Examples thereof include a 2-valent organic group represented by the following formula.

[ chemical 25]

[ chemical 26]

Wherein, represents a bond.

As other Ar _1′ Ar and Ar _3′ Examples thereof include a 2-valent organic group represented by the following formula.

[ chemical 27]

Wherein, represents a bond.

<<Ar _2′ Ar and Ar _4′ >>

As Ar _2′ Ar and Ar _4′ The 4-valent organic group having 3 or more aromatic rings in (3) may be Ar ₂ Ar and Ar ₄ A 4-valent organic group having 3 or more aromatic rings is exemplified in the description of (a).

As Ar _2′ Ar and Ar _4′ 4-valent organic groups not having 3 or more aromatic rings, for example Examples thereof include a 4-valent organic group having 1 or 2 aromatic rings and a 4-valent organic group having no aromatic rings. A 4-valent organic group having 1 or 2 aromatic rings, for example, from an aromatic tetracarboxylic dianhydride derivative. Further, the 4-valent organic group having no aromatic ring is derived from, for example, an aliphatic tetracarboxylic anhydride derivative. The 4-valent organic group is not particularly limited, and examples thereof include the following 4-valent organic groups.

[ chemical 28]

[ chemical 29]

Wherein, represents a bond.

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 preferably 10 to 100 mol%, more preferably 50 to 100 mol%, from the viewpoint of obtaining sufficient photosensitivity. The 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 whole structural units of the polyamic acid is not particularly limited, but is preferably 1 to 90 mol%, more preferably 1 to 50 mol%.

When the imidization ratio of the polyimide is not 100%, the polyimide may have a structural unit represented by the formula (1) in addition to the structural unit represented by the formula (2).

The total proportion of the structural units represented by the formula (1) and the structural units represented by the formula (2) in all the structural units of the polyimide is not particularly limited, but is preferably 10 to 100 mol%, more preferably 50 to 100 mol%, from the viewpoint of obtaining sufficient photosensitivity.

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 total ratio of the structural unit represented by the formula (1 ') to the structural unit represented by the formula (2') in the whole structural units of the polyimide is not particularly limited, but is preferably 1 to 90 mol%, more preferably 1 to 50 mol%.

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

< method for producing reaction product >

The reaction product is obtained by reacting an aromatic diamine compound having a photopolymerizable group, a tetracarboxylic acid derivative having 3 or more aromatic rings, and if necessary, another diamine compound with another tetracarboxylic acid derivative.

The method for producing the reaction product is not particularly limited, and examples thereof include known methods for obtaining polyamic acid or polyimide by reacting a diamine compound with a tetracarboxylic acid derivative. The polyamic acid and polyimide can be synthesized by a known method described in, for example, WO 2013/157586.

The reaction product is produced, for example, by reacting (polycondensing) a diamine component containing an aromatic diamine compound having a photopolymerizable group with a tetracarboxylic acid derivative component having 3 or more aromatic rings in a solvent.

Specific examples of the solvent include: n-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylisobutyramide, dimethylsulfoxide, 1, 3-dimethyl-2-imidazolidinone. In addition, when the solvent solubility of the polymer is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or a solvent represented by the following formulas [ D-1] to [ D-3] can be used.

[ chemical 30]

([ D-1]]In (D) ¹ Represents an alkyl group having 1 to 3 carbon atoms, and the formula [ D-2 ]]In (D) ² Represents an alkyl group having 1 to 3 carbon atoms, and the formula [ D-3 ]]In (D) ³ Represents an alkyl group having 1 to 4 carbon atoms. ).

These solvents may be used alone or in combination. Further, even if the solvent does not dissolve the reaction product, the solvent may be used in combination within a range where the reaction product is not precipitated.

When the diamine component and the tetracarboxylic acid derivative component are reacted in a solvent, the reaction can be carried out at an arbitrary concentration, and is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction may be carried out at a high concentration at the beginning of the reaction, and then a solvent may be added.

In the reaction, the ratio of the total mole number of the diamine component to the total mole number of the tetracarboxylic acid derivative component is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resultant reaction product.

In the case of reacting the diamine component with 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 the thermal polymerization inhibitor include: hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, ethylene glycol diethylether diamine tetraacetic 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 to be used is not particularly limited.

Polyimide is obtained by dehydrating and ring-closing a polyamic acid which is a reaction product obtained in the above reaction.

Examples of the method for obtaining polyimide include thermal imidization in which a solution of polyamic acid, which is a reaction product obtained in the above reaction, is directly heated, and chemical imidization in which a catalyst is added to a solution of polyamic acid. The temperature in the case of thermal imidization in the solution is 100 to 400 ℃, preferably 120 to 250 ℃, and it is preferable to conduct the imidization while removing water generated by the imidization reaction to the outside of the system.

The chemical imidization can be performed by adding an alkaline catalyst and an acid anhydride to a solution of the polyamic acid obtained in the reaction and stirring the mixture at-20 to 250 ℃, preferably 0 to 180 ℃. The amount of the basic catalyst is 0.1 to 30 mol times, preferably 0.2 to 20 mol times, that of the amide acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 1.5 to 30 mol times, that of the amide acid group. The basic catalyst may be pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, or the like, and among these, triethylamine is preferable because it is not easy to produce a polyisoimide as a by-product. The acid anhydride may be acetic anhydride, trimellitic anhydride, pyromellitic anhydride, or the like, and among them, if acetic anhydride is used, purification after completion of the reaction is easy, so that it is preferable. The imidization rate (also referred to as the ratio of the recurring units to the total recurring units of the polyimide precursor, the ring closure rate) by chemical imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

In the case of recovering the imide compound produced from the imidized reaction solution, the reaction solution may be put into a solvent to precipitate the imide compound. Examples of the solvent used for precipitation include: methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, etc. The polymer precipitated in the solvent can be recovered by filtration and dried at normal or reduced pressure, normal temperature or by heating.

Part or all of the repeating units of polyimide are closed-loop. The imidization rate in the polyimide is preferably 20 to 99%, more preferably 30 to 99%, and even more preferably 50 to 99%.

The polyimide may be end-capped. The method of blocking is not particularly limited, and conventionally known methods using monoamines or anhydrides can be used, for example.

< solvent >

As the solvent contained in the photosensitive resin composition, an organic solvent is preferably used in view of solubility in the reaction product. Specifically, there may be mentioned: n, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylisobutyramide, dimethylsulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, gamma-butyrolactone, alpha-acetyl-gamma-butyrolactone, tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, 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 a solvent represented by the following formulae [ D-1] to [ D-3], and the like, which can be used alone or in combination of 2 or more.

[ 31]

([ D-1 ]]In (D) ¹ Represents an alkyl group having 1 to 3 carbon atoms, and the formula [ D-2 ]]In (D) ² Represents an alkyl group having 1 to 3 carbon atoms, and the formula [ D-3 ]]In (D) ³ Represents an alkyl group having 1 to 4 carbon atoms. ).

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

< other Components >)

In an embodiment, the photosensitive resin composition may further contain a reaction product and other components than a solvent. Examples of the other components include: a photo radical polymerization initiator (also referred to as a "photo radical initiator"), a crosslinkable compound (also referred to as a "crosslinking agent"), a thermosetting agent, other resin components, a filler, a sensitizer, an adhesion promoter, a thermal polymerization inhibitor, an azole compound, a hindered phenol compound, and the like.

Photo radical polymerization initiator

The photo radical polymerization initiator is not particularly limited as long as it is a compound having absorption against a light source used at the time of photo curing, and examples thereof include: tert-butyl peroxy-isobutyrate, 2, 5-dimethyl-2, 5-bis (benzoylperoxy) hexane, 1, 4-bis [ alpha- (tert-butylperoxy) -isopropoxy ] benzene, di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexene hydroperoxide, alpha- (isopropylphenyl) -isopropyl hydroperoxide, tert-butyl hydroperoxide, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane, 4-bis (tert-butylperoxy) butyl valerate, cyclohexanone peroxide, 2',5,5' -tetra (t-butylperoxy carbonyl) benzophenone, 3', 4' -tetra (t-amyl peroxy carbonyl) benzophenone, 3', organic peroxides such as 4,4' -tetrakis (t-hexylperoxycarbonyl) benzophenone, 3 '-bis (t-butylperoxycarbonyl) -4,4' -dicarboxybenzophenone, t-butyl peroxybenzoate, and di-t-butyl peroxyisophthalate; quinones such as 9, 10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 1, 2-benzanthraquinone; benzoin derivatives such as benzoin methyl ether, benzoin ethyl ether, α -methylbenzin, α -phenylbenzoin, and the like; alkylbenzene-based compounds such as 2, 2-dimethoxy-1, 2-diphenylethan-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-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one; acyl phosphine oxide compounds such as bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide and 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide; oxime ester compounds such as 2- (O-benzoyl oxime) -1- [4- (phenylthio) phenyl ] -1, 2-octanedione, 1- (O-acetyl oxime) -1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone.

