KR20230160249A - Photosensitive resin composition - Google Patents

Abstract

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

Description

Photosensitive resin composition

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

Conventionally, polyimide resins, which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic components and as passivation films, surface protective films, and interlayer insulating films for semiconductor devices. Among these polyimide resins, those provided in the form of photosensitive polyimide precursors can easily form a heat-resistant relief pattern film by thermal imidization treatment by application, exposure, development, and curing of the precursor. . This photosensitive polyimide precursor has the characteristic of enabling a significant shortening of the process compared to a conventional non-photosensitive polyimide resin.

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

Patent Document 1: Japanese Patent Application Publication No. 2000-347404 Patent Document 2: Japanese Patent Publication No. 2012-516927

In recent years, in semiconductor devices, the frequency of electrical signals has been increasing due to the need to transmit and process large amounts of information at high speeds. Because high-frequency electrical signals are prone to attenuation, transmission loss needs to be kept low. Therefore, resins used in semiconductor devices are required to have a low dielectric loss tangent.

On the other hand, resins with low dielectric loss tangents tend to be brittle and, for example, cannot keep up with the thermal expansion of adjacent materials during heat treatment processes such as inversion reflow processes, resulting in breakage or deterioration in interlayer adhesion. there is. Therefore, high tensile elongation is required for resins used in semiconductor devices.

Additionally, when forming a cured relief pattern, development using a developer is performed, but generally an aqueous alkaline solution developer or an organic solvent developer is used. The photosensitive resin for obtaining a cured relief pattern is a positive type in which the photosensitive resin in the exposed area dissolves in the developer through exposure and development, and the photosensitive resin in the unexposed area remains, and the photosensitive resin in the unexposed area dissolves in the developer and the photosensitive resin in the exposed area remains. It can be divided into negative type in which photosensitive resin remains. In particular, although the negative type is inferior to the positive type in resolution, it is easy to thicken and film, and has excellent reliability, so it is used in the manufacture of semiconductor devices that require such characteristics. However, in the conventional negative photosensitive resin containing polyamic acid, the solubility in an aqueous alkaline developer solution is very high, so it is difficult to control the dissolution rate, and there is a concern that it is difficult to obtain a desired relief pattern. Additionally, since the negative photosensitive resin containing polyamic acid has a high affinity for an aqueous alkaline developer, it is prone to swelling during development, and the formed relief pattern is prone to peeling off from the substrate due to stress generated during drying. There was. From this, for negative photosensitive resins containing polyamic acid, organic solvent development is suitable because control of the dissolution rate is relatively easy and there is little risk of substrate peeling.

Therefore, there is a demand for a photosensitive resin composition that is capable of organic solvent development, has a low dielectric loss tangent in the obtained cured film, and has high tensile elongation.

However, the photosensitive resin composition described in Patent Document 1 and Patent Document 2 cannot satisfy all of those characteristics.

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

As a result of repeated studies to achieve the above problems, the present inventors have made the photosensitive resin composition contain a reaction product of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings, It was discovered that organic solvent development was possible, that a photosensitive resin composition having a low dielectric loss tangent and high tensile elongation in the obtained cured film could be obtained, and the present invention was completed.

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

[2] The photosensitive resin composition according to [1], wherein the reaction product is a polyamic acid or a polyimide obtained by dehydrating and ring-closing a polyamic acid.

[3] The polyamic acid has at least a structural unit represented by the following formula (1),

The photosensitive resin composition according to [2], wherein the polyimide has at least a structural unit represented by the following formula (2).

[In formula (1), Ar ₁ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar ₂ represents a tetravalent organic group having 3 or more aromatic rings.]

[In formula (2), Ar ₃ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar ₄ represents a tetravalent organic group having 3 or more aromatic rings.]

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

[In formula (3), X ₁ and X ₂ each independently represent a direct bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, or sulfonyl bond. R ₁ and R ₂ each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms. Y represents a divalent organic group represented by the following formula (3-1) or (3-2). n1 and n2 each independently represent an integer from 0 to 3. When R ₁ is plural, the plural R ₁ may be the same or different. When R ₂ is plural, the plural R ₂ may be the same or different. * indicates a combined hand.]

[In formula (3-1), Z ₁ represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a thioether bond, or a sulfonyl bond. R ₃ and R ₄ each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. m1 represents an integer from 0 to 3. n3 and n4 each independently represent an integer from 0 to 4. When Z ₁ is plural, the plural Z ₁ may be the same or different. When n4 is plural, the plural n4 may be the same or different. When R ₃ is plural, the plural R ₃ may be the same or different. When R ₄ is plural, the plural R ₄ may be the same or different. * represents the bonding hand.

In formula (3-2), Z ₂ represents a divalent organic group represented by the following formula (4) or (5). R ₅ and R ₆ each independently represent a hydrocarbon group having 1 to 6 carbon atoms which may be substituted. n5 and n6 each independently represent an integer from 0 to 4. When R ₅ is plural, the plural R ₅ may be the same or different. When R ₆ is plural, the plural R ₆ may be the same or different. * indicates a combined hand.]

[In formula (4), R ₇ and R ₈ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom. * represents the bonding hand.

In formula (5), R ₉ and R ₁₀ each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms. * indicates a combined hand.]

[5] The photosensitive resin composition according to [3] or [4], wherein Ar ₁ in the formula (1) and Ar ₃ in the formula (2) are divalent organic groups represented by the following formula (6).

[In formula (6), Z ₃ represents an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond, and Z ₄ represents a direct bond, an ester bond, or an amide bond. Z ₅ represents a direct bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, or sulfonyl bond. m2 represents an integer from 0 to 1. R ₁₁ represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group, and R ₁₂ represents a hydrogen atom or a methyl group. * indicates a combined hand.]

[6] The photosensitive resin composition according to [5], wherein Z ₃ and Z ₄ in the formula (6) are ester bonds.

[7] The photosensitive resin composition according to [5] or [6], wherein R ₁₁ in the formula (6) is a 1,2-ethylene group.

[8] The photosensitive resin composition according to any one of [1] to [7], further comprising a radical photopolymerization initiator.

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

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

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

[12] A resin film that is a baked product of a coating film of the photosensitive resin composition according to any one of [1] to [11].

[13] The resin film described in [12], which is an insulating film.

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

[15] (1) A process of applying the photosensitive resin composition according to any one of [1] to [11] onto a substrate to form a photosensitive resin layer on the substrate;

(2) exposing the photosensitive resin layer to light;

(3) developing the photosensitive resin layer after the exposure to form a relief pattern;

(4) Process of heat treating the relief pattern to form a hardened relief pattern

A method for manufacturing a substrate with a cured relief pattern attached, comprising:

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

[17] A substrate with a cured relief pattern manufactured by the method described in [15] or [16].

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

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

(Photosensitive resin composition)

The photosensitive resin composition of this invention contains at least a reaction product and a solvent, and further contains other components as needed.

<Reaction product>

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

The reaction product contains, as components, an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings, and, if necessary, other diamine compounds and other tetracarboxylic acids as components. It may contain a derivative.

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

When the reaction product contains an aromatic diamine compound having a photopolymerizable group as a component, photosensitivity is imparted to the resin composition containing the reaction product.

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

In an aromatic diamine compound having a photopolymerizable group, two amino groups may be bonded to one aromatic ring or may be bonded to each of two aromatic rings. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles.

In addition, the aromatic diamine compound may have an aromatic ring to which an amino group is not bonded.

Examples of photopolymerizable groups include radical polymerizable groups, cationic polymerizable groups, and anionic polymerizable groups. Among these, a radical polymerizable group is preferable.

Examples of the radical polymerizable group include acryloyl group, methacryloyl group, propenyl ether group, vinyl ether group, and vinyl group.

The reaction product, which contains an aromatic diamine compound having three or more aromatic rings as a diamine compound other than an aromatic diamine compound having a photopolymerizable group as a constituent, has a lower dielectric loss tangent and higher tensile strength in the cured film obtained. This is preferable in that elasticity is obtained.

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

Regarding the method of counting aromatic rings in “three or more aromatic rings,” a polycyclic aromatic ring formed by condensation of two or more aromatic rings, such as a naphthalene ring or anthracene ring, is counted as one aromatic ring. Therefore, a naphthalene ring is counted as one aromatic ring. On the other hand, since the biphenyl ring is not a condensed ring, it is counted as two aromatic rings. In addition, the perylene ring is considered to be a structure formed by two naphthalene rings bonded, and is counted as two aromatic rings.

Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles.

Examples of tetracarboxylic acid derivatives in “tetracarboxylic acid derivatives” include tetracarboxylic acid dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, and tetracarboxylic acid dialkyl ester dihalide, especially tetracarboxylic acid. 2 Anhydrous is preferred.

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

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

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

The ratio of the aromatic tetracarboxylic acid derivative having three or more aromatic rings to all tetracarboxylic acid derivatives constituting the reaction product is not particularly limited, but from the viewpoint of appropriately obtaining the effect of the present invention, it is 20 to 100 mol. % is preferable, and 50 to 100 mol% is more preferable.

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

It is preferable that the polyamic acid has at least a structural unit represented by the following formula (1).

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

[In formula (1), Ar ₁ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar ₂ represents a tetravalent organic group having 3 or more aromatic rings.]

[In formula (2), Ar ₃ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar ₄ represents a tetravalent organic group having 3 or more aromatic rings.]

<<Ar ₁ and Ar ₃ >

Ar ₁ and Ar ₃ are divalent organic groups having a photopolymerizable group and an aromatic ring, and are not particularly limited as long as they achieve the effect of the present invention. In addition, the divalent organic group having a photopolymerizable group and an aromatic ring is a residue obtained by removing two amino groups from an aromatic diamine compound having a photopolymerizable group.

Examples of the photopolymerizable group include the photopolymerizable group described above.

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

[In formula (6), Z ₃ represents an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), or a urea bond (-NHCONH-). and Z ₄ represents a direct bond, an ester bond (-COO-), or an amide bond (-NHCO-). Z ₅ is a direct bond, ether bond (-O-), ester bond (-COO-), amide bond (-NHCO-), urethane bond (-NHCOO-), urea bond (-NHCONH-), thioether bond ( -S-) or sulfonyl bond (-SO ₂ -). m2 represents an integer from 0 to 1. R ₁₁ represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group, and R ₁₂ represents a hydrogen atom or a methyl group. * indicates a combined hand.]

