TW202338002A - resin composition - Google Patents

Abstract

A resin composition comprising at least one resin selected from the group consisting of polyimide, polybenzoethazole and these precursors, a compound represented by the following formula (A), and a solvent, [In formula (A), R _a represents a hydrogen atom, a hydroxyl group, a hydroxymethyl group, or an alkyl group having 1 to 30 carbon atoms; R _b represents an alkyl group having 1 to 30 carbon atoms; m represents an integer of 0 to 3 , n represents an integer from 1 to 4, and the maximum sum of m and n is 4].

Description

resin composition

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

In the past, polyimide resin and polybenzoconazole, which have excellent heat resistance, electrical properties, and mechanical properties, were used as insulating materials for electronic parts and passivation films, surface protective films, interlayer insulating films, etc. of semiconductor devices. Resin, etc. (refer to Patent Document 1).

When an insulating film or the like is formed from a resin composition containing a polyimide-based resin, if the insulating film or the like is formed on metal wiring (for example, copper wiring, copper alloy wiring, etc.), the adhesion may be reduced. Therefore, in order to suppress the decrease in adhesiveness, it has been proposed that the photosensitive polyimide-based resin composition contains triazole or a derivative thereof (Patent Document 2).

Furthermore, when an insulating film or the like is formed from a resin composition containing a polyimide-based resin, if the insulating film or the like is formed on metal wiring (for example, copper or copper alloy wiring), the metal wiring may be oxidized. Therefore, in order to suppress oxidation of metal wiring, it has been proposed to contain an antioxidant such as a phenol-based antioxidant in a polyimide resin composition (Patent Document 3). [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2012-194520 [Patent Document 2] Japanese Patent Application Publication No. 2005-010360 [Patent Document 3] Pamphlet International Publication No. 2015/020020

[Problem to be solved by the invention]

In recent years, semiconductor devices have required high-speed transmission and processing of large-capacity information, and therefore electronic signals have been increasing in frequency. High-frequency electronic signals are prone to attenuation, so it is necessary to reduce transmission losses. Therefore, resins used in semiconductor devices are required to have a low loss tangent.

Therefore, there is a need for a resin composition that can provide a film having excellent adhesion, excellent oxidation resistance, and low loss tangent on a substrate with metal wiring on the surface. However, the resin compositions described in Patent Documents 1 to 3 cannot satisfy all of these characteristics.

In view of the above situation, the object of the present invention is to provide a resin composition that can obtain a film having excellent adhesion, excellent oxidation resistance, and low loss tangent on a substrate with metal wiring on the surface. A resin film obtained from the composition, a photosensitive resist film using the resin composition, a method for manufacturing a substrate with a hardened relief pattern, and a semiconductor device. [Means used to solve problems]

The inventors of the present invention conducted intensive studies in order to achieve the above-mentioned subject, and as a result found that by making a resin composition containing polyimide and the like contain a compound represented by the following formula (A), a substrate capable of having metal wiring on the surface can be obtained As a result, a resin composition of a film having excellent adhesion, excellent oxidation resistance, and low loss tangent was obtained, leading to the completion of the present invention.

[1] A resin composition containing at least one resin selected from the group consisting of polyimide, polybenzoethazole and these precursors, a compound represented by the following formula (A), and a solvent , [chemistry 1] [In formula (A), R _a represents a hydrogen atom, a hydroxyl group, a hydroxymethyl group, or an alkyl group having 1 to 30 carbon atoms; R _b represents an alkyl group having 1 to 30 carbon atoms; m represents an integer of 0 to 3 , n represents an integer from 1 to 4, and the maximum sum of m and n is 4]. [2] The resin composition according to [1], wherein the resin is at least one resin selected from the group consisting of polyimide and its precursors. [3] The resin composition according to [1] or [2], wherein the resin is a polyamide having a structural unit represented by the following formula (1-a) and the following formula (1-b-1) Amine or a polyimide precursor having a structural unit represented by the following formula (3) and the following formula (1-b-2), [Chemical 2] [In formula (1-a) and formula (1-b-1), Ar ₁ represents a tetravalent organic group, and X ₁₁ represents a divalent organic group having a photopolymerizable group; Formula (3) and formula (1-b) In -2), Ar ₃ represents a tetravalent organic group, L ₁ and L ₂ each independently represent a univalent organic group, X ₁₂ represents a divalent organic group, and at least one of L ₁ , L ₂ and X ₁₂ is photopolymerizable base]. [4] The resin composition according to any one of [1] to [3], wherein the resin has a divalent organic group represented by the following formula (9-a), [Chemical 3] [In formula (9-a), V ₁ represents a direct bond, ether bond, ester bond, amide bond, urethane bond, or urea bond, W ₁ represents an oxygen atom or an NH group, and R ₁₅ represents a direct bond. An alkylene group with 2 to 6 carbon atoms that can be bonded or substituted by a hydroxyl group, R ₁₆ represents a hydrogen atom or a methyl group, and * represents a bond]. [5] The resin composition according to [4], wherein V ₁ in the formula (9-a) represents an ester bond, and W ₁ further represents an oxygen atom. [6] The resin composition according to [4] or [5], wherein R ₁₅ in the formula (9-a) represents 1,2-ethylidene group. [7] The resin composition according to any one of [1] to [6], wherein R _a in the formula (A) represents a hydrogen atom. [8] The resin composition according to any one of [1] to [7], wherein m in the formula (A) represents 0. [9] The resin composition according to any one of [1] to [8], wherein the compound represented by the formula (A) contains 1H-benzotriazole-5-carboxylic acid and 1H-benzotriazole -At least any one of 4-carboxylic acids. [10] The resin composition according to any one of [1] to [9], further comprising a photoradical polymerization initiator. [11] The resin composition according to any one of [1] to [10], further containing a crosslinking compound. [12] The resin composition according to any one of [1] to [11], which is used for forming an insulating film. [13] The resin composition according to any one of [1] to [12], which is a photosensitive resin composition. [14] The resin composition according to any one of [1] to [13], which is a negative photosensitive resin composition. [15] A resin film which is a fired product of a coating film of the resin composition according to any one of [1] to [14]. [16] The resin film according to [15], which is an insulating film. [17] A photosensitive resist film having a base film, a photosensitive resin layer formed of the resin composition according to [13] or [14], and a cover film. [18] A method of manufacturing a substrate with a hardened relief pattern, which includes: (1) Coating the resin composition as described in [13] or [14] on the substrate, and forming a photosensitive resin layer on the substrate Steps; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) heating the relief pattern to form a hardened relief pattern steps. [19] The method of manufacturing a substrate with a hardened relief pattern according to [18], wherein in the step (1), the resin composition is applied to the substrate having metal wiring on its surface. [20] The method of manufacturing a substrate with a hardened relief pattern as described in [18] or [19], wherein the developer used for the development is an organic solvent. [21] A substrate with a hardened relief pattern, which is produced by the method described in any one of [18] to [20]. [22] A semiconductor device including a semiconductor element and a cured film provided on an upper part or a lower part of the semiconductor element, wherein the cured film is made of any one of [1] to [14] A hardened film formed from a resin composition. [23] The semiconductor device according to [22], wherein the resin composition is a photosensitive resin composition, and the cured film is a cured relief pattern formed from the photosensitive resin composition. [Effects of the invention]

According to the present invention, it is possible to obtain a resin composition capable of obtaining a film having excellent adhesion, excellent oxidation resistance, and low loss tangent on a substrate having metal wiring on the surface, and a resin obtained from the resin composition. A film, a photosensitive resist film using the resin composition, a method for manufacturing a substrate with a hardened relief pattern, and a semiconductor device.

(resin composition) The resin composition of the present invention includes at least one resin selected from the group consisting of polyimide, polybenzoethazole and these precursors, a compound represented by formula (A), and a solvent.

＜Polyimide, etc.＞ The resin composition contains at least one resin selected from the group consisting of polyimide, polybenzoethazole and these precursors (hereinafter sometimes referred to as "polyimide, etc.").

From the viewpoint of imparting photosensitivity when using a resin composition as a photosensitive resin composition, polyimide and the like preferably have a photopolymerizable group, and more preferably have a polymerizable unsaturated group, and have ( A meth)acrylyl group is more preferred, and a divalent organic group represented by the following formula (9-a) is particularly preferred. [Chemical 4] [In formula (9-a), V ₁ represents direct bonding, ether bond (-O-), ester bond (-COO-), amide bond (-NHCO-), urethane bond (-NHCOO -), or urea bond (-NHCONH-), W ₁ represents an oxygen atom or an NH group, R ₁₅ represents a direct bond, or an alkylene group with 2 to 6 carbon atoms that can also be substituted by a hydroxyl group, R ₁₆ represents hydrogen Atom or methyl group, * indicates bonding bond].

＜＜Polyimide and its precursors＞＞ Examples of polyamide imide and its precursors include polyamide imide, polyamide acid, polyamide ester, and the like.