The photo radical polymerization initiator is commercially available, and examples thereof include: IRGACURE [ registered trademark ]651, IRGACURE 184, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, IRGACURE 819DW, IRGACURE 1800, IRGACURE 1870, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE03, IRGACURE OXE04, IRGACURE 250, IRGACURE 1173, IRGACURE MBF, IRGACURE TPO, IRGACURE 4265, IRGACURE TPO (manufactured by BASF corporation above), KAYACURE [ registered trademark ] DETX-S, KAYACURE MBP, KACURE DMBI, KAYACURE EPA, KAYACURE KAYACURE OA (manufactured by japan chemical Co., ltd.), VICURE-10, VICURE-55 (manufactured by starlight co.LTD), esaceu KIP 150, esaceu TZT, esaceu 1001, esaceu KTO46, esaceu KB1, esaceu KL 200, esaceu KS 300, esaceu EB3, triazine-PMS, triazine a, triazine B (manufactured by japan siberner Co., ltd.), ADEKA OPTOMER N-1717, ADEKA OPTOOMER N-1414, ADEKA OPTOMER N-1606, ADEKA ARKLS N-1919T, ADEKA ARKLS NCI-E, ADEKA ARKLS NCI-930, ADEKAARKLS NCI-730 (manufactured by ADEKA Co., ltd.).

These photo radical polymerization initiators may be used alone or in combination of two or more.

The content of the photo radical polymerization initiator is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, from the viewpoint of photosensitivity characteristics, based on 100 parts by mass of the reaction product. When the photo radical polymerization initiator is contained in an amount of 0.1 parts by mass or more relative to 100 parts by mass of the reaction product, the photosensitivity of the photosensitive resin composition is easily improved, while when the photo radical polymerization initiator is contained in an amount of 20 parts by mass or less, the thick film curability of the photosensitive resin composition is easily improved.

Crosslinkable compound

In the embodiment, in order to improve the resolution of the uneven pattern, a monomer (crosslinkable compound) having a photoradically polymerizable unsaturated bond may be optionally contained in the photosensitive resin composition.

The crosslinkable compound is preferably a (meth) acrylic compound that undergoes radical polymerization by a photo radical polymerization initiator, and is not particularly limited to the following, and examples thereof include: diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, ethylene glycol or polyethylene glycol mono-or di (meth) acrylate, propylene glycol or polypropylene glycol mono-or di (meth) acrylate, glycerol mono-, di-or tri (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, cyclohexanedi (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, and di (meth) acrylate of tricyclodecanedimethanol, di (meth) acrylate of dioxane glycol, mono-or di (meth) acrylate of bisphenol A, di (meth) acrylate of bisphenol F, di (meth) acrylate of hydrogenated bisphenol A, trimethacrylate, di (meth) acrylate of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, isobornyl (meth) acrylate, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, trimethylol propyl (meth) acrylate, di-or tri (meth) acrylate of glycerol, di-, tri-or tetra (meth) acrylic acid esters of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds, 2-isocyanatoethyl (meth) acrylate or isocyanate-containing (meth) acrylic acid esters, and blocking agents such as methyl ethyl ketoxime, epsilon-caprolactam, gamma-caprolactam, 3, 5-dimethylpyrazole, diethyl malonate, ethanol, isopropanol, n-butanol, 1-methoxy-2-propanol, and the like are added thereto. These compounds may be used alone or in combination of 2 or more. In the present specification, (meth) acrylate means acrylate and methacrylate.

The content of the crosslinkable compound is not particularly limited, but is preferably 1 part by mass to 100 parts by mass, more preferably 1 part by mass to 50 parts by mass, based on 100 parts by mass of the reaction product.

Thermosetting agent

Examples of the thermosetting agent include: hexamethoxymethyl melamine, tetramethoxymethyl glycoluril, tetramethoxymethyl benzoguanamine, 1,3,4, 6-tetra (methoxymethyl) glycoluril, 1,3,4, 6-tetra (butoxymethyl) glycoluril, 1,3,4, 6-tetra (hydroxymethyl) glycoluril, 1, 3-bis (hydroxymethyl) urea, 1, 3-tetra (butoxymethyl) urea, 1, 3-tetra (methoxymethyl) urea, and the like.

The content of the thermosetting agent in the photosensitive resin composition is not particularly limited.

Filler >)

Examples of the filler include inorganic fillers, and specifically, sols such as silica, aluminum nitride, boron nitride, zirconia, and alumina.

The content of the filler in the photosensitive resin composition is not particularly limited.

Other resin component

In an embodiment, the photosensitive resin composition may further contain a resin component other than the reaction product. Examples of the resin component that can be contained in the photosensitive resin composition include polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, silicone resin, and acrylic resin.

The content of these resin components is not particularly limited, but is preferably in the range of 0.01 to 20 parts by mass based on 100 parts by mass of the reaction product.

Sensitizer

In the embodiment, a sensitizer may be optionally blended into the photosensitive resin composition in order to improve photosensitivity.

Examples of the sensitizer include: midson, 4 '-bis (diethylamino) benzophenone, 2, 5-bis (4' -diethylaminobenzylidene) cyclopentane, 2, 6-bis (4 '-diethylaminobenzylidene) cyclohexanone, 2, 6-bis (4' -diethylaminobenzylidene) -4-methylcyclohexanone, 4 '-bis (dimethylamino) chalcone, 4' -bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenyl biphenylene) -benzothiazole, 2- (p-dimethylaminophenyl vinylene) benzothiazole, and 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1, 3-bis (4 '-dimethylaminobenzylidene) acetone, 1, 3-bis (4' -diethylaminobenzylidene) acetone, 3 '-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N' -ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1, 2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, and the like.

They may be used alone or in combination of plural kinds.

The content of the sensitizer is not particularly limited, but is preferably 0.1 to 25 parts by mass per 100 parts by mass of the reaction product.

Bonding aid

In the embodiment, an adhesion promoter may be optionally blended in the photosensitive resin composition in order to improve adhesion between a film formed using the photosensitive resin composition and a substrate.

Examples of the adhesion promoter include: silane coupling agents such as gamma-aminopropyl dimethoxysilane, N- (. Beta. -aminoethyl) -gamma-aminopropyl methyldimethoxysilane, gamma-glycidoxypropyl methyldimethoxysilane, gamma-mercaptopropyl methyldimethoxysilane, 3- (meth) acryloxypropyl dimethoxymethylsilane, 3- (meth) acryloxypropyl trimethoxysilane, dimethoxymethyl-3-piperidylpropylsilane, diethoxy-3-glycidoxypropyl methylsilane, 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) propylsuccinic anhydride, N-phenylaminopropyl trimethoxysilane, aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), aluminum diisopropropylacetate, and the like.

Among these adhesion aids, a silane coupling agent is more preferably used in terms of adhesion.

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

Thermal polymerization inhibitor

In the embodiment, particularly, a thermal polymerization inhibitor may be optionally blended in order to improve the viscosity and the stability of photosensitivity of the photosensitive resin composition when stored in a state of a solution containing a solvent.

As the thermal polymerization inhibitor, for example, there can be used: hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-t-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2, 6-di-t-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 content of the thermal polymerization inhibitor is not particularly limited, but is preferably in the range of 0.005 to 12 parts by mass based on 100 parts by mass of the reaction product.

Azole compound

For example, in the case of using a substrate containing copper or a copper alloy, an azole compound may be optionally blended in the photosensitive resin composition in order to suppress discoloration of the substrate.