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

As Z ₃ , an ester bond is preferable.

As Z ₄ , an ester bond is preferable.

As R ₁₁ , a 1,2-ethylene group is preferable.

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

In the formula, * represents a binding hand. For example, the two bonding hands are located in the meta position with respect to the substituent having a photopolymerizable group.

<<Ar ₂ and Ar ₄ >>

Ar ₂ in formula (1) and Ar ₄ in formula (2) are not particularly limited as long as they are tetravalent organic groups that have three or more aromatic rings and achieve the effects of the present invention, but are suitable for the effects of the present invention. From the viewpoint of obtaining it, it is preferably a divalent organic group represented by the following formula (3).

[In formula (3), X _{1 and} , urea linkage (-NHCONH-), thioether linkage (-S-) or sulfonyl linkage (-SO ₂ -). R ₁ and R ₂ each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms. Y represents a divalent organic group represented by the following formula (3-1) or (3-2). n1 and n2 each independently represent an integer from 0 to 3. When R ₁ is plural, the plural R ₁ may be the same or different. When R ₂ is plural, the plural R ₂ may be the same or different. * indicates a combined hand.]

Examples of the alkyl group having 1 to 6 carbon atoms that may be substituted for R ₁ and R ₂ include alkyl groups having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group. In this specification, unless otherwise specified, the alkyl group may be linear, branched, cyclic, or a combination of two or more thereof.

Substituents for the alkyl group having 1 to 6 carbon atoms that may be substituted include, for example, a halogen atom, hydroxy group, mercapto group, carboxyl group, cyano group, formyl group, haloformyl group, sulfo group, amino group, nitro group, A nitroso group, an oxo group, a thioxy group, an alkoxy group having 1 to 6 carbon atoms, etc. are included.

In addition, “1 to 6 carbon atoms” in the “alkyl group having 1 to 6 carbon atoms which may be substituted” refers to the number of carbon atoms in the “alkyl group” excluding the substituents. Additionally, the number of substituents is not particularly limited.

[In formula (3-1), Z ₁ is a direct bond, ether bond (-O-), ester bond (-COO-), amide bond (-NHCO-), urethane bond (-NHCOO-), urea bond ( -NHCONH-), a thioether bond (-S-), or a sulfonyl bond (-SO ₂ -). R ₃ and R ₄ each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. m1 represents an integer from 0 to 3. n3 and n4 each independently represent an integer from 0 to 4. When Z ₁ is plural, the plural Z ₁ may be the same or different. When n4 is plural, the plural n4 may be the same or different. When R ₃ is plural, the plural R ₃ may be the same or different. When R ₄ is plural, the plural R ₄ may be the same or different. * represents the bonding hand.

In formula (3-2), Z ₂ represents a divalent organic group represented by the following formula (4) or (5). R ₅ and R ₆ each independently represent a hydrocarbon group having 1 to 6 carbon atoms which may be substituted. n5 and n6 each independently represent an integer from 0 to 4. When R ₅ is plural, the plural R ₅ may be the same or different. When R ₆ is plural, the plural R ₆ may be the same or different. * indicates a combined hand.]

Examples of the optionally substituted hydrocarbon group of 1 to 6 carbon atoms for R ₃ , R ₄ , R ₅ , and R ₆ include an optionally substituted alkyl group of 1 to 6 carbon atoms, which may be substituted. A phenyl group may be mentioned. Substituents include, for example, a halogen atom, hydroxy group, mercapto group, carboxyl group, cyano group, formyl group, haloformyl group, sulfo group, amino group, nitro group, nitroso group, oxo group, thioxy group, and 1 to 6 carbon atoms. Alkoxy groups, etc. can be mentioned.

In addition, “1 to 6 carbon atoms” in “hydrocarbon group with 1 to 6 carbon atoms which may be substituted” refers to the number of carbon atoms in the “hydrocarbon group” excluding the substituents. Additionally, the number of substituents is not particularly limited.

Specific examples of alkyl groups having 1 to 6 carbon atoms that may be substituted for R ₃ , R ₄ , R ₅ , and R ₆ include, for example, the optionally substituted alkyl groups exemplified in the description of R ₁ and R ₂ Examples include alkyl groups having 1 to 6 carbon atoms.

[In formula (4), R ₇ and R ₈ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom. * represents the bonding hand.

In formula (5), R ₉ and R ₁₀ each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms. * indicates a combined hand.]

Examples of hydrocarbon groups having 1 to 6 carbon atoms that may be substituted with halogen atoms for R ₇ and R ₈ include alkyl groups having 1 to 6 carbon atoms, halogenated alkyl groups having 1 to 6 carbon atoms, phenyl groups, A halogenated phenyl group etc. are mentioned. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group. Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Halogenation in the halogenated alkyl group having 1 to 6 carbon atoms and the halogenated phenyl group may be present in some or all of the halogenated groups.

Substituents for the alkylene group having 1 to 6 carbon atoms that may be substituted for R ₉ and R ₁₀ include, for example, a halogen atom, a hydroxy group, a mercapto group, a carboxyl group, a cyano group, a formyl group, and a haloformyl group. , sulfo group, amino group, nitro group, nitroso group, oxo group, thioxy group, alkoxy group having 1 to 6 carbon atoms, etc.

Examples of alkylene groups having 1 to 6 carbon atoms that may be substituted include alkylene groups having 1 to 6 carbon atoms, halogenated alkylene groups having 1 to 6 carbon atoms, etc. Examples of the alkylene group having 1 to 6 carbon atoms include methylene group, ethylene group, propylene group, and butylene group.

In addition, “1 to 6 carbon atoms” in the “alkylene group having 1 to 6 carbon atoms which may be substituted” refers to the number of carbon atoms in the “alkylene group” excluding the substituents. Additionally, the number of substituents is not particularly limited.

Substituents for the arylene group having 6 to 10 carbon atoms that may be substituted for R ₉ and R ₁₀ include, for example, a halogen atom, an alkyl group having 1 to 6 carbon atoms that may be halogenated, or an alkyl group having 1 to 6 carbon atoms that may be halogenated. and an alkoxy group having 1 to 6 carbon atoms. Additionally, halogenation may be present in some or all of the elements.

Examples of the arylene group include phenylene group and naphthylene group.

In addition, “6 to 10 carbon atoms” in the “arylene group having 6 to 10 carbon atoms which may be substituted” refers to the number of carbon atoms in the “arylene group” excluding the substituents. Additionally, the number of substituents is not particularly limited.

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

In the formula, * represents a binding hand.

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

In the formula, R ₁₃ to R ₁₅ each independently represent 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 from 0 to 4. When R ₁₃ is plural, the plural R ₁₃ may be the same or different. When R ₁₄ is plural, the plural R ₁₄ may be the same or different. When R ₁₅ is plural, the plural R ₁₅ may be the same or different. * represents the bonding hand.

Specific examples of alkyl groups having 1 to 6 carbon atoms that may be substituted with halogen atoms in R ₁₃ to R ₁₅ include alkyl groups having 1 to 6 carbon atoms, and halogenated alkyl groups having 1 to 6 carbon atoms. You can.

Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group.

Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Halogenation in the halogenated alkyl group having 1 to 6 carbon atoms may be present in some or all of the halogenated alkyl groups.

Specific examples of the alkoxy group having 1 to 6 carbon atoms that may be substituted with a halogen atom for R ₁₃ to R ₁₅ include those in which an alkyl group having 1 to 6 carbon atoms that may be substituted with a halogen atom is used as an alkoxy group.

Examples of Ar ₂ and Ar ₄ include tetravalent organic groups represented by the following formula.

In the formula, * represents a binding hand.

<Other structural units>

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

Polyimide may have structural units other than those represented by formula (2). Examples of other structural units include structural units represented by the following formula (2').

[In formula (1'), Ar _1' represents a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring, or a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _2' represents 3. It refers to a tetravalent organic group having 3 or more aromatic rings or a tetravalent organic group not having 3 or more aromatic rings. However, the case where Ar _1' is a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _2' is a tetravalent organic group having 3 or more aromatic rings is excluded.]

[In formula (2'), Ar _3' represents a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring, or a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _4' represents 3. It refers to a tetravalent organic group having 3 or more aromatic rings or a tetravalent organic group not having 3 or more aromatic rings. However, the case where Ar _3' is a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _4' is a tetravalent organic group having 3 or more aromatic rings is excluded.]

Combinations of Ar _1' and Ar _2' include combinations of (i) to (iii) below.

(i): A combination in which Ar _1' represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _2' represents a tetravalent organic group not having 3 or more aromatic rings.

(ii): A combination in which Ar _1' represents a divalent organic group other than a photopolymerizable group and a divalent organic group having an aromatic ring, and Ar _2' represents a tetravalent organic group not having 3 or more aromatic rings.

(iii): A combination in which Ar _1' represents a divalent organic group other than a photopolymerizable group and a divalent organic group having an aromatic ring, and Ar _2' represents a tetravalent organic group having 3 or more aromatic rings.

Combinations of Ar _3' and Ar _4' include combinations of (iv) to (vi) below.

(iv): A combination in which Ar _3' represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _4' represents a tetravalent organic group not having 3 or more aromatic rings.

(v): A combination in which Ar _3' represents a divalent organic group other than a photopolymerizable group and a divalent organic group having an aromatic ring, and Ar _4' represents a tetravalent organic group not having 3 or more aromatic rings.

(vi): A combination in which Ar _3' represents a divalent organic group other than a photopolymerizable group and a divalent organic group having an aromatic ring, and Ar _4' represents a tetravalent organic group having 3 or more aromatic rings.

<<Ar _1' and Ar _3' >>

Examples of the divalent organic group having a photopolymerizable group and an aromatic ring for Ar _1' and Ar _3' include the divalent organic groups having a photopolymerizable group and an aromatic ring exemplified in the description of Ar ₁ and Ar ₃ You can raise your flag.

The divalent organic group other than the photopolymerizable group and the aromatic ring-containing divalent organic group in Ar _1' and Ar _3' is not particularly limited, but in the resulting cured film, lower dielectric loss tangent and higher tensile elongation. Since it can be obtained, a divalent organic group having three or more aromatic rings is preferable.

The divalent organic group having three or more aromatic rings is not particularly limited, but is preferably a divalent organic group represented by the following formula (13).