Examples of the polyimide include the following polyimide (1). Examples of the polyamide include the following polyamide (2). Examples of the polyamide ester include the following polyamide ester (3). Polyimide (1) is a polyimide having structural units represented by the following formula (1-a) and the following formula (1-b). Polyamic acid (2) is a polyamic acid having a structural unit represented by the following formula (2) and the following formula (1-b). The polyamic acid ester (3) is a polyamic acid ester having a structural unit represented by the following formula (3) and the following formula (1-b).

[Chemistry 5] [In formula (1-a), Ar ₁ represents a tetravalent organic group. In formula (1-b), X represents a divalent organic group].

[Chemical 6] [In formula (2), Ar ₂ represents a tetravalent organic group].

[Chemical 7] [In formula (3), Ar ₃ represents a tetravalent organic group, and L ₁ and L ₂ each independently represent a monovalent organic group].

An example of the polyimide is a polyimide having a structural unit represented by formula (1-a) and the following formula (1-b-1). An example of the polyimide precursor is a polyimide precursor having a structural unit represented by formula (3) and the following formula (1-b-2). However, in this polyimide precursor, at least one of L ₁ , L ₂ and X ₁₂ has a photopolymerizable group. [Chemical 8] [In formula (1-b-1), X ₁₁ represents a divalent organic group having a photopolymerizable group. In formula (1-b-2), X ₁₂ represents a divalent organic group].

<<< Ar ₁ , Ar ₂ , and Ar ₃ >> Ar ₁ , Ar ₂ , and Ar ₃ represent tetravalent organic groups. The tetravalent organic group is not particularly limited, and examples thereof include: a tetravalent organic group derived from aliphatic tetracarboxylic dianhydride, a tetravalent organic group derived from alicyclic tetracarboxylic dianhydride, and an aromatic tetravalent organic group. The 4-valent organic group of tetracarboxylic dianhydride, etc. As a tetravalent organic group, a tetravalent organic group having three or more aromatic rings is preferable from the viewpoint of obtaining a film having a lower loss tangent.

The number of aromatic rings included in Ar ₁ , Ar ₂ , and Ar ₃ is preferably 3 or more, and more preferably 4 or more, from the viewpoint that a film having a lower loss tangent can be obtained. 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 counting method of aromatic rings in "three or more aromatic rings", polycyclic aromatic ring systems formed by condensation of two or more aromatic rings such as naphthalene rings and anthracene rings are counted as one aromatic ring. . Therefore, the naphthalene ring system counts as 1 aromatic ring. On the other hand, since the biphenyl ring is not a condensed ring, it is counted as two aromatic rings. Furthermore, the perylene ring system counts as 2 aromatic rings. Examples of the aromatic ring include aromatic hydrocarbon rings, aromatic heterocyclic rings, and the like.

As Ar ₁ , Ar ₂ , and Ar ₃ , from the viewpoint of ideally obtaining the effects of the present invention, it is preferable to represent a tetravalent organic group represented by the following formula (4). [Chemical 9] [In formula (4), X ₁ and X ₂ independently represent direct bonding, ether bond (-O-), ester bond (-COO-), amide bond (-NHCO-), and urethane bond. (-NHCOO-), urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO ₂ -). R _a1 and R _a2 each independently represent an alkyl group having 1 to 6 carbon atoms that may be substituted. Z ₁ represents a divalent organic group represented by the following formula (5-a), the following formula (5-b), or the following formula (5-c). n1 and n2 independently represent integers from 0 to 3. When there are multiple R _a1's , the multiple R _a1's may be the same or different. When there are multiple R _a2's , the multiple R _a2's may be the same or different. * indicates bonding key].

Examples of the optionally substituted alkyl group having 1 to 6 carbon atoms in R _a1 and R _a2 in formula (4) include an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like. In this specification, an alkyl group or an alkylene group may be linear, branched, or cyclic, or a combination of two or more of these unless their structure is specifically mentioned. . Examples of the substituent in the alkyl group having 1 to 6 carbon atoms that may be substituted include a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, a cyano group, a formyl group, a haloformyl group, a sulfo group, and an amine. group, nitro group, nitroso group, lateral oxy group, lateral sulfide group, alkoxy group with 1 to 6 carbon atoms, etc. In addition, "carbon number 1 to 6" in "alkyl group having 1 to 6 carbon atoms which may be substituted" refers to the number of carbon atoms of the "alkyl group" excluding substituents. In addition, the number of substituents is not particularly limited.

[Chemical 10] [In formula (5-a), R ₃ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and m ₁ represents an alkyl group having 0 to 4 carbon atoms. integer. When m ₁ is 2 or more, R ₃ may be the same or different. In the formula (5-b), Z ₂ represents a direct bond, or a divalent organic group represented by the following formula (6-a) or the following formula (6-b), and R ₄ and R ₅ each independently represent carbon For an alkyl group having 1 to 6 atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, m ₂ and m ₃ each independently represent an integer of 0 to 4. When m ₂ is 2 or more, R ₄ may be the same or different. When m ₃ is 2 or more, R ₅ may be the same or different. In formula (5-c), R ₆ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and m ₄ represents an integer of 0 to 6. . When m ₄ is 2 or more, R ₆ may be the same or different. * indicates bonding key].

[Chemical 11] [In formula (6-a), R ₇ and R ₈ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms that may be substituted by a halogen atom. In formula (6-b), R ₉ and R ₁₀ each independently represent an alkylene group having 1 to 6 carbon atoms that may be substituted or an aryl group having 6 to 12 carbon atoms that may be substituted. * indicates bonding key].

From the viewpoint of ideally obtaining the effects of the present invention, Z ₁ is preferably a divalent organic group represented by the formula (5-b).

Examples of the alkyl group having 1 to 6 carbon atoms in R ₇ and R ₈ that may be substituted by a halogen atom include an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, etc. . Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like. Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenation in the halogenated alkyl group having 1 to 6 carbon atoms may be a part or all of it.

Examples of the substituent in the optionally substituted alkylene group having 1 to 6 carbon atoms in R ₉ and R ₁₀ include: halogen atom, hydroxyl group, mercapto group, carboxyl group, cyano group, formyl group, halogen group Formyl group, sulfo group, amino group, nitro group, nitroso group, lateral oxy group, lateral sulfide group, alkoxy group with 1 to 6 carbon atoms, etc. Examples of the alkylene group having 1 to 6 carbon atoms that may be substituted include an alkylene group having 1 to 6 carbon atoms, a halogenated alkylene group having 1 to 6 carbon atoms, and the like. Examples of the alkylene group having 1 to 6 carbon atoms include methylene, ethylene, propylene, butylene, and the like. In addition, the "carbon number 1 to 6" of 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 substituent. In addition, the number of substituents is not particularly limited.

Examples of the substituent in the optionally substituted aryl group having 6 to 10 carbon atoms in R ₉ and R ₁₀ include: a halogen atom, an optionally halogenated alkyl group having 1 to 6 carbon atoms, It may also be a halogenated alkoxy group having 1 to 6 carbon atoms, etc. In addition, halogenation may be part or all of it. Examples of the aryl group include phenylene group, naphthylene group, and the like. In addition, the "carbon number 6 to 10" of the "arylene group having 6 to 10 carbon atoms which may be substituted" refers to the number of carbon atoms of the "arylene group" excluding the substituent. In addition, the number of substituents is not particularly limited.

Examples of the divalent organic group represented by the formula (6-a) include divalent organic groups represented by the following formulas. [Chemical 12] In the formula, * represents the bonding bond.

Examples of the divalent organic group represented by the formula (6-b) include divalent organic groups represented by the following formulas. [Chemical 13] In the formula, R ₃₁ to R ₃₃ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms that may be substituted by a halogen atom, or an alkoxy group having 1 to 6 carbon atoms that may be substituted with a halogen atom. n31 represents an integer from 0 to 5. n32 and n33 independently represent integers from 0 to 4. When there are multiple R _31s , the multiple R _31s may be the same or different. When there are multiple R _32s , the multiple R _32s may be the same or different. When there are multiple R _33s , the multiple R _33s may be the same or different. *Indicates bonding key.

Specific examples of the alkyl group having 1 to 6 carbon atoms that can be substituted by a halogen atom in R ₃₁ to R ₃₃ include, for example, an alkyl group having 1 to 6 carbon atoms, and a halogenated group having 1 to 6 carbon atoms. alkyl. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like. Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenation in the halogenated alkyl group having 1 to 6 carbon atoms may be a part or all of it. Specific examples of the alkoxy group having 1 to 6 carbon atoms that can also be substituted by a halogen atom in R ₃₁ to R ₃₃ include: an alkyl group with 1 to 6 carbon atoms that can also be substituted with a halogen atom. It is an alkoxy group.

Examples of Ar ₁ , Ar ₂ , and Ar ₃ include tetravalent organic groups represented by the following formulas. [Chemical 14] [Chemical 15] In the formula, * represents the bonding bond.

Furthermore, Ar ₁ , Ar ₂ , and Ar ₃ may be, for example, a tetravalent organic group represented by the following formula. [Chemical 16] [Chemical 17] In the formula, * represents the bonding bond.