Examples of the azole compound include: 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4, 5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, hydroxyphenyl triazole, 1, 5-dimethyltriazole, 4, 5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [ 2-hydroxy-3, 5-bis (. Alpha., alpha-dimethylbenzyl) phenyl ] -benzotriazole, 2- (3, 5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, hydroxyphenyl benzotriazole, tolyltriazole, 5-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. Tolyltriazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole are particularly preferred.

In addition, 1 kind of these azole compounds may be used, or a mixture of 2 or more kinds may be used.

The content of the azole compound is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 5 parts by mass, from the viewpoint of photosensitivity characteristics, based on 100 parts by mass of the reaction product. When the content of the azole compound is 0.1 part by mass or more relative to 100 parts by mass of the reaction product, discoloration of the surface of copper or copper alloy is suppressed in the case of forming a photosensitive resin composition on copper or copper alloy, and on the other hand, when it is 20 parts by mass or less, photosensitivity is excellent, so that it is preferable.

Hindered phenol compound

In the embodiment, a hindered phenol compound may be optionally blended into the photosensitive resin composition in order to suppress discoloration on copper.

Examples of the hindered phenol compound include: 2, 6-di-tert-butyl-4-methylphenol, 2, 5-di-tert-butyl-hydroquinone, octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, isooctyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 4 '-methylenebis (2, 6-di-tert-butylphenol), 4' -thio-bis (3-methyl-6-tert-butylphenol), 4 '-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2-thio-diethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 2 '-methylenebis (4-methyl-6-tert-butylphenol), 2' -methylenebis (4-ethyl-6-tert-butylphenol), pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-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-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione 1,3, 5-tris (4-sec-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris [4- (1-ethylpropyl) -3-hydroxy-2, 6-dimethylbenzyl ] -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris [ 4-triethylmethyl-3-hydroxy-2, 6-dimethylbenzyl ] -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (3-hydroxy-2, 6-dimethyl-4-phenylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 5, 6-trimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-5-ethyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione 1,3, 5-tris (4-tert-butyl-6-ethyl-3-hydroxy-2, 5-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-5, 6-diethyl-3-hydroxy-2-methylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 5-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl) -1,3, 5-triazine-2, 4,6- (1 h,3h,5 h) -trione and the like, but is not limited thereto.

Of these, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione is particularly preferred.

The content of the hindered phenol compound is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, from the viewpoint of photosensitivity characteristics, relative to 100 parts by mass of the reaction product. When the content of the hindered phenol compound is 0.1 part by mass or more relative to 100 parts by mass of the reaction product, for example, when the photosensitive resin composition is formed on copper or copper alloy, discoloration and corrosion of copper or copper alloy are prevented, and when it is 20 parts by mass or less, photosensitivity is excellent, so that it is preferable.

The photosensitive resin composition can be suitably used as a negative photosensitive resin composition for producing a cured uneven pattern to be described later.

(resin film)

The resin film of the present invention is a fired product of a coating film of the photosensitive resin composition of the present invention.

As the coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating by a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like, a method of spray coating by a spray coater, or the like can be used.

As a method of firing when the fired product is obtained, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature-raising oven capable of setting a temperature program can be selected. The firing can be performed, for example, at 130 to 250℃for 30 minutes to 5 hours. As an atmosphere gas at the time of heat curing, air may be used, 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. Mu.m, more preferably 2 μm to 50. Mu.m.

The resin film is, for example, an insulating film.

(photosensitive resist film)

The photosensitive resin composition of the present invention can be used for a photosensitive resist film (so-called dry film resist).

The photosensitive resist film includes a base film, a photosensitive resin layer (photosensitive resin film) formed from the photosensitive resin composition of the present invention, and a cover film.

Generally, a photosensitive resin layer and a cover film are laminated in this order on a base film.

The photosensitive resist film can be produced, for example, by coating a photosensitive resin composition on a substrate film, drying the composition to form a photosensitive resin layer, and then laminating a cover film on the photosensitive resin layer.

Examples of the method of drying include conditions of 20℃to 200℃and 1 minute to 1 hour.

The thickness of the photosensitive resin layer to be obtained is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm.

As the base film, a known base film, for example, a thermoplastic resin film or the like can be used. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 μm to 150 μm.

As the cover film, a known cover film can be used, and for example, a polyethylene film, a polypropylene film, or the like can be used. The cover film is preferably a film having smaller adhesion to the photosensitive resin layer than the base film. The thickness of the cover film is preferably 2 μm to 150. Mu.m, more preferably 2 μm to 100. Mu.m, particularly preferably 5 μm to 50. Mu.m.

The base film and the cover film may be the same film material, or different films may be used.

(method for producing substrate with cured relief Pattern)

The method for manufacturing a substrate with a cured relief pattern according to the present invention comprises the steps of:

(1) The photosensitive resin composition of the present invention is applied on a substrate, a photosensitive resin layer (photosensitive resin film) is formed on the substrate,

(2) The photosensitive resin layer is subjected to exposure to light,

The following describes each step.

(1) A step of applying the photosensitive resin composition of the present invention on a substrate and forming a photosensitive resin layer on the substrate

In this step, the photosensitive resin composition of the present invention is applied to a substrate, and if necessary, 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, or the like, a method of spray coating with a spray coater, or the like can be used.

The coating film containing the photosensitive resin composition may be dried as needed, and as a drying method, for example, a method such as air drying, heat drying by an oven or a hot plate, vacuum drying, or the like may be used. Specifically, when air-drying or heat-drying is performed, drying can be performed under conditions of 20 to 200 ℃ for 1 minute to 1 hour. Thus, a photosensitive resin layer can be formed on the substrate.

(2) Exposing the photosensitive resin layer

In this step, the photosensitive resin layer formed in the step (1) is exposed to light using an exposure device such as a contact lithography machine, a mirror projection, or a stepper, through a photomask or a reticle (reticle) having a pattern, or directly using an ultraviolet light source or the like.

Examples of the light source used for exposure include g-line, h-line, i-line, ghi-line broadband and KrF excimer laser. The exposure is desirably 25mJ/cm ² ～2000mJ/cm ² 。

Then, for the purpose of improving photosensitivity or the like, a post-exposure bake (PEB) and/or a pre-development bake based on an arbitrary combination of temperature and time may be performed as needed. The baking condition is preferably in the range of 50 to 200℃and the time is preferably in the range of 10 to 600 seconds, but the baking condition is not limited to this range as long as the properties of the photosensitive resin composition are not impaired.

(3) Developing the exposed photosensitive resin layer to form a concave-convex pattern

In this step, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any method may be selected from conventionally known developing methods of photoresists, for example, a spin spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, and the like. In addition, after development, in order to remove the developer, rinsing may be performed. Further, for the purpose of adjusting the shape of the concave-convex pattern, post-development baking based on a combination of an arbitrary temperature and time may be performed as needed.

As the developer used in the development, an organic solvent is preferable. The organic solvent is preferably, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-dimethylacetamide, cyclopentanone, cyclohexanone, gamma-butyrolactone, alpha-acetyl-gamma-butyrolactone, or the like. In addition, 2 or more solvents, for example, a plurality of solvents may be used in combination.

The rinse liquid used for the rinse is preferably an organic solvent which is miscible with the developer and has low solubility in the photosensitive resin composition. Examples of the rinse liquid include methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, toluene, and xylene. In addition, 2 or more solvents, for example, a plurality of solvents may be used in combination.

(4) A step of heating the uneven pattern to form a cured uneven pattern

In this step, the relief pattern obtained by the development is heated and converted into a cured relief pattern. When the reaction product is a polyamic acid, the polyimide is thermally imidized by heating to obtain a cured uneven pattern containing polyimide. As a method of heat curing, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature-raising oven capable of setting a temperature program can be selected. The heating may be performed, for example, at 130 to 250℃for 30 minutes to 5 hours. As an atmosphere gas at the time of heat curing, air may be used, or an inert gas such as nitrogen or argon may be used.

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

(semiconductor device)

In an embodiment, a semiconductor device including a semiconductor element and a cured film provided on an upper portion or a lower portion of the semiconductor element is also provided. The cured film is a cured relief pattern formed from the photosensitive resin composition of the present invention. The cured relief pattern can be obtained, for example, by steps (1) to (4) in the above-described method for producing a substrate with a cured relief pattern.