[In formula ( ₁₃ ) _, , urea linkage (-NHCONH-), thioether linkage (-S-) or sulfonyl linkage (-SO ₂ -). R ₂₁ and R ₂₂ each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms. Y ₂₀ represents a divalent organic group represented by the following formula (13-1) or (13-2). n21 and n22 each independently represent an integer from 0 to 4. When R ₂₁ is plural, the plural R ₂₁ may be the same or different. When R ₂₂ is plural, the plural R ₂₂ may be the same or different. * indicates a combined hand.]

Specific examples of the optionally substituted alkyl group having 1 to 6 carbon atoms for R ₂₁ and R ₂₂ include the optionally substituted alkyl group having 1 to 6 carbon atoms exemplified in the description of R ₁ and R ₂ . there is.

In addition, “1 to 6 carbon atoms” in the “alkyl group having 1 to 6 carbon atoms which may be substituted” refers to the number of carbon atoms in the “alkyl group” excluding the substituents. Additionally, the number of substituents is not particularly limited.

[In formula (13-1), Z ₂₁ is a direct bond, ether bond (-O-), ester bond (-COO-), amide bond (-NHCO-), urethane bond (-NHCOO-), urea bond ( -NHCONH-), a thioether bond (-S-), or a sulfonyl bond (-SO ₂ -). R ₂₃ and R ₂₄ each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. m21 represents an integer from 0 to 3. n23 and n24 each independently represent an integer from 0 to 4. When Z ₂₁ is plural, the plural Z ₂₁ may be the same or different. When n24 is plural, the plural n24 may be the same or different. When R ₂₃ is plural, the plural R ₂₃ may be the same or different. When R ₂₄ is plural, the plural R ₂₄ may be the same or different. * represents the bonding hand.

In formula (13-2), Z ₂₂ represents a divalent organic group represented by the following formula (14) or (15). R ₂₅ and R ₂₆ each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. n25 and n26 each independently represent an integer from 0 to 4. When R ₂₅ is plural, the plural R ₂₅ may be the same or different. When R ₂₆ is plural, the plural R ₂₆ may be the same or different. * indicates a combined hand.]

Specific examples of hydrocarbon groups having 1 to 6 carbon atoms that may be substituted for R ₂₃ , R ₂₄ , R ₂₅ , and R ₂₆ are those exemplified in the description of R ₃ , R ₄ , R ₅ , and R ₆ Examples include hydrocarbon groups having 1 to 6 carbon atoms which may be substituted.

In addition, “1 to 6 carbon atoms” in “hydrocarbon group with 1 to 6 carbon atoms which may be substituted” refers to the number of carbon atoms in the “hydrocarbon group” excluding the substituents. Additionally, the number of substituents is not particularly limited.

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

[In formula (14), R ₂₇ and R ₂₈ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom. * represents the bonding hand.

In formula (15), R ₂₉ and R ₃₀ each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms. * indicates a combined hand.]

Specific examples of hydrocarbon groups having 1 to 6 carbon atoms that may be substituted with halogen atoms for R ₂₇ and R ₂ include 1 to 6 carbon atoms that may be substituted with halogen atoms as exemplified in the description of R ₇ and R ₈ Hydrocarbon groups can be mentioned.

Specific examples of the optionally substituted alkylene groups having 1 to 6 carbon atoms for R ₂₉ and R ₃₀ include the optionally substituted alkylene groups having 1 to 6 carbon atoms exemplified in the description of R ₉ and R ₁₀ I can hear it.

In addition, “1 to 6 carbon atoms” in the “alkylene group having 1 to 6 carbon atoms which may be substituted” refers to the number of carbon atoms in the “alkylene group” excluding the substituents. Additionally, the number of substituents is not particularly limited.

Specific examples of the optionally substituted arylene group having 6 to 10 carbon atoms for R ₂₉ and R ₃₀ include the optionally substituted arylene group having 6 to 10 carbon atoms exemplified in the description of R ₉ and R ₁₀ I can hear it.

In addition, “6 to 10 carbon atoms” in the “arylene group having 6 to 10 carbon atoms which may be substituted” refers to the number of carbon atoms in the “arylene group” excluding the substituents. Additionally, the number of substituents is not particularly limited.

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

In the formula, * represents a binding hand.

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

In the formula, R ₃₃ to R ₃₅ each independently represent 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 from 0 to 4. When R ₃₃ is plural, the plural R ₃₃ may be the same or different. When there is a plurality of R ₃₄ , the plurality of R ₃₄ may be the same or different. When there is a plurality of R ₃₅ , the plurality of R ₃₅ may be the same or different. * represents the bonding hand.

Specific examples of alkyl groups having 1 to 6 carbon atoms that may be substituted with halogen atoms in R ₃₃ to R ₃₅ include alkyl groups having 1 to 6 carbon atoms that may be substituted with the halogen atoms exemplified in the description of R ₁₃ to R ₁₅ An alkyl group may be mentioned.

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

Examples of Ar _1' and Ar _3' include divalent organic groups represented by the following formula.

In the formula, * represents a binding hand.

Other examples of Ar _1' and Ar _3' include divalent organic groups represented by the following formula.

In the formula, * represents a binding hand.

<<Ar _2' and Ar _4' >>

Examples of the tetravalent organic group having 3 or more aromatic rings for Ar _2' and Ar _4' include the tetravalent organic groups having 3 or more aromatic rings exemplified in the description of Ar ₂ and Ar ₄ . You can.

Examples of the tetravalent organic group that does not have three or more aromatic rings for Ar _2' and Ar _4' include, for example, a tetravalent organic group that has one or two aromatic rings or a tetravalent organic group that does not have an aromatic ring. You can raise your flag. The tetravalent organic group having one or two aromatic rings is derived, for example, from an aromatic tetracarboxylic acid dianhydride derivative. Additionally, the tetravalent organic group without an aromatic ring is derived from, for example, an aliphatic tetracarboxylic anhydride derivative. Such tetravalent organic groups are not particularly limited, but examples include the following tetravalent organic groups.

In the formula, * represents a binding hand.

The ratio of the structural unit represented by formula (1) in all structural units of the polyamic acid is not particularly limited, but is preferably 10 to 100 mol%, and 50 to 100 mol% from the viewpoint of obtaining sufficient photosensitivity. is more preferable. Additionally, a structural unit is also a repeated unit.

When the polyamic acid has a structural unit represented by the formula (1'), the ratio of the structural unit represented by the formula (1') to all structural units of the polyamic acid is not particularly limited, but is 1 to 90 mol. % is preferable, and 1 to 50 mol% is more preferable.

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

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

When the polyimide has at least one of the structural unit represented by formula (1') and the structural unit represented by formula (2'), the structure represented by formula (1') in all structural units of the polyimide The ratio of the total of the unit and the structural unit represented by formula (2') is not particularly limited, but is preferably 1 to 90 mol%, and more preferably 1 to 50 mol%.

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

<Method for producing reaction product>

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

The method for producing the reaction product is not particularly limited, and examples include known methods of reacting a diamine compound and a tetracarboxylic acid derivative to obtain a polyamic acid or polyimide. Polyamic acid and polyimide can be synthesized by known methods such as those described in, for example, WO2013/157586.

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

Specific examples of the solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, N, Examples include N-dimethylpropion amide, N,N-dimethylisobutyric acid amide, dimethyl sulfoxide, and 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 the following formulas [D-1] to formula [D A solvent represented by [-3] can be used.

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

These solvents may be used individually or in mixture. Additionally, even if the solvent does not dissolve the reaction product, it may be used by mixing with the solvent as long as the reaction product does not precipitate.

When reacting the diamine component and the tetracarboxylic acid derivative component in a solvent, the reaction can be performed at any concentration, but is preferably 1 to 50 mass%, more preferably 5 to 30 mass%. The initial reaction may be carried out at a high concentration, and then a solvent may be added.

In the reaction, the ratio of the total number of moles of the diamine component and the total number of moles of the tetracarboxylic acid derivative component is preferably 0.8 to 1.2. Like a normal polycondensation reaction, the closer this molar ratio is to 1.0, the greater the molecular weight of the reaction product produced.

When reacting the diamine component and the tetracarboxylic acid derivative component, a thermal polymerization inhibitor may be added to the reaction system to avoid polymerization of the photopolymerizable group.

Examples of thermal polymerization inhibitors include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1 , 2-Cyclohexanediamine tetraacetic acid, glycol etherdiamine 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-phenyl hydroxyl amine ammonium salt, N-nitroso-N (1- Naphthyl) hydroxylamine ammonium salt, etc. may be mentioned.

The amount of the thermal polymerization inhibitor used is not particularly limited.

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

Methods for obtaining polyimide include thermal imidization in which a solution of polyamic acid, which is a reaction product obtained in the above reaction, is heated as is, or chemical imidization in which a catalyst is added to a solution of polyamic acid. The temperature for thermal imidization in solution is 100 to 400°C, preferably 120 to 250°C, and it is preferably carried out while excluding water generated by the imidization reaction from the system.

The chemical imidization can be performed by adding a basic catalyst and an acid anhydride to a solution of polyamic acid obtained from the reaction and stirring at -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is 0.1 to 30 mole times the amidic acid group, preferably 0.2 to 20 mole times, and the amount of the acid anhydride is 1 to 50 mole times the amidic acid group, preferably 1.5 to 30 mole times. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, triethylamine is preferable because polyisoimide, which is a by-product, is difficult to form. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among these, acetic anhydride is preferred because it facilitates purification after completion of the reaction. The imidization rate by chemical imidization (ratio of ring-closed repeating units to all repeating units of the polyimide precursor, also called ring-closure ratio) is controlled by adjusting the amount of catalyst, reaction temperature, and reaction time. can do.

When recovering the produced imidate from the imidization reaction solution, the reaction solution may be added to a solvent to cause precipitation. Solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated by adding it to the solvent can be recovered by filtration and then dried under normal or reduced pressure, at room temperature, or by heating.

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

Polyimide may be terminal-blocked. The method of end capping is not particularly limited, and for example, a conventionally known method using a monoamine or an acid anhydride can be used.

<Solvent>

As a solvent contained in the photosensitive resin composition, it is preferable to use an organic solvent from the viewpoint of solubility in the reaction product. Specifically, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylpropion amide, N, N-dimethylisobutyric acid amide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl -2-imidazorinone, 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, Examples include methyl 2-hydroxyisobutyrate, ethyl lactate, and solvents represented by the following formulas [D-1] to [D-3], and these can be used alone or in combination of two or more.