＜＜＜X, X ₁₁ , and X ₁₂ ＞＞＞X represents a divalent organic group. X represents, for example, a divalent aromatic group having a photopolymerizable group. X ₁₁ represents a divalent organic group having a photopolymerizable group. X ₁₁ represents, for example, a divalent aromatic group having a photopolymerizable group. X ₁₂ represents a divalent organic group. X ₁₂ has, for example, a photopolymerizable group. X ₁₂ represents, for example, a divalent organic group having a photopolymerizable group. X ₁₂ represents, for example, a divalent aromatic group having a photopolymerizable group.

Examples of the photopolymerizable group include radical polymerizable groups, cationic polymerizable groups, and anionic polymerizable groups. Among these, radically polymerizable groups are preferred. Examples of the radically polymerizable group include an acrylic group, a methacrylic group, an acryl ether group, a vinyl ether group, a vinyl group, and the like.

Examples of the aromatic ring in the divalent aromatic group having a photopolymerizable group include a benzene ring, a naphthalene ring, an anthracene ring, and the like.

The divalent aromatic group having a photopolymerizable group is, for example, a residue obtained by removing two amine groups from an aromatic diamine compound having a photopolymerizable group.

As the divalent aromatic group having a photopolymerizable group, a divalent organic group represented by the following formula (9-a) is preferred. [Chemical 18] [In formula (9-a), V ₁ represents direct bonding, ether bond (-O-), ester bond (-COO-), amide bond (-NHCO-), urethane bond (-NHCOO -), or urea bond (-NHCONH-), W ₁ represents an oxygen atom or an NH group, R ₁₅ represents a direct bond, or an alkylene group with 2 to 6 carbon atoms that can also be substituted by a hydroxyl group, R ₁₆ represents hydrogen Atom or methyl group, * indicates bonding bond].

The two bonds in formula (9-a) are, for example, bonds bonded to nitrogen atoms.

In this specification, examples of the alkylene group having 2 to 6 carbon atoms that may be substituted by a hydroxyl group include: 1,1-ethylene group, 1,2-ethylene group, and 1,2-propylene group. , 1,3-propylene, 1,4-butylene, 1,2-butylene, 2,3-butylene, 1,2-pentylene, 2,4-pentylene, 1 ,2-Hexylene, 1,2-cyclopropyl, 1,2-cyclobutyl, 1,3-cyclobutyl, 1,2-cyclopentyl, 1,2-cyclohexyl, Alkylene groups in which at least part of the hydrogen atoms are substituted by hydroxyl groups (for example: 2-hydroxy-1,3-propylene group), etc.

V ₁ preferably represents an ester bond (-COO-). W ₁ preferably represents an oxygen atom. R ₁₅ preferably represents 1,2-ethylidene group.

Examples of the divalent organic group represented by formula (9-a) include divalent organic groups represented by the following formulas. [Chemical 19] In the formula, * represents the bonding bond. The two bonding bonds are, for example, located in meta position with respect to the substituent having a photopolymerizable group.

From the viewpoint of obtaining a film with a lower loss tangent, it is preferable that X and X ₁₂ represent a divalent organic group having three or more aromatic rings. The divalent organic group having three or more aromatic rings here refers to an organic group different from the divalent aromatic group having the above-mentioned photopolymerizable group.

The divalent organic group having three or more aromatic rings is, for example, a residue obtained by removing two amine groups from an aromatic diamine compound having three or more aromatic rings.

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

The 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). [Chemistry 20] [In formula (13), X ₂₁ and X ₂₂ independently represent direct bonding, ether bond (-O-), ester bond (-COO-), amide bond (-NHCO-), and urethane bond. (-NHCOO-), urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO ₂ -). R ₂₁ and R ₂₂ each independently represent an alkyl group having 1 to 6 carbon atoms which may be substituted. Y ₂₀ represents a divalent organic group represented by the above formula (5-a), the above formula (5-b) or the above formula (5-c). n21 and n22 independently represent integers from 0 to 4. When there are multiple R _21s , the multiple R _21s may be the same or different. When there are multiple R _22s , the multiple R _22s may be the same or different. * indicates bonding key].

Examples of the optionally substituted alkyl group having 1 to 6 carbon atoms in R ₂₁ and R ₂₂ in formula (13) include an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like. In this specification, an alkyl group or an alkylene group may be linear, branched, or cyclic, or a combination of two or more of these unless their structure is specifically mentioned. . Examples of the substituent in the alkyl group having 1 to 6 carbon atoms that may be substituted include a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, a cyano group, a formyl group, a haloformyl group, a sulfo group, and an amine. group, nitro group, nitroso group, lateral oxy group, lateral sulfide group, alkoxy group with 1 to 6 carbon atoms, etc. In addition, "carbon number 1 to 6" in "alkyl group having 1 to 6 carbon atoms which may be substituted" refers to the number of carbon atoms of the "alkyl group" excluding substituents. In addition, the number of substituents is not particularly limited.

Examples of the divalent organic group having three or more aromatic rings include divalent organic groups represented by the following formulas. [Chemistry 21] [Chemistry 22] In the formula, * represents the bonding bond.

Examples of other divalent organic groups include divalent organic groups represented by the following formulas. Such divalent organic groups are, for example, residues obtained by removing two amine groups from diamine. [Chemistry 23] In the formula, * represents the bonding bond.

＜＜＜ L ₁ and L ₂ ＞＞＞ L ₁ and L ₂ each independently represent a monovalent organic group. Examples of the monovalent organic group include an alkyl group having 1 to 30 carbon atoms. Examples of the alkyl group having 1 to 30 carbon atoms include a linear alkyl group, a branched chain alkyl group, an alicyclic alkyl group, and the like. Examples of the linear alkyl group having 1 to 30 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, amyl, hexyl, heptyl, octyl, nonyl, and decyl. Base, undecyl, dodecayl (lauryl), thirteenth base, tetradecyl (myristyl), 15th base, hexadecyl (palmyl), seventeenth base (heptadecyl, margaryl), 18th base Base (stearyl), nineteen base, twenty base (peanut base), twenty one base, twenty two base (docosyl, behenyl), twenty three base, twenty four base (tetracosyl, lignoceryl), two Fifteen bases, twenty-six bases, twenty-seven bases, etc. Examples of the branched chain alkyl group having 1 to 30 carbon atoms include: isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, Secondary isopentyl, isohexyl, neohexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2- Ethylpentyl, heptan-3-yl, heptan-4-yl, 4-methylhexan-2-yl, 3-methylhexan-3-yl, 2,3-dimethylpentane -2-yl, 2,4-dimethylpentan-2-yl, 4,4-dimethylpentan-2-yl, 6-methylheptyl, 2-ethylhexyl, octane-2 -yl, 6-methylheptan-2-yl, 6-methyloctyl, 3,5,5-trimethylhexyl, nonan-4-yl, 2,6-dimethylheptan-3 -yl, 3,6-dimethylheptan-3-yl, 3-ethylheptan-3-yl, 3,7-dimethyloctyl, 8-methylnonyl, 3-methylnonyl Alk-3-yl, 4-ethyloctan-4-yl, 9-methyldecyl, undecyl-5-yl, 3-ethylnonan-3-yl, 5-ethylnonan- 5-yl, 2,2,4,5,5-pentamethylhexan-4-yl, 10-methylundecyl, 11-methyldodecanyl, tridecane-6-yl, tridecyl Alk-7-yl, 7-ethyl undecyl-2-yl, 3-ethyl undecyl-3-yl, 5-ethyl undecyl-5-yl, 12-methyltridecyl, 13-methyltetradecanyl, pentadecyl-7-yl, pentadecyl-8-yl, 14-methylpentadecanyl, 15-methylhexadecanyl, heptadecan-8-yl, heptadecanyl Alk-9-yl, 3,13-dimethylpentadecan-7-yl, 2,2,4,8,10,10-hexamethylundecan-5-yl, 16-methylheptadecan-yl base, 17-methyloctadecyl, nonadecan-9-yl, nonadecan-10-yl, 2,6,10,14-tetramethylpentadecan-7-yl, 18-methyldecanoyl Nonayl, 19-methyleicosanyl, hecosan-10-yl, 20-methyleicosanyl, 21-methyleicosanyl, triicosan-11-yl, 22-methyl Tricosyl tricosyl, 23-methyl tetracosyl, pentacos-12-yl, pentacos-13-yl, 2,22-dimethylcos-11-yl, 3 , 21-dimethyltricocanos-11-yl, 9,15-dimethyltricocanosyl-11-yl, 24-methylpentacontanoyl, 25-methylpentacontanoyl, di Heptadecan-13-yl, etc. Examples of the alicyclic alkyl group having 1 to 30 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-tertiary butylcyclohexyl, and 1,6-dimethylcyclohexyl. Hexyl, menthyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptan-2-yl, camphenyl, isobornyl, 1-adamantyl, 2-adamantyl, tricyclo[5.2. 1.0 ^2,6 ]decan-4-yl, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl, cyclododecyl, etc.