The present invention is also applicable to a method for manufacturing a semiconductor device including the method for manufacturing a substrate with a cured uneven pattern as part of a process, as well as a semiconductor element used as a substrate. The semiconductor device of the present invention can be manufactured by forming the cured concave-convex pattern into a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for flip chip devices, a protective film for semiconductor devices having a bump structure, or the like, and combining the same with a known manufacturing method of semiconductor devices.

(display device)

In an embodiment, a display device is provided that includes a display element and a cured film provided on an upper portion of the display element, the cured film being the cured concave-convex pattern described above. Here, the cured concave-convex pattern may be laminated in direct contact with the display element, or may be laminated with other layers interposed therebetween. Examples of the cured film include a surface protective film, an insulating film, and a planarizing film for TFT (Thin Film Transistor ) liquid crystal display elements and color filter elements, a projection for MVA (Multi-domain Vertical Alignment ) liquid crystal display devices, and a partition wall for cathodes of organic EL (electroluminescence) elements.

The photosensitive resin composition of the present invention is useful for applications such as interlayer insulating films for multilayer circuits, coverlay coatings for flexible copper clad laminates, solder resist films, and liquid crystal alignment films, in addition to the above-described semiconductor devices.

Examples

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

The weight average molecular weight (Mw) shown in the following synthesis examples is a measurement result based on gel permeation chromatography (hereinafter abbreviated as GPC in the present specification). GPC apparatus (HLC-8320 gPC (manufactured by Tosoh Co., ltd.) was used for measurement, and measurement conditions were as follows.

Column: shodex [ registered trademark ] KD-805/Shodex [ registered trademark ] KD-803 (manufactured by Showa electric Co., ltd.)

Column temperature: 50 DEG C

Flow rate: 1 mL/min

Eluent: n, N-Dimethylformamide (DMF), lithium bromide monohydrate (30 mM)/phosphoric acid (30 mM)/tetrahydrofuran (1%)

Standard sample: polyethylene oxide

The chemical imidization ratio shown in the following synthesis examples was calculated by the following method. 100mg of polyimide powder was placed in an NMR sample tube (NMR sample tube standard,from straw science co., ltd.) was added deuterated dimethyl sulfoxide (DMSO-d 6,0.05% tms (tetramethylsilane) mixture) (0.53 ml), and the mixture was completely dissolved by ultrasonic waves. The solution was subjected to proton NMR at 500MHz using an NMR measuring device (JNM-ECA 500) (manufactured by Japanese electronics Co., ltd.). The chemical imidization rate is determined by taking a proton derived from a structure which does not change before and after imidization as a reference proton The peak accumulation value of the protons and the peak accumulation value of protons derived from NH groups of amic acid occurring in the vicinity of 9.5ppm to 11.0ppm are used to determine the peak accumulation value of protons by the following formula.

Chemical imidization ratio (%) = (1- α·x/y) ×100

In the above formula, x is a proton peak accumulation value of NH groups derived from amic acid, y is a peak accumulation value of reference protons, and α is a number ratio of reference protons to NH group protons of 1 amic acid in the case of polyamic acid (imidization rate is 0%).

Synthesis example 1 Synthesis of Polyamic acid (P-1)

11.00g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 0.05g of 2, 6-di-tert-butyl-p-cresol, and 33.14g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 21.45g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, and 42.68g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 1 hour, the mixture was stirred at 60℃for 93 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-1), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 22,868.

[ chemical 32]

Synthesis example 2 Synthesis of Polyamic acid (P-2)

9.85g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 12.84g of 1, 4-bis [2- (4-aminophenyl) -2-propyl ] benzene, 0.04g of 2, 6-di-tert-butyl-p-cresol, and 53.04g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 37.25g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride and 86.91g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 3 hours, the mixture was stirred at 50℃for 89 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-2), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 25,273.

[ 33]

Synthesis example 3 Synthesis of Polyamic acid (P-3)

10.18g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 11.26g of 1, 4-bis (4-aminophenoxy) benzene, 0.04g of 2, 6-di-t-butyl-p-cresol, and 50.13g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 38.49g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride and 89.82g of N-ethyl-2-pyrrolidone were added to the system, and the mixture was stirred at room temperature for 3 hours and then stirred at 50℃for 89 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-3), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 26,998.

[ chemical 34]

Synthesis example 4 Synthesis of > Polyamic acid (P-4)

13.73g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 9.14g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 0.06g of 2, 6-di-t-butyl-p-cresol, and 53.50g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 37.08g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride and 86.53g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 2 hours, the mixture was stirred at 50℃for 88 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-4), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 24,973.

[ 35]

Synthesis example 5 Synthesis of Polyamic acid (P-5)

9.47g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 14.70g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 0.04g of 2, 6-di-t-butyl-p-cresol, and 56.49g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 35.79g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride and 83.51g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 3 hours, the mixture was stirred at 50℃for 89 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-5), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 27,852.

[ 36]

Synthesis example 6 Synthesis of Polyamic acid (P-6)

3.59g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 13.01g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 0.01g of 2, 6-di-t-butyl-p-cresol, and 66.47g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 23.33g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride and 93.33g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 3 hours and then stirring at 50℃for 95 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-6), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 56,737.

[ 37]

Synthesis example 7 Synthesis of Polyamic acid (P-7)

1.16g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 16.22g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 0.01g of 2, 6-di-t-butyl-p-cresol, and 69.53g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 22.62g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride and 90.47g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 3 hours and then stirring at 50℃for 95 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-7), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 58,225.

[ 38]

Synthesis example 8 Synthesis of Polyamic acid (P-8)

9.71g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 13.54g of 4,4' -bis (4-aminophenoxy) biphenyl, 0.04g of 2, 6-di-tert-butyl-p-cresol, and 54.34g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 36.72g of 4,4' - (4, 4' -isopropylidenediphenoxy) diphthalic anhydride and 85.67g of N-ethyl-2-pyrrolidone were added to the system, and the mixture was stirred at room temperature for 3 hours and then stirred at 50℃for 92 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-8), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 33,012.

[ 39]

Synthesis example 9 Synthesis of Polyamic acid (P-9)

6.22g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 10.18g of bis [4- (4-aminophenoxy) phenyl ] sulfone, 0.03g of 2, 6-di-t-butyl-p-cresol, and 65.70g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 23.52g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride and 94.08g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 2 hours and then stirring at 50℃for 92 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-9), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 31,175.

[ 40]

Synthesis example 10 Synthesis of Polyamic acid (P-10)

6.62g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 13.34g of 9, 9-bis [4- (4-aminophenoxy) phenyl ] fluorene (BPF-AN, manufactured by JFE chemical industries, ltd.), and 79.86g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 25.04g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride and 25.14g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 3 hours, the mixture was stirred at 40℃for 42 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-10), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 25,249.

[ chemical 41]

Synthesis example 11 Synthesis of > Polyamic acid (P-11)

7.94g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 10.46g of bis (4-aminophenyl) terephthalate, 0.05g of 4-methoxyphenol, and 87.05g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 29.98g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride and 58.04g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 3 hours, the mixture was stirred at 50℃for 74 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-11), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 29,792.

[ chemical 42]

Synthesis example 12 Synthesis of Polyamic acid (P-12)

7.94g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 10.46g of 1, 4-phenylenebis (4-aminobenzoate), 0.05g of 4-methoxyphenol, and 87.05g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 29.98g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, and 58.04g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 3 hours, the mixture was stirred at 50℃for 74 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-12), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 24,660.

[ chemical 43]

Synthesis example 13 Synthesis of > Polyamic acid (P-13)

10.95g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 17.01g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 0.05g of 2, 6-di-t-butyl-p-cresol, and 112.00g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under Air, 32.00g of hydroquinone diphthalic anhydride (HQDA, air Water Co., ltd.) and 28.00g of N-ethyl-2-pyrrolidone were added to the system, and the mixture was stirred at room temperature for 2 hours and then at 40℃for 39 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-13), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 21,092.