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

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

<Other ingredients>

In embodiments, the photosensitive resin composition may further contain other components other than the reaction product and the solvent. Other components include, for example, a radical photopolymerization initiator (also referred to as a “photo radical initiator”), a crosslinking compound (also referred to as a “crosslinking agent”), a thermosetting agent, other resin components, fillers, sensitizers, adhesion aids, Examples include thermal polymerization inhibitors, azole compounds, and hindered phenol compounds.

<<Photo radical polymerization initiator>>

The photo radical polymerization initiator is not particularly limited as long as it is a compound that absorbs the light source used during photo curing, but examples include tert-butyl peroxy-iso-butyrate, 2,5-dimethyl-2,5-bis ( Benzoyldioxy) hexane, 1,4-bis[α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert -butyldioxy) hexene hydroperoxide, α-(iso-propylphenyl)-iso-propyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butyldioxy)-3,3, 5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy)valerate, cyclohexanone peroxide, 2,2',5,5'-tetra(tert-butylperoxycarbonyl)benzo Phenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl) benzophenone, 3,3',4,4'-tetra(tert-amylperoxycarbonyl) benzophenone, 3, 3',4,4'-tetra(tert-hexylperoxycarbonyl) benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butyl Organic peroxides such as peroxybenzoate and di-tert-butyldiperoxyisophthalate; Quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 1,2-benzanthraquinone; Benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin, and α-phenylbenzoin; 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-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-methylpropionyl) benzyl}-phenyl]-2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-mor Polinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-( Alkylphenone-based compounds such as 4-morpholin-4-yl-phenyl)-butan-1-one; Acyl phosphine oxide-based compounds such as bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methyl Oxime ester-based compounds such as benzoyl)-9H-carbazol-3-yl]ethanone can be mentioned.

Photoradical polymerization initiators are available as commercial products, for example, IRGACURE [registered trademark] 651, 184, 2959, 127, 907, 369, 379EG, 819, 819DW. , 1800, 1870, 784, OXE01, OXE02, OXE03, OXE04, 250, 1173, MBF, TPO, 4265, TPO (above, manufactured by BASF), KAYACURE [registered Trademark] DETX-S, MBP, DMBI, EPA, OA (manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, 55 (manufactured by STAUFFER Co. LTD), ESACURE KIP150, TZT , 1001, KTO46, KB1, KL200, KS300, EB3, triazine-PMS, triazine A, triazine B (manufactured by Nihon Sieberhegner Co., Ltd.), Adeka Optomer N- Examples include 1717, N-1414, N-1606, Adeka Acruz N-1919T, NCI-831E, NCI-930, and NCI-730 (manufactured by ADEKA Co., Ltd.).

These radical photopolymerization initiators may be used individually, or may be used in combination of two or more types.

The content of the radical photopolymerization initiator is not particularly limited, but is preferably 0.1 parts by mass to 20 parts by mass, and more preferably 0.5 parts by mass to 15 parts by mass from the viewpoint of photosensitivity characteristics, relative to 100 parts by mass of the reaction product. When the radical photopolymerization initiator is contained in an amount of 0.1 parts by mass or more with respect to 100 parts by mass of the reaction product, the light sensitivity of the photosensitive resin composition is likely to be improved. On the other hand, when the radical photopolymerization 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. This is easy to improve.

<<Cross-linkable compound>>

In the embodiment, in order to improve the resolution of the relief pattern, a monomer (crosslinkable compound) having a photo-radically polymerizable unsaturated bond can be optionally contained in the photosensitive resin composition.

As such a crosslinkable compound, a (meth)acrylic compound that undergoes a radical polymerization reaction using a photo radical polymerization initiator is preferable, and is not particularly limited to the following, but includes diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. Acrylates, mono or di(meth)acrylates of ethylene glycol or polyethylene glycol, mono or di(meth)acrylates of propylene glycol or polypropylene glycol, mono, di or tri(meth)acrylates of glycerol, 1,4- Di(meth)acrylate of butanediol, di(meth)acrylate of 1,6-hexanediol, di(meth)acrylate of 1,9-nonanediol, di(meth)acrylate of 1,10-decanediol , di(meth)acrylate of neopentyl glycol, cyclohexane di(meth)acrylate, di(meth)acrylate of cyclohexane dimethanol, di(meth)acrylate of tricyclodecane dimethanol, dioxane glycol. Di(meth)acrylate, mono or di(meth)acrylate of bisphenol A, di(meth)acrylate of bisphenol F, di(meth)acrylate of hydrogenated bisphenol A, benzene trimethacrylate, 9,9- Di(meth)acrylate of bis[4-(2-hydroxyethoxy)phenyl]fluorene, di(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, isobornyl(meth)acrylate ester, acryl amide and its derivatives, methacryl amide and its derivatives, trimethylolpropane tri(meth)acrylate, di or tri(meth)acrylate of glycerol, di, tri, or tetra(meth)acrylate of pentaerythritol. esters, and compounds such as ethylene oxide or propylene oxide adducts of these compounds, 2-isocyanate ethyl (meth)acrylate or isocyanate-containing (meth)acrylate, and methyl ethyl ketone oxime, ε-caprolactam, γ-acrylate, etc. Compounds to which blocking agents such as caprolactam, 3,5-dimethylpyrazole, diethyl malonate, ethanol, isopropanol, n-butanol, and 1-methoxy-2-propanol are added can be mentioned. In addition, these compounds may be used individually or in combination of two or more types. Additionally, in this 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.

<<thermal curing agent>>

As a heat curing agent, for example, hexamethoxymethylmelamine, tetramethoxymethylglycoluril, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl) glycoluril, 1,3 ,4,6-tetrakis(butoxymethyl) glycoluril, 1,3,4,6-tetrakis(hydroxymethyl) glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3 , 3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) urea, etc.

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

<<Filler>>

Examples of fillers include inorganic fillers, and specific examples include sols such as silica, aluminum nitride, boron nitride, zirconia, and alumina.

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

<<Other resin components>>

In embodiments, the photosensitive resin composition may further contain resin components other than the reaction product. Examples of resin components that can be contained in the photosensitive resin composition include polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, and acrylic resin.

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

<<Sensitizer>>

In the embodiment, a sensitizer can be optionally added to the photosensitive resin composition to improve photosensitivity.

As a sensitizer, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis( 4'-diethylaminobenzal) cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino), 4,4 ＇-bis(diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p -Dimethylaminophenylvinylene) benzothiazole, 2-(p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4) '-diethylaminobenzal) acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin , 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethyl Ethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimi Dazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostylyl) benzoxazole, 2-(p-dimethylaminostylyl) benzthiazole, 2- (p-dimethylaminostylyl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, etc. can be mentioned.

These can be used individually or in combination of two or more.

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

<<Adhesive aid>>

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

Examples of adhesion aids include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-mercaptopropyl. Methyldimethoxysilane, 3-(meth)acryloxypropyldimethoxymethylsilane, 3-(meth)acryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycylate Doxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl) succinimide, N-[3-(triethoxysilyl) propyl]phthalamidic 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) Silane coupling agents such as propyl anhydride and N-phenylaminopropyltrimethoxysilane, and aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethyl acetoacetate aluminum diiso. Aluminum-based adhesive aids such as propyrate, etc. can be mentioned.

Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength.

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

<<Thermal polymerization inhibitor>>

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

Examples of thermal polymerization inhibitors include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1 , 2-Cyclohexanediamine tetraacetic acid, glycol etherdiamine 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, etc. are used.

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

<<Azole Compound>>

For example, when using a substrate made of copper or a copper alloy, an azole compound can be optionally blended into the photosensitive resin composition to suppress discoloration of the substrate.

Examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, and 5-phenyl-1H-triazole. , 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylamino Ethyl) triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5 -methyl-2-hydroxyphenyl) benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di- t-butyl-2-hydroxyphenyl) benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl -2-hydroxyphenyl) benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzo Triazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl -1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. are mentioned. Particularly preferred examples include tolyltriazole, 5-methyl-1H-triazole, and 4-methyl-1H-benzotriazole.

In addition, these azole compounds may be used alone or in a mixture of two or more types.

The content of the azole compound is not particularly limited, but is preferably 0.1 parts by mass to 20 parts by mass, and more preferably 0.5 parts by mass to 5 parts by mass from the viewpoint of photosensitivity characteristics, with respect to 100 parts by mass of the reaction product. When the content of the azole compound is 0.1 parts by mass or more with respect to 100 parts by mass of the reaction product, discoloration of the surface of the copper or copper alloy is suppressed when the photosensitive resin composition is formed on copper or copper alloy, while the content is 20 parts by mass or less. In this case, it is preferable because it has excellent light sensitivity.

<<Hindad phenol compound>>

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

As hindered phenol compounds, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di- t-butyl-4-hydroxyphenyl) propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylene bis(2, 6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t- butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5- di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] , N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol) , 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)pro cypionate], tris(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di- t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4 ,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine- 2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5- Triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]- 1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethyl Benzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4- Phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2 ,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5 -Ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris( 4-t-Butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3 ,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H) -Trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6 -(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4, 6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2 ,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5 -Triazine-2,4,6-(1H,3H,5H)-trione, etc. are included, but are not limited to these.

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

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

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

(resin film)

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

Application methods include methods that have been conventionally used to apply photosensitive resin compositions, such as application with a spin coater, bar coater, blade coater, curtain coater, screen printer, etc., spray application with a spray coater, etc. Available.

As a firing method for obtaining a fired product, various methods can be selected, such as using a hot plate, using an oven, or using a temperature rising oven that can set a temperature program. Firing can be performed, for example, at 130°C to 250°C for 30 minutes to 5 hours. As an atmospheric gas during 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 μm, and more preferably 2 μm to 50 μm.

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

(Photosensitive resist film)

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

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

Usually, the photosensitive resin layer and the cover film are laminated in this order on the base film.

The photosensitive resist film can be manufactured, for example, by applying a photosensitive resin composition onto a base film, drying it to form a photosensitive resin layer, and then laminating a cover film on the photosensitive resin layer.

Application methods include methods that have been conventionally used to apply photosensitive resin compositions, such as application with a spin coater, bar coater, blade coater, curtain coater, screen printer, etc., spray application with a spray coater, etc. Available.