Moreover, _L1 and _L2 may have a photopolymerizable group. That is, L ₁ and L ₂ may be a monovalent organic group having a photopolymerizable group. Examples of the photopolymerizable group include radical polymerizable groups, cationic polymerizable groups, and anionic polymerizable groups. Among these, radically polymerizable groups are preferred. Examples of the radically polymerizable group include an acrylic group, a methacrylic group, an acryl ether group, a vinyl ether group, a vinyl group, and the like.

As the monovalent organic group having a photopolymerizable group, a monovalent organic group represented by the following formula (9-b) is preferred. [Chemistry 24] [In formula (9-b), W ₂ represents an oxygen atom or an NH group, R ₁₇ represents an alkylene group having 2 to 6 carbon atoms that is directly bonded or may be substituted by a hydroxyl group, and R ₁₈ represents a hydrogen atom or a methyl group. base, * indicates bonding bond].

W ₂ preferably represents an oxygen atom. R ₁₇ preferably represents 1,2-ethylidene group.

The polyamide (1) is, for example, an amide imide of polyamide acid which is a reaction product of a diamine component and a tetracarboxylic acid derivative. The imidization rate of polyimide (1) does not need to be 100%. The imidization rate of the polyimide (1) may be, for example, 90% or more, 95% or more, or 98% or more.

The polyamide (2) is, for example, a reaction product of a diamine component and a tetracarboxylic acid derivative. The polyamide ester (3) is, for example, a reaction product of a diamine component and a tetracarboxylic acid diester.

Here, examples of tetracarboxylic acid derivatives include tetracarboxylic acid, tetracarboxylic acid diester, tetracarboxylic acid dihalide, tetracarboxylic acid dianhydride, and the like.

＜＜Production method of polyimide and its precursor＞＞ The method for producing polyamide and its precursor is not particularly limited. Examples thereof include reacting a diamine component with a tetracarboxylic acid derivative to obtain polyamide, polyamide ester, or polyimide. well-known method. Polyamic acid, polyamic acid ester, and polyimide can be synthesized by a well-known method as described in WO2013/157586, for example.

Polyamic acid or polyamic acid ester is produced, for example, by reacting a diamine component and a tetracarboxylic acid derivative in a solvent (condensation polymerization).

Specific examples of the solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N ,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutylamide, dimethylstyrene, 1,3-dimethyl-2-imidazole ketinone. 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 formula [D -1]~solvent represented by formula [D-3]. [Chemical 25] (In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms. In formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms. In formula [D-3] , D ³ represents an alkyl group having 1 to 4 carbon atoms).

These solvents can be used individually or mixed. In addition, even if it is a solvent which does not dissolve polyamic acid, it can also be used by mixing with the said solvent in the range which polyamic acid or polyamic acid ester does not precipitate.

When the diamine component and the tetracarboxylic acid derivative are reacted in the solvent, the reaction can be carried out at any concentration, but it is preferably 1 to 50 mass%, and more preferably 5 to 30 mass%. The reaction is carried out at a high concentration in the initial stage, and thereafter, the solvent may be added. In the reaction, the ratio of the total molar number of the diamine components to the total molar number of the tetracarboxylic acid derivatives is preferably 0.8 to 1.2. As in a normal condensation polymerization reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamide acid produced becomes.

When the diamine component and the tetracarboxylic acid derivative are reacted, a thermal polymerization inhibitor may be added to the reaction system in order to avoid polymerization of the photopolymerizable group. Examples of thermal polymerization inhibitors include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tertiary butylcatechol, phenthiamine, and N-phenylnaphthylamine. , ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di(tertiary 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-phenylhydroxylammonium ammonium salt, N-nitroso-N(1-naphthyl)hydroxylammonium ammonium salt, etc. The usage amount of the thermal polymerization inhibitor is not particularly limited.

Polyimide is obtained by dehydrating and ring-closing the polyamide acid obtained by the above reaction. Methods for obtaining polyimide include thermal imidization by heating the polyamide acid solution obtained by the above reaction, or chemical imidization by adding a catalyst to the polyamide acid solution. When thermally imidizing the solution in a solution, the temperature is 100°C to 400°C, preferably 120°C to 250°C, and the water generated by the imidization reaction is removed from the system. For better.

The above-mentioned chemical imidization can be performed by adding an alkaline catalyst and an acid anhydride to the polyamide acid solution obtained by the reaction, and stirring at -20°C to 250°C, preferably 0°C to 180°C. The amount of the alkaline catalyst is 0.1 mole times to 30 mole times of the amide acid group, preferably 0.2 mole times to 20 mole times, and the amount of the acid anhydride is 1 mole times to 50 mole times of the amide acid group. molar times, preferably 1.5 molar times to 30 molar times. Examples of the alkaline catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, triethylamine is preferred because it is less likely to produce polyisoamide as a by-product. Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is preferred because purification after completion of the reaction becomes easy. The imidization rate achieved by chemical imidization (the ratio of closed repeating units relative to all repeating units possessed by the polyimide precursor, also known as the ring-closing rate) can be adjusted by adjusting the catalyst The amount, reaction temperature and reaction time are controlled.

When recovering the generated imide from the reaction solution of the above-mentioned imidization, it is only necessary to put the reaction solution into a solvent and allow it to precipitate. Examples of solvents used for precipitation include: methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl siloxane, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. wait. The polymer precipitated after being put into the solvent can be filtered and recovered, and then dried under normal pressure or reduced pressure, at normal temperature or by heating.

Polyimide and its precursors can also be end-capped. The capping method is not particularly limited, and for example, a conventionally known method using a monoamine or an acid anhydride can be used.

＜＜Polybenzoethazole and its precursors＞＞ The polybenzoethazole is not particularly limited as long as it is a polymer containing benzoethazole in the repeating unit, and it may be a copolymer having other repeating units. Polybenzoethazole can be obtained, for example, by dehydration and ring-closure of a dicarboxylic acid and a bisaminophenol compound as a diamine using polyphosphoric acid. In addition, polybenzoethazole can be obtained by dehydrating and ring-closing polyhydroxyamide through reaction using heating or phosphoric anhydride, an alkali or a carbodiimide compound, for example.

The polybenzoethazole precursor is not particularly limited as long as it is a polymer containing a structural unit providing a benzoethazole unit, and it may also be a copolymer having other repeating units. The polybenzoconazole precursor can be obtained, for example, by reacting a dicarboxylic acid, a corresponding dicarboxylic acid dichloride or a dicarboxylic acid active diester, and a bisaminophenol compound as a diamine. Examples of the polybenzoethazole precursor include polyhydroxyamide.

When the resin composition is a photosensitive resin composition, the polybenzoethazole and its precursor preferably have polymerizable unsaturated groups. Examples of the polymerizable unsaturated group include (meth)acrylyl group.

The weight average molecular weight of polyimide, etc. is not particularly limited, but the weight average molecular weight is measured by gel permeation chromatography (hereinafter referred to as GPC in this specification) using polyethylene oxide conversion. 5,000 to 100,000 is preferred, 7,000 to 50,000 is more preferred, 10,000 to 50,000 is further preferred, and 10,000 to 40,000 is particularly preferred.

<Compound represented by formula (A)> The resin composition contains a compound represented by the following formula (A). By including a compound represented by formula (A) in a resin composition containing polyimide, etc., it is possible to achieve both excellent adhesion, excellent oxidation resistance, and low loss tangent on a substrate with metal wiring on the surface. membrane.

The present inventors conducted intensive research in order to obtain a resin composition that can provide a film having excellent adhesion, excellent oxidation resistance, and low loss tangent on a substrate with metal wiring on the surface. Among them, triazole compounds (for example: 5-methyl-1H-benzotriazole, etc.), phenol antioxidants (for example: IRGANOX [registered trademark] 3114, etc.), and silane coupling agents (for example: KBM-5103, etc.) are used ), trisulfide series metal ion scavengers (for example: 2,4-diamino-6-butylamino-1,3,5-trissaccharide, 2,4-diamino-6-diallyl Various additives such as amino-1,3,5-trisulfan, 6-(dibutylamino)-1,3,5-tris-2,4-dithiol, etc. were studied, and it was found that By using the compound represented by formula (A), a resin composition can be obtained that can provide a film having excellent adhesion, excellent oxidation resistance, and low loss tangent on a substrate having metal wiring on the surface. [Chemical 26] [In formula (A), R _a represents a hydrogen atom, a hydroxyl group, a hydroxymethyl group, or an alkyl group having 1 to 30 carbon atoms. R _b represents an alkyl group having 1 to 30 carbon atoms. m represents an integer from 0 to 3, n represents an integer from 1 to 4, and the maximum sum of m and n is 4].

As the alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 1 to 6 carbon atoms is particularly preferred. good.