[ 44]

Synthesis example 14 Synthesis of Polyamic acid (P-14)

8.63g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 13.41g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 0.04g of 2, 6-di-t-butyl-p-cresol, and 88.32g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and after that, 37.92g of bis- (1, 3-dioxo-1, 3-dihydroisobenzofuran-5-carboxylic acid) propane-2, 2-diylbis (2-methyl-4, 1-phenylene) and 51.68g of N-ethyl-2-pyrrolidone were added to the system, and the mixture was stirred at room temperature for 2 hours and then at 40℃for 39 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-14), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 16,379.

[ 45]

Synthesis example 15 Synthesis of > Polyamic acid (P-15)

6.23g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 9.68g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, and 63.64g of N-ethyl-2-pyrrolidone were stirred under air at room temperature to be dissolved, and then, 29.09g of 9, 9-bis [4- (3, 4-dicarboxyphenoxy) phenylfluorene dianhydride (BPF-PA, manufactured by JFE chemical Co., ltd.) and 41.36g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 42 hours at 40 ℃. The obtained polyamic acid had a repeating unit structure represented by the following (P-15), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 24,559.

[ chemical 46]

Synthesis example 16 Synthesis of Polyamic acid (P-16)

5.29g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 10.36g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 0.04g of 4-methoxyphenol, and 65.87g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 9, 9-bis [4- (3, 4-dicarboxyphenoxy) phenylfluorene dianhydride (BPF-PA, manufactured by JFE chemical Co., ltd.) was added to the system, 24.68g, and 28.23g of N-ethyl-2-pyrrolidone were stirred at room temperature for 4 hours, and then stirred at 50℃for 26.5 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-16), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 28,330.

[ 47]

Synthesis example 17 Synthesis of > Polyamic acid (P-17)

6.181g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 9.60g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 0.04g of 4-methoxyphenol, and 79.65g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 24.0g of 5-isobenzofuran carboxylic acid, 1, 3-dihydro-1, 3-dioxo-cyclohexylidene-4, 1-phenylene ester (BPZ-TME, manufactured by Wako pure chemical industries, ltd.), and 39.82g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 1 hour, the mixture was stirred at 50℃for 63 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-17), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 13,550.

[ 48]

< Synthesis example 18> Synthesis of Polyamic acid (P-18)

8.65g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 13.44g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 0.053g of 4-methoxyphenol, and 105.62g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 15.0g of p-phenylenebis (trimellitic anhydride) (TAHQ, manufactured by MANAC Co., ltd.), 15.67g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, and 52.81g of N-ethyl-2-pyrrolidone were added to the mixture, and the mixture was stirred at room temperature for 1 hour and then stirred at 50℃for 40 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-18), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 36,287.

[ 49]

< Synthesis example 19> Synthesis of Polyamic acid (P-19)

8.65g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 13.44g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 0.054g of 4-methoxyphenol, and 107.24g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 9.0g of p-phenylenebis (trimellitic anhydride) (TAHQ, manufactured by MANAC Co., ltd.), 22.49g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, and 53.62g of N-ethyl-2-pyrrolidone were added to the mixture, and the mixture was stirred at room temperature for 1 hour and then stirred at 50℃for 40 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-19), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 34,006.

[ 50]

Synthesis example 20 Synthesis of Polyamic acid (P-20)

7.418g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 11.52g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 0.047g of 4-methoxyphenol, and 126.47g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 15.0g of p-biphenylene bis (trimellitic acid monoester anhydride) (BP-TME, manufactured by Benzhou chemical Co., ltd.), 13.44g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, and 63.23g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 40 hours at 50 ℃. The obtained polyamic acid had a repeating unit structure represented by the following (P-20), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 28,962.

[ 51]

Synthesis example 21 Synthesis of Polyamic acid (P-21)

7.418g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 11.52g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 0.047g of 4-methoxyphenol, and 126.47g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 9.0g of p-biphenylene bis (trimellitic acid monoester anhydride) (BP-TME, manufactured by Benzhou chemical Co., ltd.), 19.28g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, and 63.23g of N-ethyl-2-pyrrolidone were added to the mixture, and the mixture was stirred at room temperature for 1 hour and then at 50℃for 40 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-21), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 26,182.

[ 52]

< Synthesis example 22> Synthesis of solvent-soluble polyimide (P-22)

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

[ 53]

Synthesis example 23 Synthesis of solvent-soluble polyimide (P-23)

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

[ 54]

< Synthesis example 24> Synthesis of solvent-soluble polyimide (P-24)

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

[ 55]

Comparative Synthesis example 1 Synthesis of Polyamic acid (P-25)

30.00g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 0.13g of 2, 6-di-tert-butyl-p-cresol, and 90.38g of N-ethyl-2-pyrrolidone were stirred under air at room temperature to dissolve them, 24.51g of pyromellitic anhydride and 37.11g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 13 hours, the mixture was stirred at 80℃for 51 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-25), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 10,579.

[ 56]

Comparative Synthesis example 2 Synthesis of Polyamic acid (P-26)

42.28g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 0.09g of 4-methoxyphenol, and 144.42g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 46.13g of 3,3', 4' -biphenyltetracarboxylic dianhydride and 61.89g of N-ethyl-2-pyrrolidone were added to the system, followed by stirring at room temperature for 1 hour and then stirring at 80℃for 75 hours. A polyamic acid having a repeating unit structure represented by the following (P-26) was obtained.

[ 57]

Comparative Synthesis example 3 Synthesis of Polyamic acid (P-27)

After 31.71g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 0.09g of 4-methoxyphenol, and 137.13g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 52.24g of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride and 58.77g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 3 hours, the mixture was stirred at 80℃for 75 hours. A polyamic acid having a repeating unit structure represented by the following (P-27) was obtained.

[ 58]

Comparative Synthesis example 4 Synthesis of Polyamic acid (P-28)

After 18.00g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 0.08g of 2, 6-di-tert-butyl-p-cresol and 54.23g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 13.22g of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride and 30.40g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 62 hours, the mixture was stirred at 40℃for 34 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-28), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 42,930.

[ 59]

Comparative Synthesis example 5 Synthesis of Polyamic acid (P-29)

15.00g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 0.06g of 2, 6-di-tert-butyl-p-cresol, and 45.19g of N-ethyl-2-pyrrolidone were stirred under air at room temperature to dissolve them, then 17.21g of 1,1' -bicyclohexane-3, 3', 4' -tetracarboxylic acid-3, 3', 4' -dianhydride (BPDA-H, manufactured by Wako pure chemical industries, ltd.) and 30.12g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 62 hours, the mixture was stirred at 40℃for 34 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-29), and a weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 45,136.

[ chemical 60]

Comparative Synthesis example 6 Synthesis of solvent-soluble polyimide (P-30)

8.60g of 2- (methacryloyloxy) ethyl 3, 5-diaminobenzoate (BEM-S, manufactured by Wako pure chemical industries, ltd.), 16.85g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 0.05g of 4-methoxyphenol, and 148.85g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 27.72g of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, and 63.79g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 1 hour, the mixture was stirred at 50℃for 87 hours. The weight average molecular weight (Mw) of the obtained polyamic acid was 27,335 as measured by GPC in terms of polystyrene.

To 60.00g of the obtained polyamic acid were added 60.00g of N-ethyl-2-pyrrolidone, 4.49g of acetic anhydride, and 0.58g of pyridine, and the mixture was stirred at room temperature for 30 minutes under air, and then stirred at 50℃for 3 hours. The solution was slowly added to 437.76g of methanol under stirring and stirred for 10 minutes, and the resulting precipitate was filtered off. The precipitate was washed with 875.52g of methanol and dried under reduced pressure at 60℃to obtain a solvent-soluble polyimide powder having a repeating unit structure represented by the following (P-30). The chemical imidization rate was 93.2%.

[ chemical 61]

Example 1 >

A solution containing 27.75g of the polyamic acid (P-1) obtained in Synthesis example 1 (solid content: 30% by weight), 1.67g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.42g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), and 0.17g of KBM-5103 (3-acryloxypropyl trimethoxysilane, manufactured by Xinyue chemical Co., ltd.) as a crosslinking agent were mixed and dissolved, and then filtered using a polypropylene filter having a pore size of 5. Mu.m, to thereby prepare a solution of the negative photosensitive resin composition.