Examples of drying methods include conditions of 1 minute to 1 hour at 20°C to 200°C.

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

As a base film, a well-known thing can be used, for example, a thermoplastic resin film etc. can be used. Examples of this thermoplastic resin include polyester such as polyethylene terephthalate. The thickness of the base film is preferably 2 μm to 150 μm.

As a cover film, a known cover film can be used, for example, a polyethylene film, a polypropylene film, etc. can be used. As a cover film, a film whose adhesive force with the photosensitive resin layer is smaller than that of the base film is preferable. The thickness of the cover film is preferably 2 μm to 150 μm, more preferably 2 μm to 100 μm, and particularly preferably 5 μm to 50 μm.

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

(Method for manufacturing substrate with cured relief pattern)

The method for manufacturing a substrate with a cured relief pattern of the present invention includes:

(1) applying the photosensitive resin composition according to the present invention on a substrate to form a photosensitive resin layer (photosensitive resin film) on the substrate;

(2) exposing the photosensitive resin layer to light;

(3) developing the photosensitive resin layer after the exposure to form a relief pattern;

(4) Process of heat treating the relief pattern to form a hardened relief pattern

Includes.

Hereinafter, each process will be described.

(1) A process of applying the photosensitive resin composition according to the present invention on a substrate to form a photosensitive resin layer on the substrate.

In this process, the photosensitive resin composition according to the present invention is applied onto a substrate and, if necessary, dried thereafter to form a photosensitive resin layer. Application methods include methods that have been conventionally used to apply photosensitive resin compositions, such as application with a spin coater, bar coater, blade coater, curtain coater, screen printer, etc., spray application with a spray coater, etc. Available.

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

(2) Process of exposing the photosensitive resin layer

In this process, the photosensitive resin layer formed in the above step (1) is exposed using an exposure device such as a contact aligner, mirror projection, stepper, or directly through a photomask or reticle having a pattern, or by an ultraviolet light source, etc. expose.

Light sources used during exposure include, for example, g-line, h-line, i-line, ghi-line broadband, and KrF excimer laser. The exposure amount is preferably 25 mJ/cm ² to 2000 mJ/cm ² .

Thereafter, for the purpose of improving light sensitivity, etc., post-exposure bake (PEB) and/or pre-development bake may be performed at any combination of temperature and time as needed. The range of bake conditions is preferably 50°C to 200°C, and preferably 10 to 600 seconds for the time, but is not limited to this range unless various properties of the photosensitive resin composition are impaired.

(3) Process of developing the photosensitive resin layer after the exposure and forming a relief pattern.

In this process, 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 used from among conventionally known photoresist developing methods, such as the rotary spray method, the paddle method, and the immersion method involving ultrasonic treatment. You can select and use it. Additionally, after development, rinsing may be performed for the purpose of removing the developing solution. Additionally, for purposes such as adjusting the shape of the relief pattern, post-development baking may be performed at any combination of temperature and time as needed.

As a developer used for development, an organic solvent is preferable. Examples of organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, and cyclopentanone. , cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferred. In addition, two or more types of each solvent, for example, can be used in combination of several types.

The rinse liquid used for rinsing is preferably an organic solvent that is miscible with the developer and has low solubility in the photosensitive resin composition. Preferred rinse solutions include, for example, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, toluene, and xylene. In addition, two or more types of each solvent, for example, can be used in combination of several types.

(4) Process of heat treating the relief pattern to form a hardened relief pattern

In this process, the relief pattern obtained through the above development is heated and converted into a hardened relief pattern. When the reaction product is a polyamic acid, thermal imidization is performed by this heating, and a cured relief pattern containing polyimide can be obtained. As a method of heat curing, for example, various methods can be selected, such as using a hot plate, using an oven, or using a temperature rising oven that can set a temperature program. Heating can be performed, for example, at 130°C to 250°C for 30 minutes to 5 hours. As an atmospheric gas during 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, and 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 or below the semiconductor element is also provided. A cured film is a cured relief pattern formed from the photosensitive resin composition of the present invention. The cured relief pattern can be obtained, for example, through steps (1) to (4) in the method for manufacturing a substrate with a cured relief pattern described above.

Additionally, the present invention can be applied to a semiconductor device manufacturing method that uses a semiconductor element as a substrate and includes the above-described manufacturing method of a substrate with a cured relief pattern as part of the process. The semiconductor device of the present invention forms a cured relief pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure, etc., using a known semiconductor device manufacturing method, It can be manufactured by combining.

(display device)

In an embodiment, a display device is provided including a display element and a cured film provided on an upper part of the display element, wherein the cured film is the above-mentioned cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer interposed therebetween. For example, the cured film includes a surface protective film, an insulating film, and a planarization film for a TFT (Thin Film Transistor) liquid crystal display element and a color filter element, a protrusion for an MVA (Multi-domain Vertical Alignment) type liquid crystal display device, and an organic liquid crystal display device. A partition for an EL (Electro-Luminescence) device cathode is included.

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

[Example]

Next, the content of the present invention will be described in detail with reference to examples, but the present invention is not limited to these.

The weight average molecular weight (Mw) shown in the following synthesis examples is the result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). For the measurement, a GPC device (HLC-8320 GPC (manufactured by Tosoh Corporation)) was used, and the measurement conditions were as follows.

Column: Shodex [registered trademark] KD-805 / Shodex [registered trademark] KD-803 (made by Showa Denko Co., Ltd.)

·Column temperature: 50℃

·Flow rate: 1mL/min

Eluent: N,N-dimethylformamide (DMF), lithium bromide hydrate (30mM)/phosphoric acid (30mM)/tetrahydrofuran (1%)

·Standard sample: polyethylene oxide

The chemical imidation rate shown in the following synthesis examples was calculated by the following method. 100 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard, ϕ5 (manufactured by Kusano Chemical Co., Ltd.)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) was added. (0.53 ml) was added and ultrasonic waves were applied to completely dissolve. Proton NMR of this solution was measured at 500 MHz using an NMR measuring device (JNM-ECA500) (manufactured by Nippon Electronics Co., Ltd.). The chemical imidization rate sets the proton derived from the structure that does not change before and after imidization as the reference proton, and calculates the peak integrated value of this proton and the integrated peak value of the proton derived from the NH group of amidic acid appearing around 9.5 ppm to 11.0 ppm. was obtained using the formula below.

Chemical imidization rate (%) = (1-α·x/y)Х100

In the above formula, x is the proton peak integration value derived from the NH group of amidic acid, y is the peak integration value of the reference proton, and α is the NH group of amidic acid in the case of polyamic acid (imidation rate of 0%). It is the ratio of the number of standard protons to one proton.

<Synthesis Example 1> Synthesis of polyamic acid (P-1)

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

<Synthesis Example 2> Synthesis of polyamic acid (P-2)

9.85 g of 3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 1,4-bis[2-(4-aminophenyl)-2 -Propyl] 12.84 g of benzene, 0.04 g of 2,6-di-tert-butyl-p-cresol, and 53.04 g of N-ethyl-2-pyrrolidone were stirred and dissolved at room temperature under air, then 4,4 37.25 g of '-(4,4'-isopropylidenediphenoxy) diphthalic anhydride and 86.91 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 3 hours, and then heated to 89°C at 50°C. Time stirred. The obtained polyamic acid had a repeating unit structure shown below (P-2), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 25,273.

<Synthesis Example 3> Synthesis of polyamic acid (P-3)

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

<Synthesis Example 4> Synthesis of polyamic acid (P-4)

3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 13.73 g, 2,2-bis[4-(4-aminophenoxy)phenyl ] After dissolving 9.14 g of propane, 0.06 g of 2,6-di-tert-butyl-p-cresol, and 53.50 g of N-ethyl-2-pyrrolidone by stirring at room temperature under air, 4,4'- (4,4'-isopropylidenediphenoxy) 37.08 g of diphthalic anhydride and 86.53 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 2 hours, and then stirred at 50°C for 88 hours. did. The obtained polyamic acid had a repeating unit structure shown below (P-4), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 24,973.

<Synthesis Example 5> Synthesis of polyamic acid (P-5)

9.47 g of 3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-bis[4-(4-aminophenoxy)phenyl ] After dissolving 14.70 g of propane, 0.04 g of 2,6-di-tert-butyl-p-cresol, and 56.49 g of N-ethyl-2-pyrrolidone by stirring at room temperature under air, 4,4'- (4,4'-isopropylidenediphenoxy) 35.79 g of diphthalic anhydride and 83.51 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 3 hours, and then stirred at 50°C for 89 hours. did. The obtained polyamic acid had a repeating unit structure shown below (P-5), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 27,852.

<Synthesis Example 6> Synthesis of polyamic acid (P-6)

3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 3.59 g, 2,2-bis[4-(4-aminophenoxy)phenyl ] 13.01 g of propane, 0.01 g of 2,6-di-tert-butyl-p-cresol, and 66.47 g of N-ethyl-2-pyrrolidone were stirred and dissolved at room temperature under air, then 4,4'- (4,4'-isopropylidenediphenoxy) 23.33 g of diphthalic anhydride and 93.33 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 3 hours, and then stirred at 50°C for 95 hours. did. The obtained polyamic acid had a repeating unit structure shown below (P-6), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 56,737.

<Synthesis Example 7> Synthesis of polyamic acid (P-7)

3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 1.16 g, 2,2-bis[4-(4-aminophenoxy)phenyl ] 16.22 g of propane, 0.01 g of 2,6-di-tert-butyl-p-cresol, and 69.53 g of N-ethyl-2-pyrrolidone were stirred and dissolved at room temperature under air, then 4,4'- (4,4'-isopropylidenediphenoxy) 22.62 g of diphthalic anhydride and 90.47 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 3 hours, and then stirred at 50°C for 95 hours. did. The obtained polyamic acid had a repeating unit structure shown below (P-7), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 58,225.

<Synthesis Example 8> Synthesis of polyamic acid (P-8)

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

<Synthesis Example 9> Synthesis of polyamic acid (P-9)

3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 6.22 g, bis[4-(4-aminophenoxy)phenyl]sulfone 10.18 g , 0.03 g of 2,6-di-tert-butyl-p-cresol, and 65.70 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, then 4,4'-(4,4 23.52 g of '-isopropylidenediphenoxy) diphthalic anhydride and 94.08 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 2 hours, and then stirred at 50°C for 92 hours. The obtained polyamic acid had a repeating unit structure shown below (P-9), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 31,175.