Examples of the alkyl group having 1 to 30 carbon atoms include a linear alkyl group, a branched alkyl group, and a cyclic alkyl group. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecanyl. , fourteen bases, fifteen bases, sixteen bases, seventeen bases, eighteen bases, nineteen bases, twenty bases, twenty-one bases, twenty-two bases, etc. Examples of the branched alkyl group include isopropyl, isobutyl, isopentyl, isohexyl, 2-ethylhexyl, 3-ethylheptyl, 2-ethyloctyl, and 3-ethyldecyl. base, 2-hexyldecanyl, 2-hexyldecyl, 2-octyldecanyl, 2-octyldodecyl, 2-decyldodecyl, 2-decyltetradecanyl, 2-decyl Hexadecyl, 3-hexyldecanyl, 3-octyldecanyl, 3-octyldecanyl, 3-decyltetradecanyl, 3-decylhexadecyl, 4-hexyldecanyl, 4-octyl Basedecyl, 4-octyldodecyl, 4-decyltetradecyl, 4-decylhexadecyl, 4-cyclohexylbutyl, 8-cyclohexyloctyl, etc. Examples of the cyclic alkyl group include cyclopentyl, cyclohexyl, cycloheptyl, 3-decylcyclopentyl, 4-decylcyclohexyl, and the like.

The compound represented by Formula (A) can be used individually by 1 type or in combination of 2 or more types.

R _a is preferably a hydrogen atom. m is preferably 0. n is preferably 1.

As the compound represented by the formula (A), 1H-benzotriazole-5-carboxylic acid (5-carboxybenzotriazole), 1H-benzotriazole-4-carboxylic acid (4-carboxybenzotriazole) Azoles), and combinations thereof are preferred.

The compound represented by formula (A) may also be a commercial product. Examples of commercially available products include CBT-5 and CBT-SG manufactured by Johoku Chemical Industry Co., Ltd., and VERZONE [registered trademark] C-BTA manufactured by Daiwa Kasei Co., Ltd., etc.

The content of the compound represented by formula (A) in the resin composition is not particularly limited, but from the viewpoint of ideally obtaining the effects of the present invention, 0.1 mass parts per 100 mass parts of polyimide, etc. Parts by mass to 20 parts by mass are preferred, 0.3 parts by mass to 10 parts by mass are more preferred, and parts by mass 0.5 to 5 parts by mass are particularly preferred.

<Solvent> As the solvent contained in the resin composition, from the viewpoint of solubility in polyimide and the like, it is preferable to use an organic solvent. Specifically, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylpropylamine, N,N-dimethylisobutyrylamide, dimethyltrisoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone , α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolone, N-cyclohexyl-2-pyrrolidinone, propylene glycol monomethyl ether acetate, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methyl 2-hydroxyisobutyrate, ethyl lactate or the following formulas [D-1] to formulas [D-3] solvents, etc., which can be used alone or in combination of two or more. [Chemical 27] (In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms. In formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms. In formula [D-3] , D ³ represents an alkyl group having 1 to 4 carbon atoms).

Depending on the desired coating film thickness and viscosity of the resin composition, the solvent may be in the range of, for example, 30 parts by mass to 1,500 parts by mass, preferably 100 parts by mass to 1,000 parts by mass relative to 100 parts by mass of polyimide or the like. Use the range of parts by mass.

＜Other ingredients＞ In an embodiment, the resin composition may further contain components other than polyimide, a compound represented by formula (A), and a solvent. Examples of other components include: photoradical polymerization initiator (also referred to as "photoradical initiator"), crosslinking compound (also referred to as "crosslinking agent"), thermosetting agent, and other resins Ingredients, fillers, sensitizers, adhesion aids, thermal polymerization inhibitors, azole compounds, hindered phenol compounds, etc.

＜＜Photoradical polymerization initiator＞＞ When using a resin composition as the photosensitive resin composition, the resin composition may contain a photoradical polymerization initiator, for example. The photoradical polymerization initiator is not particularly limited as long as it is a compound that absorbs the light source used for photocuring. Examples thereof include: tertiary butyl peroxyisobutyrate, 2,5-dimethyl -2,5-bis(benzyldioxy)hexane, 1,4-bis[α-(tertiary butyldioxy)isopropoxy]benzene, bis(tertiary butyl)peroxide Oxide, 2,5-dimethyl-2,5-bis(tertiary butyldioxy)hexene hydroperoxide, α-(isopropylphenyl)isopropyl hydroperoxide, tris Grade butyl hydroperoxide, 1,1-bis(tertiary butyldioxy)-3,3,5-trimethylcyclohexane, 4,4-bis(tertiary butyldioxy) Butyl valerate, cyclohexanone peroxide, 2,2',5,5'-tetrakis(tertiary butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetrakis( Tertiary butylperoxycarbonyl) benzophenone, 3,3',4,4'-tetrakis (tertiary pentylperoxycarbonyl) benzophenone, 3,3',4,4'- Tetrakis(tertiary hexylperoxycarbonyl)benzophenone, 3,3'-bis(tertiary butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, peroxybenzoic acid tertiary Butyl ester, diperoxyisophthalate di(tertiary butyl) and other organic peroxides; 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, 1, Quinones such as 2-phenythraquinone; benzoin derivatives such as benzoin methyl ether, benzoin ethyl ether, α-methyl benzoin, α-phenyl benzoin; 2,2-dimethoxy-1,2-diphenylethyl- 1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl] -2-Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propyl)benzyl}-phenyl ]-2-Methyl-propan-1-one, methyl phenylglyoxylate, 2-methyl-1-[4-(methylthio)phenyl]-2-N-𠰌linylpropan- 1-ketone, 2-benzyl-2-dimethylamino-1-(4-N-𠰌linylphenyl)-1-butanone, 2-dimethylamino-2-(4-methyl Alkyl benzyl)-1-(4-𠰌lin-4-yl-phenyl)-butan-1-one and other alkylphenone compounds; bis(2,4,6-trimethylbenzyl) -Phenyl phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and other phenylsulfine oxide compounds; 2-(O-benzoyl oxime)-1-[4 -(Phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H -Oxime ester compounds such as carbazol-3-yl]ethanone.

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

The content of the photoradical polymerization initiator is not particularly limited, but is preferably 0.1 to 20 parts by mass based on 100 parts by mass of polyimide, etc., and from the viewpoint of photosensitivity characteristics, 0.5 Parts by mass to 15 parts by mass are more preferred. When 0.1 parts by mass or more of the photoradical polymerization initiator is contained relative to 100 parts by mass of polyimide or the like, it is easy to improve the photosensitivity of the resin composition. On the other hand, when 20 parts by mass or less is contained, it is easy to Improve the thick film hardening properties of resin compositions.

＜＜Crosslinking compound＞＞ In an embodiment, when a resin composition is used as the photosensitive resin composition, in order to improve the resolution of the relief pattern, a monomer (crosslinking compound) having a photoradically polymerizable unsaturated bond may be used. Optionally contained in the resin composition. As such a crosslinking compound, a compound containing a polymerizable group that undergoes a radical polymerization reaction by a photoradical polymerization initiator is preferred, and examples thereof include (meth)acrylic compounds and maleimides. compounds, but are not particularly limited to the following. Examples of (meth)acrylic compounds include diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol or polyethylene glycol mono- or di(meth)acrylate. Acrylate, mono- or di(meth)acrylate of propylene glycol or polypropylene glycol, mono-, di- or tri(meth)acrylate of glycerol, di(meth)acrylate of 1,4-butanediol, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl Diol di(meth)acrylate, cyclohexane di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate , Dimethanediol di(meth)acrylate, bisphenol A mono- or di(meth)acrylate, bisphenol F di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate ) acrylate, benzenetrimethacrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]benzobis(meth)acrylate, benzene(2-hydroxyethyl)isotrisacrylate Polycyanate bis(meth)acrylate, isocamphenyl (meth)acrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane tri(meth)acrylic acid Esters, di- or tri-(meth)acrylate of glycerol, di-, tri-, or tetra-(meth)acrylate of neopentyl erythritol, and ethylene oxide or propylene oxide adducts of these compounds and other compounds, 2-isocyanate ethyl (meth)acrylate or isocyanate-containing (meth)acrylate, and methyl ethyl ketoxime, ε-caprolactam, γ-caprolactam added to these Compounds of end-capping agents such as amide, 3,5-dimethylpyrazole, diethyl malonate, ethanol, isopropyl alcohol, n-butanol, 1-methoxy-2-propanol, etc. Examples of the maleimide compound include 1,2-bis(maleimide)ethane, 1,4-bis(maleimide)butane, and 1,6-bis(maleimide)butane. Leimide)hexane, N,N'-1,4-phenylene dimaleimide, N,N'-1,3-phenylene dimaleimide, 4,4' -Bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(2-maleimideethyl)disulfide Ether, 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, 1,6'-bismaleimide-(2,2,4-trimethyl) Hexane etc. Examples of commercially available maleimide compounds include BMI-689, BMI-1500, BMI-1700, and BMI-3000 (manufactured by Designer Molecules Inc.). In addition, these compounds may be used individually or in combination of 2 or more types. In addition, in this specification, (meth)acrylate means acrylate and methacrylate.

The content of the crosslinking compound is not particularly limited, but is preferably 1 to 100 parts by mass, and more preferably 1 to 50 parts by mass relative to 100 parts by mass of polyimide or the like.