Example 2 >

A negative-type filter resin composition was prepared by dissolving and using a photosensitive resin composition comprising 32.24g of the solution (solid content: 30% by weight) of the polyamic acid (P-2) obtained in Synthesis example 2, 1.93g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhongcun chemical Co., ltd.), 0.15g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.48g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), and 0.19g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xingin chemical Co., ltd.) in a pore size of polypropylene.

Example 3 >

A negative filter was prepared by mixing 33.16g of the solution (solid content: 30% by weight) containing the polyamic acid (P-2) obtained in Synthesis example 2, 1.93g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.48g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.48g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.15g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xin chemical Co., ltd.) with 0.19g of BM to prepare a negative filter composition, and dissolving the solution.

Example 4 >

A negative filter was prepared by mixing 22.08g of the solution (solid content: 30% by weight) containing the polyamic acid (P-3) obtained in Synthesis example 3, 1.32g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhongcun chemical Co., ltd.), 0.10g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.33g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.13g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xingin chemical Co., ltd.) and 5.04 g of polypropylene, and then dissolving the solution in a negative filter to prepare a negative filter.

Example 5 >

A solution containing 32.49g of the polyamic acid (P-3) (solid content: 30% by weight) obtained in Synthesis example 3, 0.97g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.15g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.49g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.15g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xin chemical Co., ltd.) and 0.19g of BM-ethyl ketone were mixed together to prepare a solution, and a filter was prepared by mixing the solution with the solution.

Example 6 >

A negative filter was prepared by mixing 33.16g of the solution (solid content: 30% by weight) containing the polyamic acid (P-4) obtained in Synthesis example 4, 0.99g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.15g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.50g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.15g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xin chemical Co., ltd.) with 0.20g of polypropylene having a pore size, and then dissolving the solution.

Example 7 >

A negative filter was prepared by mixing 29.96g of the solution (solid content: 30% by weight) containing the polyamic acid (P-5) obtained in Synthesis example 5, 1.80g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhongcun chemical Co., ltd.), 0.13g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.45g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.18g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xinchemical Co., ltd.) and 48g of polypropylene, and then dissolving the solution in a negative filter to prepare a negative filter.

Example 8 >

A solution (solid content: 30% by weight) containing 23.89g of the polyamic acid (P-5) obtained in Synthesis example 5, 0.72g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.11g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.36g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.11g of KK-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xin chemical Co., ltd.) and 0.14g of BM-ethyl ketone were mixed, and a solution was prepared, and a negative filter was prepared by mixing the above solution with a polypropylene filter having a pore size of 0.78. Mu.m.

Example 9 >

A negative-type resin composition was prepared by dissolving and using a polypropylene filter having a pore size of 5 μm in a mixture of 37.84g of the solution (solid content: 20% by weight) containing the polyamic acid (P-6) obtained in Synthesis example 6, 1.51g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhongcun chemical Co., ltd.), 0.11g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.38g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.11g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xingin chemical Co., ltd.) and 0.15g of the solution.

Example 10 >

A negative-type resin composition was prepared by dissolving and using a polypropylene filter having a pore diameter of 5 μm in a mixture of 37.84g of the solution (solid content: 20% by weight) containing the polyamic acid (P-7) obtained in Synthesis example 7, 1.51g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhongcun chemical Co., ltd.), 0.11g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.38g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), and 0.11g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xingin chemical Co., ltd.) to prepare a negative-type resin composition.

Example 11 >

A negative filter-type polypropylene filter was prepared by mixing 22.08g of the solution (solid content: 30% by weight) containing the polyamic acid (P-8) obtained in Synthesis example 8, 1.32g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhongcun chemical Co., ltd.), 0.10g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylsulfanyl) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.33g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.13g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xinchemical Co., ltd.) and 5g of polypropylene, and then dissolving the solution in a negative filter-type polypropylene filter.

Example 12 >

A solution containing 31.50g of the polyamic acid (P-8) obtained in Synthesis example 8 (solid content: 30% by weight), 0.95g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.14g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.47g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.14g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xin chemical Co., ltd.) and 0.19g of BM-ethyl ketone were mixed together to prepare a solution, and a filter was prepared by dissolving the solution.

Example 13 >

A negative-type resin composition was prepared by dissolving and using a polypropylene filter having a pore diameter of 5 μm in a mixture of 33.11g of the solution (solid content: 20% by weight) containing the polyamic acid (P-9) obtained in Synthesis example 9, 1.32g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhongcun chemical Co., ltd.), 0.10g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.33g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), and 0.10g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xingin chemical Co., ltd.) to prepare a negative-type resin composition.

Example 14 >

A solution containing 20.75g of the polyamic acid (P-10) obtained in Synthesis example 10 (solid content: 30% by weight), 1.25g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhongcun chemical Co., ltd.), 0.09g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylsulfanyl) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.31g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.12g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xinchemical Co., ltd.) and 2.47 m of polypropylene was prepared by mixing the above, and then a negative filtration resin was prepared.

Example 15 >

A solution containing 23.66g of the polyamic acid (P-11) obtained in Synthesis example 11 (solid content: 25% by weight), 0.99g of N-ethyl-2-pyrrolidone, 0.59g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.09g of IRGACURE [ registered trademark ] OXE01 (1, 2-octadione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.30g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.09g of KBM 5103 (3-acryloyloxy) and 0.12g of polypropylene resin was prepared by mixing them together, and then preparing a solution.

Example 16 >

A negative filter was prepared by mixing 24.78g of the solution (solid content: 25% by weight) containing the polyamic acid (P-12) obtained in Synthesis example 12, 0.62g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.09g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.31g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.09g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xin chemical Co., ltd.) with 0.12g of polypropylene, and then dissolving the solution to prepare a negative filter.

Example 17 >

A negative-type resin composition was prepared by dissolving and using a polypropylene filter having a pore diameter of 5 μm in a mixture of 27.64g of the solution (solid content: 30% by weight) containing the polyamic acid (P-13) obtained in Synthesis example 13, 1.66g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhongcun chemical Co., ltd.), 0.12g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.41g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), and 0.17g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xingin chemical Co., ltd.) to prepare a negative-type resin composition.

Example 18 >

A negative filter resin composition was prepared by mixing 28.42g of the solution (solid content: 30% by weight) containing the polyamic acid (P-13) obtained in Synthesis example 13, 0.85g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.13g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.43g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.13g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xin chemical Co., ltd.) and 0.17g of polypropylene having a pore size, and dissolving the solution.

Example 19 >

A negative-type resin composition was prepared by dissolving and using a polypropylene filter having a pore size of 5 μm in a mixture of 27.64g of the solution (solid content: 30% by weight) containing the polyamic acid (P-14) obtained in Synthesis example 14, 1.66g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhongcun chemical Co., ltd.), 0.12g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.41g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), and 0.17g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xingin chemical Co., ltd.) to prepare a negative-type resin composition.

Example 20 >

A negative filter resin composition was prepared by mixing 28.42g of the solution (solid content: 30% by weight) containing the polyamic acid (P-14) obtained in Synthesis example 14, 0.85g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.13g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.43g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.13g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xin chemical Co., ltd.) and 0.17g of polypropylene having a pore size, and dissolving the solution.

Example 21 >

A negative filter was prepared by mixing 21.40g of the solution (solid content: 30% by weight) containing the polyamic acid (P-15) obtained in Synthesis example 15, 1.28g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhongcun chemical Co., ltd.), 0.10g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.32g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.13g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xinchemical Co., ltd.) and 1.77g of polypropylene, and then dissolving the solution in a negative filter to prepare a negative filter.

Example 22 >

A negative filter was prepared by mixing 37.81g of the solution (solid content: 30% by weight) containing the polyamic acid (P-16) obtained in Synthesis example 16, 2.27g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.17g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.57g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.17g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xin chemical Co., ltd.) with 0.23g of BM to prepare a negative filter composition, and dissolving the solution.

Example 23 >

A negative-type filter resin composition was prepared by dissolving and using a polypropylene filter having a pore diameter of 5. Mu.m, based on 65.34g of the solution (solid content: 25% by weight) containing the polyamic acid (P-17) obtained in Synthesis example 17, 3.27g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhongcun chemical Co., ltd.), 0.25g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.82g of IRGANOX [ registered trademark ]3114 (1, 3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.) and 0.33g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xingin chemical Co., ltd.) in accordance with a solution.