<Synthesis Example 10> Synthesis of polyamic acid (P-10)

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

<Synthesis Example 11> Synthesis of polyamic acid (P-11)

3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 7.94 g, bis(4-aminophenyl) terephthalate 10.46 g, 4-methoxy 0.05 g of phenol and 87.05 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride 29.98. g, and 58.04 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 3 hours, and then stirred at 50°C for 74 hours. The obtained polyamic acid had a repeating unit structure shown below (P-11), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 29,792.

<Synthesis Example 12> Synthesis of polyamic acid (P-12)

3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 7.94 g, 1,4-phenylene bis(4-aminobenzoate) 10.46 g , 0.05 g of 4-methoxyphenol, and 87.05 g of N-ethyl-2-pyrrolidone were stirred and dissolved in air at room temperature, and then 4,4'-(4,4'-isopropylidenediphenoxy ) 29.98 g of diphthalic anhydride and 58.04 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 3 hours, and then stirred at 50°C for 74 hours. The obtained polyamic acid had a repeating unit structure shown below (P-12), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 24,660.

<Synthesis Example 13> Synthesis of polyamic acid (P-13)

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

<Synthesis Example 14> Synthesis of polyamic acid (P-14)

3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 8.63 g, 2,2-bis[4-(4-aminophenoxy)phenyl ] 13.41 g of propane, 0.04 g of 2,6-di-tert-butyl-p-cresol, and 88.32 g of N-ethyl-2-pyrrolidone were stirred and dissolved at room temperature under air, then bis-(1, 3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) propane-2,2-diyl bis(2-methyl-4,1-phenylene) 37.92 g, and N-ethyl-2-p 51.68 g of rolidone was added to the system, stirred at room temperature for 2 hours, and then stirred at 40°C for 39 hours. The obtained polyamic acid had a repeating unit structure shown below (P-14), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 16,379.

<Synthesis Example 15> Synthesis of polyamic acid (P-15)

3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 6.23 g, 2,2-bis[4-(4-aminophenoxy)phenyl ] 9.68 g of propane and 63.64 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, and then 9,9-bis[4-(3,4-dicarboxyphenoxy)phenylfluorene. 29.09 g of diacid anhydride (BPF-PA, manufactured by JFE Chemical Co., Ltd.) and 41.36 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 3 hours, and then stirred at 40°C for 42 hours. . The obtained polyamic acid had a repeating unit structure shown below (P-15), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 24,559.

<Synthesis Example 16> Synthesis of polyamic acid (P-16)

3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 5.29 g, 2,2-bis[4-(4-aminophenoxy)phenyl ] 10.36 g of hexafluoropropane, 0.04 g of 4-methoxyphenol, and 65.87 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, then 9,9-bis[4-(3 , 24.68 g of 4-dicarboxyphenoxy) phenylfluorene diacid anhydride (BPF-PA, manufactured by JFE Chemical Co., Ltd.) and 28.23 g of N-ethyl-2-pyrrolidone were added to the system and incubated at room temperature for 4 hours. After stirring, the mixture was stirred at 50°C for 26.5 hours. The obtained polyamic acid had a repeating unit structure shown below (P-16), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 28,330.

<Synthesis Example 17> Synthesis of polyamic acid (P-17)

3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 6.181 g, 2,2-bis[4-(4-aminophenoxy)phenyl ] 9.60 g of propane, 0.04 g of 4-methoxyphenol, and 79.65 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, then 5-isobenzofuran carboxylic acid, 1,3-dihydro 24.0 g of -1,3-dioxo-cyclohexylidene-4,1-phenylene ester (BPZ-TME, manufactured by Honshu Kagaku Kogyo Co., Ltd.) and 39.82 g of N-ethyl-2-pyrrolidone were added in situ. and stirred at room temperature for 1 hour, then stirred at 50°C for 63 hours. The obtained polyamic acid had a repeating unit structure shown below (P-17), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 13,550.

<Synthesis Example 18> Synthesis of polyamic acid (P-18)

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

<Synthesis Example 19> Synthesis of polyamic acid (P-19)

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

<Synthesis Example 20> Synthesis of polyamic acid (P-20)

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

<Synthesis Example 21> Synthesis of polyamic acid (P-21)

3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 7.418 g, 2,2-bis[4-(4-aminophenoxy)phenyl ] 11.52 g of propane, 0.047 g of 4-methoxyphenol, and 126.47 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, then p-biphenylene bis(trimellitic acid monoester acid) Anhydride) (BP-TME, manufactured by Honshu Chemical Co., Ltd.) 9.0 g, 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride 19.28 g, and N-ethyl-2-pyrroli 63.23 g of pork was added to the system, stirred at room temperature for 1 hour, and then stirred at 50°C for 40 hours. The obtained polyamic acid had a repeating unit structure shown below (P-21), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 26,182.

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

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

<Synthesis Example 23> Synthesis of solvent-soluble polyimide (P-23)

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

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

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

<Comparative Synthesis Example 1> Synthesis of polyamic acid (P-25)

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

<Comparative Synthesis Example 2> Synthesis of polyamic acid (P-26)

42.28 g of 3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 0.09 g of 4-methoxyphenol, and N-ethyl-2-p. After dissolving 144.42 g of rolidone by stirring at room temperature under air, 46.13 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 61.89 g of N-ethyl-2-pyrrolidone were added to the system. After adding and stirring at room temperature for 1 hour, it was stirred at 80°C for 75 hours. A polyamic acid having a repeating unit structure shown below (P-26) was obtained.

<Comparative Synthesis Example 3> Synthesis of polyamic acid (P-27)

3,5-diamino benzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 31.71 g, 0.09 g of 4-methoxyphenol, and N-ethyl-2-p. After dissolving 137.13 g of rolidone by stirring at room temperature under air, 52.24 g of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride and 58.77 g of N-ethyl-2-pyrrolidone were added to the system. was added and stirred at room temperature for 3 hours, and then at 80°C for 75 hours. A polyamic acid having a repeating unit structure shown below (P-27) was obtained.

<Comparative Synthesis Example 4> Synthesis of polyamic acid (P-28)

18.00 g of 3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 0.08 g of 2,6-di-tert-butyl-p-cresol, and 54.23 g of N-ethyl-2-pyrrolidone were dissolved by stirring at room temperature under air, 13.22 g of 1,2,3,4-cyclobutane tetracarboxylic dianhydride, and N-ethyl-2-pyrrolidone. 30.40 g of pork was added to the system, stirred at room temperature for 62 hours, and then stirred at 40°C for 34 hours. The obtained polyamic acid had a repeating unit structure shown below (P-28), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 42,930.

<Comparative Synthesis Example 5> Synthesis of polyamic acid (P-29)

15.00 g of 3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.), 0.06 g of 2,6-di-tert-butyl-p-cresol, And 45.19 g of N-ethyl-2-pyrrolidone was dissolved by stirring at room temperature under air, and then 1,1'-bicyclohexane-3,3',4,4'-tetracarboxylic acid-3,3'. , 17.21 g of 4,4'-2 anhydride (BPDA-H, manufactured by Iwatani Gas Co., Ltd.) and 30.12 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 62 hours, and then stirred at room temperature for 40 hours. It was stirred at ℃ for 34 hours. The obtained polyamic acid had a repeating unit structure shown below (P-29), and the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 45,136.

<Comparative Synthesis Example 6> Synthesis of solvent-soluble polyimide (P-30)

3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd.) 8.60 g, 2,2-bis[4-(4-aminophenoxy)phenyl ] After dissolving 16.85 g of hexafluoropropane, 0.05 g of 4-methoxyphenol, and 148.85 g of N-ethyl-2-pyrrolidone by stirring at room temperature under air, 4,4'-(hexafluoroiso 27.72 g of propylidene diphthalic anhydride and 63.79 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 1 hour, and then stirred at 50°C for 87 hours. The weight average molecular weight (Mw) of the obtained polyamic acid measured in terms of polystyrene by GPC was 27,335.

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

<Example 1>

27.75 g of solution containing polyamic acid (P-1) obtained in Synthesis Example 1 (solid content concentration: 30% by weight), NK ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. ) 1.67 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, manufactured by BASF Japan Co., Ltd. ) 0.42 g and 0.17 g of KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm. A solution of the negative photosensitive resin composition was prepared.

<Example 2>

32.24 g of solution containing polyamic acid (P-2) obtained in Synthesis Example 2 (solid concentration: 30% by weight), NK ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. ) 1.93 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, manufactured by BASF Japan Co., Ltd. ) 0.48 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6 0.15 g of (1H,3H,5H)-Trion, manufactured by BASF Japan Co., Ltd., and 0.19 g of KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) were mixed. After dissolving, a solution of the negative photosensitive resin composition was prepared by filtering it using a polypropylene filter with a pore diameter of 5 μm.

<Example 3>

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

<Example 4>

22.08 g of solution containing polyamic acid (P-3) obtained in Synthesis Example 3 (solid concentration: 30% by weight), NK ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. ) 1.32 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, manufactured by BASF Japan Co., Ltd. ) 0.33 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6 (1H,3H,5H)-Trion, manufactured by BASF Japan Co., Ltd.) 0.10 g, KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) 0.13 g, and N- After mixing and dissolving 11.04 g of ethyl-2-pyrrolidone, the mixture was filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 5>

32.49 g of solution containing polyamic acid (P-3) obtained in Synthesis Example 3 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate) as a crosslinking agent, Shin Nakamura Ka. (manufactured by Kaku Kogyo Co., Ltd.) 0.97 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. product) 0.49 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.15 g, KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.19 g and 0.71 g of N-ethyl-2-pyrrolidone were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 6>

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

<Example 7>

29.96 g of solution containing polyamic acid (P-5) obtained in Synthesis Example 5 (solid concentration: 30% by weight), NK ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. ) 1.80 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, manufactured by BASF Japan Co., Ltd. ) 0.45 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6 (1H,3H,5H)-Trion, manufactured by BASF Japan Co., Ltd.) 0.13 g, KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) 0.18 g, and N- After mixing and dissolving 2.48 g of ethyl-2-pyrrolidone, the mixture was filtered using a polypropylene filter with a pore size of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 8>

23.89 g of solution containing polyamic acid (P-5) obtained in Synthesis Example 5 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate) as a crosslinking agent, Shin Nakamura Ka. 0.72 g (manufactured by Gakukogyo Co., Ltd.), IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. product) 0.36 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.11 g, KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.14 g and 4.78 g of N-ethyl-2-pyrrolidone were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 9>

37.84 g of solution containing polyamic acid (P-6) obtained in Synthesis Example 6 (solid concentration: 20% by weight), NK ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. ) 1.51 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, manufactured by BASF Japan Co., Ltd. ) 0.38 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6 0.11 g of (1H,3H,5H)-Trion, manufactured by BASF Japan Co., Ltd., and 0.15 g of KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) were mixed. After dissolving and filtering using a polypropylene filter with a pore diameter of 5 μm, a solution of the negative photosensitive resin composition was prepared.