＜＜Thermal hardener＞＞ Examples of the thermal hardener include: hexamethoxymethylmelamine, tetramethoxymethylacetyleneurea, tetramethoxymethylbenzoguanamine, 1,3,4,6-methoxymethyl base) acetylene urea, 1,3,4,6-fourth (butoxymethyl) acetylene urea, 1,3,4,6-fourth (hydroxymethyl) acetylene urea, 1,3-bis(hydroxymethyl) ) urea, 1,1,3,3-fourth (butoxymethyl) urea and 1,1,3,3-fourth (methoxymethyl) urea, etc. The content of the thermosetting agent in the resin composition is not particularly limited.

＜＜Padding＞＞ Examples of the filler include inorganic fillers, and specific examples include sol of silica, aluminum nitride, boron nitride, zirconium dioxide, alumina, and the like. The content of the filler in the resin composition is not particularly limited.

＜＜Other resin ingredients＞＞ In an embodiment, the resin composition may further contain resin components other than polyimide and the like. Examples of the resin component that may be contained in the resin composition include polyethylene, polyethazole precursor, phenolic resin, polyamide, epoxy resin, siloxane resin, acrylic resin, and the like. The content of these resin components is not particularly limited, but is preferably in the range of 0.01 to 20 parts by mass relative to 100 parts by mass of polyimide or the like.

＜＜sensitizer＞＞ In an embodiment, when a resin composition is used as the photosensitive resin composition, a sensitizer may be optionally blended in the resin composition in order to improve the photosensitivity. Examples of the sensitizer include Michelone, 4,4'-bis(diethylamino)benzophenone, and 2,5-bis(4'-diethylaminobenzylidene) Cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone Hexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylenedihydrogen Indanone, p-dimethylaminophenylideneindanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylidene base) benzothiazole, 2-(p-dimethylaminophenylvinylidene)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis( 4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethyl Aminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine , N-phenylethanolamine, 4-N-𠰌linyl benzophenone, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1- Phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)benzothiazole , 2-(p-dimethylaminostyryl)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, etc. These can be used individually or in combination.

The content of the sensitizer is not particularly limited, but is preferably 0.1 to 25 parts by mass based on 100 parts by mass of polyimide or the like.

＜＜Adhesion aids＞＞ In an implementation form, in order to further improve the adhesion between the film formed using the resin composition and the base material, an adhesion aid can be optionally blended into the resin composition. Examples of adhesion aids include: γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-cyclohexane Oxypropoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-(meth)acryloxypropyldimethoxymethylsilane, 3-(meth)acryloxypropyldimethoxymethylsilane Methylacryloxypropyltrimethoxysilane, dimethoxymethyl-3-N-hexahydropyridylpropylsilane, diethoxy-3-epoxypropoxypropylmethylsilane , N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamide, benzophenone -3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-tris Silanes such as ethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, and N-phenylaminopropyltrimethoxysilane Coupling agents, and aluminum-based adhesive additives such as aluminum ethyl acetate acetate, aluminum ethyl acetate acetate, and aluminum ethylacetoacetate diisopropylate.

Among these adhesion aids, from the perspective of adhesion strength, it is better to use a silane coupling agent.

The content of the adhesion aid is not particularly limited, but it is preferably in the range of 0.5 to 25 parts by mass based on 100 parts by mass of polyimide or the like.

＜＜Thermal polymerization inhibitor＞＞ In an embodiment, a thermal polymerization inhibitor can be arbitrarily blended in order to improve the stability of the resin composition during storage in a solution containing a solvent and the viscosity and photosensitivity thereof. Examples of thermal polymerization inhibitors that can be used include: hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tertiary butylcatechol, phenylnaphthylamine, and N-phenylnaphthylamine. , ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di(tertiary 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-phenylhydroxylammonium ammonium salt, N-nitroso-N(1-naphthyl)hydroxylammonium ammonium salt, etc.

The content of the thermal polymerization inhibitor is not particularly limited, but is preferably in the range of 0.005 to 12 parts by mass based on 100 parts by mass of polyimide or the like.

＜＜Azole compounds＞＞ For example, when a substrate made of copper or a copper alloy is used, an azole compound may be optionally blended with the resin composition in order to further suppress oxidation of the substrate. The azole compound here refers to a compound different from the compound represented by formula (A). 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-tertiary butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5- Phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-bis Ethyl-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(tertiary butyl)-2-hydroxyphenyl)benzotriazole, 2-(3-tertiary butyl) Base-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-bis(tertiary pentyl)-2-hydroxyphenyl)benzotriazole, 2-(2' -Hydroxy-5'-tertiary octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H- Benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. . Particularly preferred ones include tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Moreover, these azole compounds may be used 1 type or in mixture of 2 or more types.

The content of the azole compound is not particularly limited, but it is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of polyamide imide, etc., in view of the light sensitivity when the resin composition is used as the photosensitive resin composition. From the viewpoint of properties, 0.5 parts by mass to 5 parts by mass is more preferred. When the content of the azole compound relative to 100 parts by mass of polyimide or the like is 0.1 part by mass or more, when the resin composition is formed on copper or copper alloy, the discoloration of the surface of copper or copper alloy is further suppressed. On the other hand, When it is 20 parts by mass or less, the photosensitivity is excellent when the resin composition is used as the photosensitive resin composition, which is preferable.

＜＜Hindered phenol compounds＞＞ In an embodiment, a hindered phenol compound may be optionally blended with the resin composition for the purpose of antioxidant of the thin film formed from the resin composition and the antioxidant of the azole compound. Examples of hindered phenol compounds include 2,6-bis(tertiary butyl)-4-methylphenol, 2,5-bis(tertiary butyl)-hydroquinone, 3-(3,5-di (Tertiary butyl)-4-hydroxyphenyl)octadecylpropionate, 3-(3,5-di(tertiary butyl)-4-hydroxyphenyl)isooctylpropionate, 4, 4'-methylene bis(2,6-bis(tertiary butyl)phenol), 4,4'-thio-bis(3-methyl-6-tertiary butylphenol), 4,4' -Butylene-bis(3-methyl-6-tertiary butylphenol), triethylene glycol-bis[3-(3-tertiary butyl-5-methyl-4-hydroxyphenyl)propionic acid ester], 1,6-hexanediol-bis[3-(3,5-di(tertiary butyl)-4-hydroxyphenyl)propionate], 2,2-thio-diethylenediol Bis[3-(3,5-bis(tertiary butyl)-4-hydroxyphenyl)propionate], N,N'hexamethylene bis(3,5-di(tertiary butyl)- 4-hydroxy-hydrocinamide), 2,2'-methylene-bis(4-methyl-6-tertiary butylphenol), 2,2'-methylene-bis(4-ethyl -6-tertiary butylphenol), neopentylerythritol-4 [3-(3,5-bis(tertiary butyl)-4-hydroxyphenyl)propionate], ginseng-(3,5- Bis(tertiary butyl)-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-bis(tertiary butyl)- )-4-Hydroxybenzyl)benzene, 1,3,5-shen(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tribenzyl-2, 4,6-(1H,3H,5H)-trione, 1,3,5-shen(4-tertiary butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5 -Tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-shen(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-tristrione-2,4,6-(1H,3H,5H)-trione, 1,3,5-shen[4-(1-ethylpropyl)-3-hydroxy- 2,6-Dimethylbenzyl]-1,3,5-tristrione-2,4,6-(1H,3H,5H)-trione, 1,3,5-shen[4-triethyl Methyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5- Ginseng(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1, 3,5-Shen(4-tertiarybutyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-trimethylbenzyl-2,4,6-(1H,3H, 5H)-triketone, 1,3,5-triketone (4-tertiary butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-trimethylbenzyl- 2,4,6-(1H,3H,5H)-trione, 1,3,5-shen(4-tertiary butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1 ,3,5-tri-butyl-2,4,6-(1H,3H,5H)-trione, 1,3,5-tributyl-6-ethyl-3-hydroxy-2 ,5-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-shen(4-tertiary butyl -5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3 ,5-Shen(4-tertiary butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-Shen(4-tertiarybutyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-trihydroxy-2,4,6-(1H,3H, 5H)-triketone, 1,3,5-triketone (4-tertiary butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4 , 6-(1H,3H,5H)-trione, etc., but are not limited thereto. Among them, 1,3,5-shen(4-tertiary butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-trihydroxy-2,4,6 -(1H,3H,5H)-trione is particularly preferred.

The content of the hindered phenol compound is not particularly limited, but is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of polyamide imide, etc., in view of the light intensity when the resin composition is used as the photosensitive resin composition. From the viewpoint of sensitivity characteristics, 0.5 parts by mass to 10 parts by mass is more preferable. When the content of the hindered phenol compound is 20 parts by mass or less based on 100 parts by mass of polyimide or the like, it is preferable because the photosensitivity is excellent when the resin composition is used as the photosensitive resin composition.

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

The resin composition of the present invention is preferably a resin composition used for forming an insulating film. The resin composition of the present invention is preferably a photosensitive resin composition, and more preferably a negative photosensitive resin composition.