Example 24 >

A negative filter resin composition was prepared by mixing 38.23g of the solution (solid content: 25% by weight) containing the polyamic acid (P-18) obtained in Synthesis example 18, 0.96g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.14g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.48g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.14g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xin chemical Co., ltd.) and 0.19g of polypropylene having a pore size, and then dissolving the solution.

Example 25 >

A negative filter resin composition was prepared by mixing 38.23g of the solution (solid content: 25% by weight) containing the polyamic acid (P-19) obtained in Synthesis example 19, 0.96g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.14g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.48g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.14g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xin chemical Co., ltd.) and 0.19g of polypropylene having a pore size, and then dissolving the solution.

Example 26 >

A negative filter resin composition was prepared by mixing 38.57g of the solution (solid content: 20% by weight) containing the polyamic acid (P-20) obtained in Synthesis example 20, 0.77g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.12g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.39g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.12g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xin chemical Co., ltd.) and 0.15g of polypropylene having a pore size, and dissolving the solution.

Example 27 >

A negative filter resin composition was prepared by mixing 38.57g of the solution (solid content: 20% by weight) containing the polyamic acid (P-21) obtained in Synthesis example 21, 0.77g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.12g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.39g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), 0.12g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Xin chemical Co., ltd.) and 0.15g of polypropylene having a pore size, and dissolving the solution.

Example 28 >

A solution of 11.02g of the powder of the solvent-soluble polyimide (P-22) obtained in Synthesis example 22, 25.71g of N-ethyl-2-pyrrolidone, 2.20g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by New Zhongcun chemical Co., ltd.), 0.17g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.55g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), and 0.17g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by BASF Japan Co., ltd.) was prepared by mixing them together, and then filtering the mixture to prepare a solution.

Example 29 >

A solution of 10.89g of the powder of the solvent-soluble polyimide (P-23) obtained in Synthesis example 23, 26.00g of N-ethyl-2-pyrrolidone, 2.18g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.16g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.54g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), and 0.16g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by BASF Japan Co., ltd.) was prepared by mixing them together, and then filtering the mixture to prepare a solution.

Example 30 >

A solution of 10.89g of the powder of the solvent-soluble polyimide (P-24) obtained in Synthesis example 24, 26.00g of N-ethyl-2-pyrrolidone, 2.18g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.16g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.54g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), and 0.16g of KB-5103 (3-acryloxypropyltrimethoxysilane, manufactured by BASF Japan Co., ltd.) was prepared by mixing them together, and then filtering the mixture to prepare a solution.

Comparative example 1 >

A solution containing 27.75g of the polyamic acid (P-25) solution obtained in comparative Synthesis example 1 (solid content: 30% by weight), 1.67g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.42g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylsulfanyl) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.17g of KBM-5103 (3-acryloxypropyl trimethoxysilane, manufactured by Xinyue chemical Co., ltd.) as a crosslinking agent, and dissolved therein was filtered using a polypropylene filter having a pore size of 5. Mu.m, to thereby prepare a solution of the negative photosensitive resin composition.

Comparative example 2 >

A solution containing 26.17g of the polyamic acid (P-26) solution obtained in comparative Synthesis example 2 (solid content: 30% by weight), 1.57g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.39g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylsulfanyl) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), and 0.16g of KBM-5103 (3-acryloxypropyl trimethoxysilane, manufactured by Xinyue chemical Co., ltd.) as a crosslinking agent were mixed and dissolved, and then filtered using a polypropylene filter having a pore size of 5. Mu.m, to prepare a negative photosensitive resin composition.

Comparative example 3 >

A solution containing 25.08g of the polyamic acid (P-27) obtained in comparative Synthesis example 3 (solid content: 30% by weight), 1.50g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.38g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylsulfanyl) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.15g of KBM-5103 (3-acryloxypropyl trimethoxysilane, manufactured by Xinyue chemical Co., ltd.) as a crosslinking agent, and dissolved therein was filtered using a polypropylene filter having a pore size of 5 μm, to thereby prepare a solution of the negative photosensitive resin composition.

Comparative example 4 >

A solution containing 27.96g of the polyamic acid (P-28) solution obtained in comparative Synthesis example 4 (solid content: 27% by weight), 1.51g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.38g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), and 0.15g of KBM-5103 (3-acryloxypropyl trimethoxysilane, manufactured by Xinyue chemical Co., ltd.) as a crosslinking agent were mixed and dissolved, and then filtered using a polypropylene filter having a pore size of 5. Mu.m, to thereby prepare a solution of the negative photosensitive resin composition.

Comparative example 5 >

A solution containing 27.75g of the polyamic acid (P-29) solution obtained in comparative Synthesis example 5 (solid content: 30% by weight), 1.67g of NK ester A-200 (polyethylene glycol diacrylate, manufactured by Xinzhou chemical Co., ltd.), 0.42g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylsulfanyl) phenyl-, 2- (O-benzoyloxime) ], manufactured by BASF Japan Co., ltd.), 0.17g of KBM-5103 (3-acryloxypropyl trimethoxysilane, manufactured by Xinyue chemical Co., ltd.) as a crosslinking agent, and dissolved therein was filtered using a polypropylene filter having a pore size of 5. Mu.m, to thereby prepare a solution of the negative photosensitive resin composition.

Comparative example 6 >

A solution of 9.14g of the powder of the solvent-soluble polyimide (P-30) obtained in comparative Synthesis example 6, 16.98g of N-ethyl-2-pyrrolidone, 1.83g of NK ester A-DOD-N (1, 10-decanediol diacrylate, manufactured by Xinzhongcun chemical Co., ltd.), 0.14g of IRGACURE [ registered trademark ] OXE01 (1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], BASF Japan Co., ltd.), 0.46g of IRGANOX [ registered trademark ]3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, manufactured by BASF Japan Co., ltd.), and 0.14g of KBM-5103 (3-acryloxypropyltrimethoxysilane Co., ltd.) was prepared by mixing them together, and then preparing a solution by filtration.

[ photosensitive 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 electronics co.) and fired at 115 ℃ for 180 seconds or 270 seconds, thereby forming a photosensitive resin film having a film thickness of 5 to 15 μm on the wafer. Next, exposure was performed using an i-line stepper (NSR-2205 i12D, nikon Co., ltd.). Further, after spray development was performed for 20 to 240 seconds using an automatic developing device (AD-1200, manufactured by Mikasa Co., ltd.) using cyclopentanone as a developer, spray rinsing was performed for 10 seconds using Propylene Glycol Monomethyl Ether Acetate (PGMEA) as a rinse solution. Film thickness and 0mJ/cm immediately after film formation were measured by an interferometer film thickness meter (Lambda Ace VM-2110, manufactured by SCREEN Co., ltd.) ² (unexposed portion) and 300mJ/cm ² The film thickness after development in (exposed portion) is compared with the film thickness of the unexposed portion and the exposed portion. The measurement results of the film thickness are shown in table 1.

TABLE 1

According to the results of Table 1, the negative photosensitive resin compositions of examples 1 to 30 showed a negative film thickness of 0mJ/cm at the unexposed portion (0 mJ/cm ² ) Is sufficiently dissolved (developed) in the photosensitive resin film, and the exposure portion (300 mJ/cm ² ) The photosensitive resin film of (a) is not dissolved (developed) but remains. That is, since a clear photosensitive resin film is obtained in the exposed portion and the unexposed portion, the film has a poor dissolution contrast (dissolution contrast), and can be suitably used as a negative photosensitive resin composition for a process of producing a relief pattern by developing with a general-purpose organic solvent such as cyclopentanone. On the other hand, the photosensitive resin compositions of comparative example 1, comparative example 2, comparative example 4 and comparative example 5 had unexposed portions (0 mJ/cm after development ² ) The photosensitive resin film of (a) is not sufficiently dissolved (developed) and remains. That is, clear dissolution contrast is not obtained in the exposed portion and the unexposed portion, and the negative photosensitive resin composition is not suitable as a negative photosensitive resin composition for a process of producing a relief pattern by developing with a general-purpose organic solvent such as cyclopentanone.