<Example 10>

37.84 g of solution containing polyamic acid (P-7) obtained in Synthesis Example 7 (solid concentration: 20% by weight), NK ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. ) 1.51 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, manufactured by BASF Japan Co., Ltd. ) 0.38 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6 0.11 g of (1H,3H,5H)-Trion, manufactured by BASF Japan Co., Ltd., and 0.15 g of KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) were mixed. After dissolving, a solution of the negative photosensitive resin composition was prepared by filtering it using a polypropylene filter with a pore diameter of 5 μm.

<Example 11>

22.08 g of solution containing polyamic acid (P-8) obtained in Synthesis Example 8 (solid content concentration: 30% by weight), NK ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. ) 1.32 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, manufactured by BASF Japan Co., Ltd. ) 0.33 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6 (1H,3H,5H)-Trion, manufactured by BASF Japan Co., Ltd.) 0.10 g, KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) 0.13 g, and N- After mixing and dissolving 11.04 g of ethyl-2-pyrrolidone, the mixture was filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 12>

31.50 g of solution containing polyamic acid (P-8) obtained in Synthesis Example 8 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate) as a crosslinking agent, Shin Nakamura Ka. 0.95 g (manufactured by Kaku Kogyo Co., Ltd.), IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. product) 0.47 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.14 g, KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.19 g and 1.75 g of N-ethyl-2-pyrrolidone were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 13>

33.11 g of solution containing polyamic acid (P-9) obtained in Synthesis Example 9 (solid concentration: 20% by weight), NK ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. ) 1.32 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, manufactured by BASF Japan Co., Ltd. ) 0.33 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6 0.10 g of (1H,3H,5H)-Trion, manufactured by BASF Japan Co., Ltd., and 0.13 g of KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) were mixed. After dissolving, a solution of the negative photosensitive resin composition was prepared by filtering it using a polypropylene filter with a pore diameter of 5 μm.

<Example 14>

20.75 g of solution (solid concentration: 30% by weight) containing polyamic acid (P-10) obtained in Synthesis Example 10, and NK Ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. ) 1.25 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, manufactured by BASF Japan Co., Ltd. ) 0.31 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6 (1H,3H,5H)-Trion, manufactured by BASF Japan Co., Ltd.) 0.09 g, KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) 0.12 g, and N- After mixing and dissolving 2.47 g of ethyl-2-pyrrolidone, the mixture was filtered using a polypropylene filter with a pore size of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 15>

A solution containing 23.66 g of polyamic acid (P-11) obtained in Synthesis Example 11 (solid concentration: 25% by weight), 0.99 g of N-ethyl-2-pyrrolidone, and NK ester A-DOD-N (1) as a crosslinking agent. , 10-decanediol diacrylate, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.) 0.59 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl) as an optical radical initiator -, 2-(O-benzoyl oxime)], BASF Japan Co., Ltd. product) 0.30 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydride) Roxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.09 g, and KBM-5103 (3-acryloxypropyltri) A solution of a negative photosensitive resin composition was prepared by mixing and dissolving 0.12 g of methoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd.) and filtering it using a polypropylene filter with a pore diameter of 5 μm.

<Example 16>

24.78 g of solution (solid concentration: 25% by weight) containing polyamic acid (P-12) obtained in Synthesis Example 12, NK ester A-DOD-N (1,10-decanediol diacrylate) as a crosslinking agent, Shin Nakamura Ka. 0.62 g (manufactured by Kaku Kogyo Co., Ltd.), IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. product) 0.31 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.09 g, and KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.12 g was mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 17>

27.64 g of solution (solid concentration: 30% by weight) containing polyamic acid (P-13) obtained in Synthesis Example 13, and NK Ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. ) 1.66 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, manufactured by BASF Japan Co., Ltd. ) 0.41 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6 0.12 g of (1H,3H,5H)-Trion, manufactured by BASF Japan Co., Ltd., and 0.17 g of KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) were mixed. After dissolving, a solution of the negative photosensitive resin composition was prepared by filtering it using a polypropylene filter with a pore diameter of 5 μm.

<Example 18>

28.42 g of solution containing polyamic acid (P-13) obtained in Synthesis Example 13 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate) as a crosslinking agent, Shin Nakamura Ka. 0.85 g (manufactured by Kaku Kogyo Co., Ltd.), IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. product) 0.43 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.13 g, and KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.17 g was mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 19>

27.64 g of solution (solid concentration: 30% by weight) containing polyamic acid (P-14) obtained in Synthesis Example 14, and NK Ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. ) 1.66 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, manufactured by BASF Japan Co., Ltd. ) 0.41 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6 0.12 g of (1H,3H,5H)-Trion, manufactured by BASF Japan Co., Ltd., and 0.17 g of KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) were mixed. After dissolving, a solution of the negative photosensitive resin composition was prepared by filtering it using a polypropylene filter with a pore diameter of 5 μm.

<Example 20>

28.42 g of solution containing polyamic acid (P-14) obtained in Synthesis Example 14 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate) as a crosslinking agent, Shin Nakamura Ka. 0.85 g (manufactured by Kaku Kogyo Co., Ltd.), IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. product) 0.43 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.13 g, and KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.17 g was mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 21>

21.40 g of solution (solid concentration: 30% by weight) containing polyamic acid (P-15) obtained in Synthesis Example 15, and NK Ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. ) 1.28 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, manufactured by BASF Japan Co., Ltd. ) 0.32 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6 (1H,3H,5H)-Trion, manufactured by BASF Japan Co., Ltd.) 0.10 g, KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) 0.13 g, and N- After mixing and dissolving 1.77 g of ethyl-2-pyrrolidone, the mixture was filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 22>

37.81 g of solution containing polyamic acid (P-16) obtained in Synthesis Example 16 (solid concentration: 30% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate) as a crosslinking agent, Shin Nakamura Ka. 2.27 g (manufactured by Kaku Kogyo Co., Ltd.), IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. product) 0.57 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.17 g, and KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.23 g was mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 23>

65.34 g of solution containing polyamic acid (P-17) obtained in Synthesis Example 17 (solid concentration: 25% by weight), NK ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. ) 3.27 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, manufactured by BASF Japan Co., Ltd. ) 0.82 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6 0.25 g of (1H,3H,5H)-Trion, manufactured by BASF Japan Co., Ltd., and 0.33 g of KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) were mixed. After dissolving, a solution of the negative photosensitive resin composition was prepared by filtering it using a polypropylene filter with a pore diameter of 5 μm.

<Example 24>

38.23 g of solution containing polyamic acid (P-18) obtained in Synthesis Example 18 (solid concentration: 25% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate) as a crosslinking agent, Shin Nakamura Ka. 0.96 g (manufactured by Kaku Kogyo Co., Ltd.), IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. product) 0.48 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.14 g, and KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.19 g was mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 25>

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

<Example 26>

38.57 g of solution containing polyamic acid (P-20) obtained in Synthesis Example 20 (solid concentration: 20% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate) as a crosslinking agent, Shin Nakamura Ka. 0.77 g (manufactured by Kaku Kogyo Co., Ltd.), IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. product) 0.39 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.12 g, and KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.15 g was mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 27>

38.57 g of solution containing polyamic acid (P-21) obtained in Synthesis Example 21 (solid concentration: 20% by weight), NK ester A-DOD-N (1,10-decanediol diacrylate) as a crosslinking agent, Shin Nakamura Ka. 0.77 g (manufactured by Kaku Kogyo Co., Ltd.), IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. product) 0.39 g, IRGANOX [registered trademark] 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trione, manufactured by BASF Japan Co., Ltd.) 0.12 g, and KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.15 g was mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 28>

11.02 g of powder of solvent-soluble polyimide (P-22) obtained in Synthesis Example 22, 25.71 g of N-ethyl-2-pyrrolidone, and NK ester A-DOD-N (1,10-decanediol diacryl) as a crosslinking agent. Rate, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.) 2.20 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-) as an optical radical initiator Benzoyl oxime)], BASF Japan Co., Ltd. product) 0.55 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3 , 5-triazine-2,4,6(1H,3H,5H)-trione, BASF Japan Co., Ltd.) 0.17 g, and KBM-5103 (3-acryloxypropyltrimethoxy silane, Shinetsu Chemical) After mixing and dissolving 0.22 g (manufactured by Kogyo Co., Ltd.), the solution was filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 29>

10.89 g of powder of solvent-soluble polyimide (P-23) obtained in Synthesis Example 23, 26.00 g of N-ethyl-2-pyrrolidone, and NK ester A-DOD-N (1,10-decanediol diacryl) as a crosslinking agent. Rate, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.) 2.18 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-) as an optical radical initiator Benzoyl oxime)], BASF Japan Co., Ltd. product) 0.54 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3 , 5-triazine-2,4,6(1H,3H,5H)-trione, BASF Japan Co., Ltd.) 0.16 g, and KBM-5103 (3-acryloxypropyltrimethoxy silane, Shinetsu Chemical) After mixing and dissolving 0.22 g (manufactured by Kogyo Co., Ltd.), the solution was filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Example 30>

10.89 g of powder of solvent-soluble polyimide (P-24) obtained in Synthesis Example 24, 26.00 g of N-ethyl-2-pyrrolidone, and NK ester A-DOD-N (1,10-decanediol diacryl) as a crosslinking agent. Rate, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.) 2.18 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-) as an optical radical initiator Benzoyl oxime)], BASF Japan Co., Ltd. product) 0.54 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3 , 5-triazine-2,4,6(1H,3H,5H)-trione, BASF Japan Co., Ltd.) 0.16 g, and KBM-5103 (3-acryloxypropyltrimethoxy silane, Shinetsu Chemical) After mixing and dissolving 0.22 g (manufactured by Kogyo Co., Ltd.), the solution was filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of the negative photosensitive resin composition.