(resin film) The resin film of the present invention is a fired product of the coating film of the resin composition of the present invention. As the coating method, methods conventionally used for coating resin compositions can be used. For example, methods using a spin coater, a bar coater, a knife coater, a curtain coater, a screen printing machine, etc., or spray coating can be used. Machine spray coating method, etc. As a method of firing to obtain a fired product, various methods can be selected, such as using a heating plate, using an oven, or using a temperature-raising oven with a settable temperature program. Firing can be performed, for example, at 130°C to 250°C for 30 minutes to 5 hours. As the ambient gas during heat hardening, air can be used, or inert gases such as nitrogen and argon can 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 photoresist film) When the resin composition of the present invention is a photosensitive resin composition, the resin composition of the present invention can be used in a photosensitive photoresist film (so-called dry film photoresist). The photosensitive resist film has a base film, a photosensitive resin layer (photosensitive resin film) formed of a photosensitive resin composition, and a cover film. Usually, a photosensitive resin layer and a cover film are laminated in sequence on the base film.

The photosensitive resist film can be produced, for example, by coating a base film with a photosensitive resin composition, drying the composition to form a photosensitive resin layer, and then laminating a cover film on the photosensitive resin layer. As the coating method, methods conventionally used for coating photosensitive resin compositions can be used. For example, methods using a spin coater, a bar coater, a knife coater, a curtain coater, a screen printing machine, etc. can be used. Methods of spray coating using a spray machine, etc. As a drying method, for example, conditions of 20°C to 200°C for 1 minute to 1 hour can be cited. The thickness of the obtained photosensitive resin layer is not particularly limited, but is preferably 1 μm to 100 μm, and more preferably 2 μm to 50 μm.

As the base film, a known one can be used, and for example, a thermoplastic resin film or the like can be used. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 μm to 150 μm. A well-known mask can be used as the covering film, for example, polyethylene film, 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 preferred. The thickness of the facial mask 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 covering film can be of the same film material, or different films can be used.

(Method for manufacturing substrate with hardened relief pattern) The manufacturing method of the substrate with hardened relief pattern of the present invention includes: (1) The step of applying a photosensitive resin composition, which is an embodiment of the resin composition of the present invention, on a substrate and forming a photosensitive resin layer (photosensitive resin film) on the substrate; (2) The step of exposing the photosensitive resin layer; (3) The step of developing the exposed photosensitive resin layer to form a relief pattern; and (4) The step of heating the relief pattern to form a hardened relief pattern.

Each step is explained below.

(1) The step of coating the photosensitive resin composition of the present invention on a substrate and forming a photosensitive resin layer on the substrate In this step, the photosensitive resin composition of the present invention is coated on the substrate, and then dried if necessary to form a photosensitive resin layer. As the coating method, methods conventionally used for coating photosensitive resin compositions can be used. For example, methods using a spin coater, a bar coater, a knife coater, a curtain coater, a screen printing machine, etc. can be used. Methods of spray coating using a spray machine, etc.

The substrate coated with the photosensitive resin composition has, for example, metal wiring on its surface. Examples of metal wiring include copper wiring, copper alloy wiring, and the like. The formation method of the metal wiring is not particularly limited, and for example, conventionally known methods can be used.

The coating film composed of the photosensitive resin composition can be dried as necessary, and as the drying method, for example, air drying, heating drying with an oven or a hot plate, vacuum drying, etc. can be used. Specifically, when air drying or heat drying is performed, drying can be performed at 20° C. to 200° C. for 1 minute to 1 hour. The photosensitive resin layer can be formed on the substrate by the above.

(2) The step of exposing the photosensitive resin layer. For this step, the photosensitive resin layer formed in the above step (1) is exposed using exposure devices such as contact aligners, mirror projections, and steppers. Exposed through a patterned mask or a reticle or directly through an ultraviolet light source. Examples of light sources used during exposure include g-rays, h-rays, i-rays, ghi-ray broadband, and KrF excimer lasers. The exposure amount is preferably 25mJ/cm ² to 2000mJ/cm ² .

Thereafter, post-exposure baking (PEB) and/or pre-development baking using any combination of temperature and time can also be implemented as needed based on the purpose of improving photosensitivity. The range of baking conditions is that the temperature is preferably 50°C to 200°C, and the time is preferably 10 seconds to 600 seconds, but it is not limited to this range as long as the various characteristics of the photosensitive resin composition are not hindered. .

(3) The step of developing the exposed photosensitive resin layer to form a relief pattern For this step, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As a development method for developing the photosensitive resin layer after exposure (irradiation), conventionally known photoresist development methods can be used, such as a rotary spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, and the like. Choose any method and use it. In addition, cleaning may be performed for the purpose of removing the developer after development. Furthermore, for the purpose of adjusting the shape of the relief pattern, etc., post-development baking using any combination of temperature and time can be implemented as needed. As a developer used for development, an organic solvent is preferred. Examples of organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, and N,N-dimethylacetamide. , cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferred. In addition, two or more types of each solvent may be combined, for example, several types may be used in combination. The cleaning liquid used for cleaning is preferably an organic solvent that is mixed with a developer and has low solubility relative to the photosensitive resin composition. As the cleaning liquid, for example, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, toluene, xylene, etc. are preferred. In addition, two or more types of each solvent may be combined, for example, several types may be used in combination.

(4) The steps of heating the relief pattern to form a hardened relief pattern For this step, the relief pattern obtained by the above-mentioned development is heated and converted into a hardened relief pattern. As a method of heating and hardening, various methods can be selected, such as using a heating plate, using an oven, or using a temperature-raising oven with a settable temperature program. Heating can be performed, for example, at 130°C to 250°C for 30 minutes to 5 hours. As the ambient gas during heat hardening, air can be used, or inert gases such as nitrogen and argon can be used.

The thickness of the hardened 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 the upper part or lower part of the semiconductor element is also provided. The cured film is a cured film formed from the resin composition of the present invention. In an embodiment, the resin composition is a photosensitive resin composition, and the cured film is a cured relief pattern formed of the photosensitive resin composition. The hardened relief pattern can be obtained, for example, by steps (1) to (4) in the above-mentioned manufacturing method of a substrate with a hardened relief pattern. Furthermore, the present invention is also applicable to a method of manufacturing a semiconductor device using a semiconductor element as a substrate and including the above-described method of manufacturing a substrate with a hardened relief pattern as a part of the steps. The semiconductor device of the present invention can be used 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 by forming a hardened relief pattern. The semiconductor device is manufactured by combining known manufacturing methods.

(display device) An embodiment is a display device including a display element and a cured film provided on an upper portion of the display element, wherein the cured film is a film formed of the resin composition of the present invention. In an embodiment, the resin composition is a photosensitive resin composition, and the cured film is a cured relief pattern formed of the photosensitive resin composition. Here, the cured film (for example, the cured relief pattern) can be laminated in direct contact with the display element, or can be laminated with other layers sandwiched between them. Examples include surface protective films, insulating films, and planarizing films for TFT (Thin Film Transistor) liquid crystal display elements and color filter elements, protrusions for MVA (Multi-domain Vertical Alignment) type liquid crystal display devices, and organic EL (Electro-Luminescence) The partition wall used for the cathode of the element serves as the cured film.

In addition to the above-mentioned applications in semiconductor devices, the resin composition of the present invention is also suitable for use in interlayer insulating films for multilayer circuits, cover coats for flexible copper-clad laminates, solder photoresist films, and liquid crystal alignment films. Also useful. [Example]

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

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

The chemical acyl imidization rate shown in the following synthesis examples was calculated using the following method. Put 100 mg of polyimide powder into an NMR sample tube (NMR Sample Tube Standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)), add deuterated dimethylstyrene (DMSO-d6, 0.05% TMS (tetramethylsilane)), and mix. product) (0.53 ml), apply ultrasonic waves to completely dissolve it. The solution was measured for proton NMR at 500 MHz using an NMR device (JNM-ECA500) (manufactured by Japan Electronics Co., Ltd.). The chemical acyl imidization rate is based on the source The proton from the structure that does not change before and after acyl imidization is determined as the reference proton, and the peak accumulation value of this proton is used, combined with the peak accumulation value of protons derived from the NH group of amide acid that appears around 9.59 ppm to 11.0 ppm. It is found by the following formula. Chemical acyl imidization rate (%) = (1-α・x/y)×100 In the above formula, x is the peak accumulation value of protons derived from the NH group of amide acid, y is the peak accumulation value of reference protons, and α is when it is polyamic acid (imidization rate is 0%). The ratio of the number of protons relative to one proton in the NH group of amide.

<Synthesis Example 1> Synthesis of polyamide (P-1) 9.71 g of 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Samsung Chemical Industry Co., Ltd.), 2,2-bis[4-(4- 35.38 g of aminophenoxy)phenyl]hexafluoropropane, 0.10 g of 4-methoxyphenol, and 218.35 g of N-ethyl-2-pyrrolidinone were stirred and dissolved in the air at room temperature. Thereafter, 25.13 g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy) ) 33.74 g of phenyl bacil anhydride (BPF-PA, manufactured by JFE Chemical Co., Ltd.) and 93.58 g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 1 hour, the mixture was stirred at 50 The mixture was stirred for 19 hours at ℃ to obtain a polyamide solution. The weight average molecular weight (Mw) of the obtained polyamide (P-1) measured by GPC was 29,554.