[ evaluation of Electrical Properties ]

The negative photosensitive resin compositions prepared in examples 1 to 30 and comparative examples 1 to 6 were spin-coated on a 4-inch silicon wafer coated with an aluminum foil having a thickness of 20 μm, and fired on a hot plate at 115 ℃ for 180 seconds or 270 seconds, thereby forming a photosensitive resin film on the aluminum foil. Next, an i-line aligner (PLA-501, manufactured by Canon Co., ltd.) was used to apply a 500mJ/cm solution to the wafer ² After the entire exposure, the film was fired at 160℃for 1 hour and then at 230℃for 1 hour in a nitrogen atmosphere. Further, the fired aluminum foil was immersed in 6N hydrochloric acid to dissolve the aluminum foil, thereby obtaining a film. The obtained film was dried at 80℃under reduced pressure for 2 hours, left to stand at a temperature of about 25℃and a humidity of about 42% for 24 hours, and then measured for dielectric loss tangent at 1GHz using a cavity resonator (TMR-1A, KEYCOM Co., ltd.). The dielectric loss tangent measurement conditions are as follows.

Measurement method: perturbation mode cavity resonator method

Vector network analyzer: fieldFox N9926A (Keysight Technologies Co., ltd.)

Cavity resonator: TMR-1A (manufactured by KEYCOM Co., ltd.)

Chamber volume: 1192822mm ³

Measurement frequency: about 1GHz

Sample tube: PTFE and inner diameter: 3mm and about 30mm in length (manufactured by KEYCOM Co., ltd.)

[ evaluation of mechanical Properties ]

The negative photosensitive resin compositions prepared in examples 1 to 30 and comparative examples 1 to 6 were spin-coated on 100nm thick aluminum wafers, and fired at 115 ℃ for 180 seconds or 270 seconds on a hot plate, thereby forming photosensitive resin films on the aluminum wafers. Next, an i-line aligner (PLA-501, manufactured by Canon Co., ltd.) was used to apply a 500mJ/cm solution to the wafer ² After the entire exposure, the film was fired at 160℃for 1 hour and then at 230℃for 1 hour in a nitrogen atmosphere. Further, after the photosensitive resin film was cut at 5mm wide intervals by a dicing saw (DAD 323, manufactured by DISCO corporation), the aluminum wafer was immersed in 6N hydrochloric acid to dissolve aluminum, thereby obtaining a film having a width of 5 mm. Next, the tensile elongation of the obtained film was measured by using a bench-type precision universal tester (Autograph AGS-10kNX, manufactured by Shimadzu corporation). The measurement conditions of the tensile elongation are as follows.

Table type precision universal tester: autograph AGS-10kNX (Shimadzu corporation)

Film width: 5mm of

Distance between clamps: 25mm of

Here, the tensile elongation of 50% means that the film is elongated to 1.5 times, in other words, the film breaks when the distance between the jigs is 1.5 times (37.5 mm).

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

TABLE 2

From the results of table 2, the films obtained from the negative photosensitive resin compositions of examples 1 to 30 have lower dielectric loss tangent values at 1GHz than those of comparative examples 1 to 5. The tensile elongation values of the films obtained from the negative photosensitive resin compositions of examples 1 to 30 were higher than those of comparative examples 1 to 6.

That is, the negative photosensitive resin compositions of examples 1 to 30 can be used to produce a concave-convex pattern, and have the characteristics of low dielectric loss tangent and high tensile elongation, and therefore can be suitably used for the production of electronic materials requiring excellent electrical and mechanical properties.

Claims

1. A photosensitive resin composition characterized by comprising:

a solvent, and

a reaction product of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having 3 or more aromatic rings.

2. 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.

3. The photosensitive resin composition according to claim 2, wherein the polyamic acid has at least a structural unit represented by the following formula (1),

The polyimide has at least a structural unit represented by the following formula (2),

in the formula (1), ar ₁ Ar represents a 2-valent organic group having a photopolymerizable group and an aromatic ring ₂ Represents a 4-valent organic group having 3 or more aromatic rings,

ar in formula (2) ₃ Ar represents a 2-valent organic group having a photopolymerizable group and an aromatic ring ₄ Represents a 4-valent organic group having 3 or more aromatic rings.

4. The photosensitive resin composition according to claim 3, wherein Ar in the formula (1) ₂ And Ar in the formula (2) ₄ A 4-valent organic group represented by the following formula (3),

in the formula (3), X ₁ X is X ₂ Each independently 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 ₁ R is R ₂ Each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted or not, Y represents a 2-valent organic group represented by the following formula (3-1) or (3-2), n1 and n2 each independently represent an integer of 0 to 3, and R ₁ In the case of a plurality of R ₁ Identical or different, in R ₂ In the case of a plurality of R ₂ Identical or different, means a bond,

in the 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 is R ₃ R is R ₄ Each independently represents 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; at Z ₁ In the case of a plurality of Z' s ₁ The same or different; in the case where n4 is plural, plural n4 are the same or different; at R ₃ In the case of a plurality of R ₃ The same or different; at R ₄ In the case of a plurality of R ₄ Identical or different, means a bond,

in the formula (3-2), Z ₂ A 2-valent organic group represented by the following formula (4) or (5); r is R ₅ R is R ₆ Each independently represents an optionally substituted hydrocarbon group having 1 to 6 carbon atoms; n5 and n6 each independently represent an integer of 0 to 4; at R ₅ In the case of a plurality of R ₅ The same or different; at R ₆ In the case of a plurality of R ₆ The same or different; * Represents a bond and is provided with a bond,

in the formula (4), R ₇ R is R ₈ Each independently represents a hydrogen atom, or a hydrocarbon group of 1 to 6 carbon atoms which may or may not be substituted with a halogen atom,

in the formula (5), R ₉ R is R ₁₀ Each independently represents an alkylene group having 1 to 6 carbon atoms which is substituted or unsubstituted, or an arylene group having 6 to 10 carbon atoms which is substituted or unsubstituted.

5. The photosensitive resin composition according to claim 3 or 4, wherein Ar in the formula (1) ₁ And Ar in the formula (2) ₃ A 2-valent organic group represented by the following formula (6),

in formula (6), Z ₃ Represents an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, Z ₄ Represents a direct bond, an ester bond or an amide bond; z is Z ₅ Represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a thioether bond, or a sulfonyl bond; m2 represents an integer of 0 to 1; r is R ₁₁ Representing a direct bond, or carbon substituted or unsubstituted by hydroxyAlkylene having 2 to 6 atoms; r is R ₁₂ Represents a hydrogen atom or a methyl group.

6. The photosensitive resin composition according to claim 5, wherein Z in the formula (6) ₃ And Z ₄ Is an ester bond.

7. The photosensitive resin composition according to claim 5 or 6, wherein R in the formula (6) ₁₁ Is 1, 2-ethylene.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the photosensitive resin composition further comprises a photo radical polymerization initiator.

9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the photosensitive resin composition further comprises a crosslinkable compound.

10. The photosensitive resin composition according to any one of claims 1 to 9, wherein the photosensitive resin composition is used for forming an insulating film.

11. The photosensitive resin composition according to any one of claims 1 to 10, wherein the photosensitive resin composition is a negative photosensitive resin composition.

12. A resin film comprising a fired product of the coating film of the photosensitive resin composition according to any one of claims 1 to 11.

13. The resin film according to claim 12, wherein the resin film is an insulating film.

14. A photosensitive resist film comprising a base film, a photosensitive resin layer formed from the photosensitive resin composition according to any one of claims 1 to 11, and a cover film.

15. A method for manufacturing a substrate with a cured relief pattern, comprising the steps of:

(1) A photosensitive resin composition according to any one of claims 1 to 11 is coated on a substrate to form a photosensitive resin layer on the substrate,

(2) The photosensitive resin layer is subjected to exposure to light,

16. The method for producing a substrate with a cured relief pattern according to claim 15, wherein the developer used in the development is an organic solvent.

17. A substrate with a cured relief pattern, characterized in that the substrate is manufactured by the method of claim 15 or 16.

18. A semiconductor device comprising a semiconductor element and a cured film provided on an upper portion or a lower portion of the semiconductor element, wherein the cured film is a cured uneven pattern formed from the photosensitive resin composition according to any one of claims 1 to 11.