<Comparative Example 1>

27.75 g of solution (solid concentration: 30% by weight) containing polyamic acid (P-25) obtained in Comparative Synthesis Example 1, and NK ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. Article) 1.67 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. (J) 0.42 g and 0.17 g of KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm. , a solution of the negative photosensitive resin composition was prepared.

<Comparative Example 2>

26.17 g of solution (solid concentration: 30% by weight) containing polyamic acid (P-26) obtained in Comparative Synthesis Example 2, and NK ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. Article) 1.57 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. (J) 0.39 g and 0.16 g of KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm. , a solution of the negative photosensitive resin composition was prepared.

<Comparative Example 3>

25.08 g of a solution (solid concentration: 30% by weight) containing polyamic acid (P-27) obtained in Comparative Synthesis Example 3, and NK Ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. Article) 1.50 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. (J) 0.38 g and 0.15 g of KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm. , a solution of the negative photosensitive resin composition was prepared.

<Comparative Example 4>

27.96 g of solution containing polyamic acid (P-28) obtained in Comparative Synthesis Example 4 (solid concentration: 27% by weight), NK ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. Article) 1.51 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. (J) 0.38 g and 0.15 g of KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm. , a solution of the negative photosensitive resin composition was prepared.

<Comparative Example 5>

27.75 g of a solution (solid concentration: 30% by weight) containing polyamic acid (P-29) obtained in Comparative Synthesis Example 5, and NK Ester A-200 (polyethylene glycol diacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd.) as a crosslinking agent. Article) 1.67 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] as an optical radical initiator, BASF Japan Co., Ltd. (J) 0.42 g and 0.17 g of KBM-5103 (3-acryloxypropyltrimethoxy silane, manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.) were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm. , a solution of the negative photosensitive resin composition was prepared.

<Comparative Example 6>

9.14 g of powder of solvent-soluble polyimide (P-30) obtained in Comparative Synthesis Example 6, 16.98 g of N-ethyl-2-pyrrolidone, and NK ester A-DOD-N (1,10-decanediol diol as a crosslinking agent) 1.83 g of acrylate, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd., IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O) as an optical radical initiator -benzoyl oxime)], manufactured by BASF Japan Co., Ltd.) 0.46 g, IRGANOX [registered trademark] 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1, 3,5-triazine-2,4,6(1H,3H,5H)-trione, BASF Japan Co., Ltd.) 0.14 g, and KBM-5103 (3-acryloxypropyltrimethoxy silane, Shin-Etsu Ka A solution of the negative photosensitive resin composition was prepared by mixing and dissolving 0.18 g (manufactured by Kaku Kogyo Co., Ltd.) and filtering it using a polypropylene filter with a pore diameter of 5 μm.

[Photosensitivity evaluation]

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

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

[Electrical characteristics evaluation]

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 a 20 μm thick aluminum foil, and heated on a hot plate at 115°C for 180 seconds. A photosensitive resin film was formed on the aluminum foil by firing for 270 seconds. Next, using an i-line aligner (PLA-501, manufactured by Canon Co., Ltd.), the entire surface was exposed to 500 mJ/cm ² on the wafer, followed by 1 hour at 160°C in a nitrogen atmosphere, and then 230° C. ℃, and baked for 1 hour. Additionally, the fired aluminum foil was immersed in 6N hydrochloric acid to dissolve the aluminum foil, thereby obtaining a film. Next, the obtained film was dried under reduced pressure at 80°C for 2 hours, left for 24 hours in an environment with a temperature of approximately 25°C and a humidity of approximately 42%, and then the dielectric loss tangent at 1 GHz was measured using a cavity resonator (TMR-1 A, Keycom). It was measured using a product manufactured by Co., Ltd. The measurement conditions for dielectric loss tangent are as follows.

·Measurement method: perturbation type cavity resonance technique

・Vector network analyzer: Field Fox N9926A (manufactured by Keysight Technologies Co., Ltd.)

Cavity resonator: TMR-1 A (manufactured by Keycom Co., Ltd.)

Cavity volume: 1192822mm ³

·Measurement frequency: approximately 1 GHz

・Sample tube: made of PTFE, inner diameter: 3 mm, length approximately 30 mm (manufactured by Kicom Co., Ltd.)

[Evaluation of machine characteristics]

The negative photosensitive resin compositions prepared in Examples 1 to 30 and Comparative Examples 1 to 6 were spin coated on a 100 nm thick aluminum wafer and baked on a hot plate at 115°C for 180 or 270 seconds to form an aluminum wafer. A photosensitive resin film was formed on the surface. Next, using an i-line aligner (PLA-501, manufactured by Canon Co., Ltd.), the entire surface was exposed to 500 mJ/cm ² on the wafer, followed by 1 hour at 160°C in a nitrogen atmosphere, and then 230° C. ℃, and baked for 1 hour. Additionally, after cutting the photosensitive resin film at intervals of 5 mm in width using a dicing saw (DAD323, manufactured by Disco Co., Ltd.), this aluminum wafer was immersed in 6 N hydrochloric acid to dissolve the aluminum, thereby obtaining a film with a width of 5 mm. . Next, the tensile elongation of the obtained film was measured using a tabletop precision universal testing machine (Autograph AGS-10 kNX, manufactured by Shimadzu Seisakusho Co., Ltd.). The measurement conditions for tensile elongation are as follows.

・Tabletop precision universal testing machine: Autograph AGS-10 kNX (manufactured by Shimadzu Seisakusho Co., Ltd.)

·Film width: 5mm

·Grip section distance: 25mm

Here, if the tensile elongation is 50%, it means that the film is stretched up to 1.5 times, or in other words, the film breaks when the distance between gripping zones is 1.5 times (37.5 mm).

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

From the results in Table 2, the films obtained from the negative photosensitive resin compositions of Examples 1 to 30 had lower dielectric loss tangent values at 1 GHz than those of Comparative Examples 1 to 5. In addition, the tensile elongation value of the films obtained from the negative photosensitive resin compositions of Examples 1 to 30 was improved compared to that of Comparative Examples 1 to 6.

That is, the negative photosensitive resin compositions of Examples 1 to 30 are capable of creating relief patterns, have a low dielectric loss tangent, and have the characteristics of high tensile elongation, so they require excellent electrical and mechanical properties. It can be suitably used in the manufacture of electronic materials.

Claims (18)

A photosensitive resin composition containing a reaction product of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings, and a solvent. In claim 1,
A photosensitive resin composition wherein the reaction product is a polyamic acid or a polyimide obtained by dehydrating and ring-closing a polyamic acid. In claim 2,
The polyamic acid has at least a structural unit represented by the following formula (1),
A photosensitive resin composition in which the polyimide has at least a structural unit represented by the following formula (2).
[Tuesday 1]

[In formula (1), Ar ₁ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar ₂ represents a tetravalent organic group having 3 or more aromatic rings.]
[Tuesday 2]

[In formula (2), Ar ₃ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar ₄ represents a tetravalent organic group having 3 or more aromatic rings.] In claim 3,
A photosensitive resin composition in which Ar ₂ in the formula (1) and Ar ₄ in the formula (2) are tetravalent organic groups represented by the following formula (3).
[Tuesday 3]

[In formula (3), X ₁ and X ₂ each independently represent a direct bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, or sulfonyl bond. R ₁ and R ₂ each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms. Y represents a divalent organic group represented by the following formula (3-1) or (3-2). n1 and n2 each independently represent an integer from 0 to 3. When R ₁ is plural, the plural R ₁ may be the same or different. When R ₂ is plural, the plural R ₂ may be the same or different. * indicates a combined hand.]
[Tuesday 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 ₃ and R ₄ each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. m1 represents an integer from 0 to 3. n3 and n4 each independently represent an integer from 0 to 4. When Z ₁ is plural, the plural Z ₁ may be the same or different. When n4 is plural, the plural n4 may be the same or different. When R ₃ is plural, the plural R ₃ may be the same or different. When R ₄ is plural, the plural R ₄ may be the same or different. * represents the bonding hand.
In formula (3-2), Z ₂ represents a divalent organic group represented by the following formula (4) or (5). R ₅ and R ₆ each independently represent a hydrocarbon group having 1 to 6 carbon atoms which may be substituted. n5 and n6 each independently represent an integer from 0 to 4. When R ₅ is plural, the plural R ₅ may be the same or different. When R ₆ is plural, the plural R ₆ may be the same or different. * indicates a combined hand.]
[Tuesday 5]

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

[In formula (6), Z ₃ represents an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond, and Z ₄ represents a direct bond, an ester bond, or an amide bond. Z ₅ represents a direct bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, or sulfonyl bond. m2 represents an integer from 0 to 1. R ₁₁ represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group, and R ₁₂ represents a hydrogen atom or a methyl group. * indicates a combined hand.] In claim 5,
A photosensitive resin composition in which Z ₃ and Z ₄ in the formula (6) are ester bonds. In claim 5 or claim 6,
A photosensitive resin composition in which R ₁₁ in the formula (6) is a 1,2-ethylene group. The method according to any one of claims 1 to 7,
A photosensitive resin composition further comprising a radical photopolymerization initiator. The method according to any one of claims 1 to 8,
A photosensitive resin composition further comprising a crosslinkable compound. The method according to any one of claims 1 to 9,
Photosensitive resin composition for forming an insulating film. The method according to any one of claims 1 to 10,
A photosensitive resin composition, which is a negative type photosensitive resin composition. A resin film, which is a baked product of a coating film of the photosensitive resin composition according to any one of claims 1 to 11. In claim 12,
Resin film, an insulating film. A photosensitive resist film comprising a base film, a photosensitive resin layer formed from the photosensitive resin composition according to any one of claims 1 to 11, and a cover film. (1) applying the photosensitive resin composition of any one of claims 1 to 11 on a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) Process of heat treating the relief pattern to form a hardened relief pattern
A method for manufacturing a substrate with a cured relief pattern attached, comprising: In claim 15,
A method for producing a substrate with a cured relief pattern, wherein the developer used for the development is an organic solvent. A substrate with a cured relief pattern manufactured by the method of claim 15 or 16. A semiconductor device comprising a semiconductor element and a cured film provided on or below the semiconductor element, wherein the cured film is a cured relief pattern formed of the photosensitive resin composition of any one of claims 1 to 11.