<Synthesis Example 2> Synthesis of solvent-soluble polyimide (P-2) To 415.9g of polyamic acid (P-1) obtained in Synthesis Example 1, 623.84g of N-ethyl-2-pyrrolidinone, 32.16g of acetic anhydride and 5.31g of triethylamine were added, and the mixture was stirred at room temperature under air. 30 minutes and then stir at 60°C for 3 hours. This solution was slowly added to 3,770 g of stirring methanol, and the mixture was stirred for 10 minutes, and the resulting precipitate was filtered. The precipitate was washed with 3,770 g of methanol, and then the obtained precipitate was filtered. The precipitate was further washed with 3,770 g of methanol again, and the obtained precipitate was filtered and dried under reduced pressure at 50° C. to obtain a powder of solvent-soluble polyimide (P-2). The chemical imidization rate is 95.3%.

<Synthesis Example 3> Synthesis of polyamide (P-3) 4.62 g of 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Samsung Chemical Industry Co., Ltd.), 2,2-bis[4-(4- After stirring and dissolving 16.84g of aminophenoxy)phenyl]hexafluoropropane, 0.05g of 4-methoxyphenol and 80.9g of N-ethyl-2-pyrrolidinone in air and room temperature, Mix 11.97g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride and 9,9-bis[4-(3,4-dicarboxyphenoxy)benzene 16.07g of stilbeneic anhydride (BPF-PA, manufactured by JFE Chemical Co., Ltd.) and 34.65g of N-ethyl-2-pyrrolidinone were added to the system, stirred at room temperature for 1 hour, and then stirred at 40°C. 20 hours to obtain a polyamic acid solution. The weight average molecular weight (Mw) of the obtained polyamide (P-3) measured by GPC was 32,482.

<Synthesis Example 4> Synthesis of polyamide (P-4) 31.78 g of 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Samsung Chemical Industries Co., Ltd.), 4-octadecyloxy-1,3 -Phenylenediamine (DAB-C18, manufactured by Wakayama Seika Industry Co., Ltd.) 38.81g, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane 62.34g and N-ethyl After stirring and dissolving 1012.4 g of methyl-2-pyrrolidinone in the air at room temperature, dodecahydro-5,5'-di-2-benzofuran-1,1'3,3'- was added. 31.57 g of tetraketone (H-BPDA, manufactured by WeiHai Newera Kesense New Materials Co., Ltd.), stirred for 40 minutes, and then added 2,2',3,3',5,5'-hexamethyl-[1,1'- Benzene]-4,4'-diylbis(1,3-bisoxy-1,3-dihydroisobenzofuran-5-carboxylate) (TMPBP-TME, manufactured by Honshu Chemical Industry Co., Ltd. ) 85.00g, stir for 1.5 hours, add 48.28g of 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride (SD1100-P: manufactured by Sabic Corporation), and stir at 50 Stir for 20 hours at ℃ to obtain a polyamide solution. The weight average molecular weight (Mw) of the obtained polyamide (P-4) measured by GPC was 29,350.

<Synthesis Example 5> Synthesis of solvent-soluble polyimide (P-5) To 1985.1g of polyamic acid (P-4) obtained in Synthesis Example 4, 992.6g of N-ethyl-2-pyrrolidinone, 105.22g of acetic anhydride and 17.38g of triethylamine were added, and the mixture was stirred at room temperature in the air. 30 minutes and then stir at 60°C for 3 hours. Thereafter, 992.6 g of N-ethyl-2-pyrrolidone was added to dilute the solution, 1922 g was distributed, and 4265 g of methanol was slowly added to the stirring solution. After stirring for 10 minutes, the resulting precipitate was filtered. After washing the precipitate with 1,922 g of methanol, the obtained precipitate was filtered. The precipitate was further washed with 1,922 g of methanol, and the obtained precipitate was filtered and dried under reduced pressure at 60° C. to obtain a powder of solvent-soluble polyimide (P-5). The chemical imidization rate is 98.6%.

<Synthesis Example 6> Synthesis of polyamic acid ester (P-6): 200.00g (0.68mol) of 4,4'-diphthalic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was put into a 2-liter container In a four-necked flask, add 176.92g (1.366mol) of 2-hydroxyethyl methacrylate (manufactured by Sigma-Aldrich Japan GK), 0.74g (0.007mol) of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) and γ-butylene 600 g of ester was stirred at 23° C., 108.63 g (1.36 mol) of pyridine was added, the temperature was raised to 50° C., and the mixture was stirred at 50° C. for 2 hours to obtain a solution containing a compound represented by the following formula. [Chemical 28]

82.46g of the obtained solution and 19.45g of γ-butyrolactone were put into a four-necked flask with a capacity of 500 ml, and 13.13g of N,N'-diisopropylcarbodiimide (DIC, manufactured by Tokyo Chemical Industry Co., Ltd.) A solution dissolved in 30 g of γ-butyrolactone was added dropwise to the reaction solution at about 5°C over 0.5 hours while stirring, and after the dropping, the solution was stirred for 0.5 hours. Next, 19.68 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 30 g of N-methyl-tetrahydropyrrole-2-one. It took 2 hours to drip while stirring. Thereafter, the temperature was raised to about 25° C., and after stirring for 6 hours, 4.5 g of ethanol was added and stirred for 1 hour. The obtained reaction mixture was added to 1500 g of methanol to form a precipitate consisting of a crude polymer. The supernatant liquid was decanted to separate the crude polymer, and it was dissolved in 150.0 g of N-methyl-tetrahydropyrrol-2-one to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 2250g of water to precipitate the polymer. After filtering the obtained precipitate, it was washed twice with 600g of methanol and dried in vacuum to obtain powdery polyamide ester (P-6). . The weight average molecular weight (Mw) of the obtained polyamide ester (P-6) measured by GPC was 8,016. The yield is 73.6%.

The main compounds shown in the Examples and Comparative Examples are shown below.・NK ESTER A-DOD-N: 1,10-decanediol diacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) ・IRGACURE [registered trademark] OXE01: 1,2-octanedione, 1-[4- (Phenylthio)phenyl-,2-(O-benzoyl oxime)] (manufactured by BASF Japan Co., Ltd.) ・IRGANOX [registered trademark] 3114: (1,3,5-shen(3,5- Di(tertiary butyl)-4-hydroxybenzyl)-1,3,5-tris-2,4,6(1H,3H,5H)-triketone (manufactured by BASF Japan Co., Ltd.)・KBM- 5103: 3-propenyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) ・BMI-689: 1H-pyrrole-2,5-dione, 1,1'-C ₃₆ -alkylene Double-(Made by Designer Molecules Inc.)

<Example 1> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photoradical initiator, 0.081g of IRGACURE [registered trademark] OXE01 and 0.024g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.) were mixed and dissolved, and then polypropylene with a pore diameter of 5 μm was used. Make a filter and filter, thereby preparing a negative photosensitive resin composition.

<Example 2> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photoradical initiator, 0.081g of IRGACURE [registered trademark] OXE01 and 0.049g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.) were mixed and dissolved, and then polypropylene with a pore diameter of 5 μm was used. Make a filter and filter, thereby preparing a negative photosensitive resin composition.

<Example 3> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photoradical initiator, 0.081g of IRGACURE [registered trademark] OXE01 and 0.081g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.) were mixed and dissolved, and then polypropylene with a pore diameter of 5 μm was used. Make a filter and filter, thereby preparing a negative photosensitive resin composition.

<Example 4> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photoradical initiator, IRGACURE [registered trademark] OXE01 0.081g, 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.) 0.024g, and 1,2,3-benzotriazole (Tokyo Chemical Industry Co., Ltd.) 0.024 g was mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a negative photosensitive resin composition.

<Example 5> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photoradical initiator, 0.081g of IRGACURE [registered trademark] OXE01, 0.024g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.), and 0.024g of IRGANOX [registered trademark] 3114 are mixed. After dissolving, it was filtered using a polypropylene filter with a pore diameter of 5 μm, thereby preparing a negative photosensitive resin composition.

<Example 6> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photoradical initiator, IRGACURE [registered trademark] OXE01 0.081g, 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.) 0.024g, and 5-methyl-1H-benzotriazole ( Tokyo Chemical Industry Co., Ltd.) 0.024 g was mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Example 7> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photoradical initiator, 0.081g of IRGACURE [registered trademark] OXE01, 0.049g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.), and 0.033g of KBM-5103 are mixed and dissolved. A negative photosensitive resin composition was prepared by filtering using a polypropylene filter with a pore diameter of 5 μm.

<Example 8> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photoradical initiator, IRGACURE [registered trademark] OXE01 0.081g, 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.) 0.049g, and 5-methyl-1H-benzotriazole ( Tokyo Chemical Industry Co., Ltd.) 0.024 g was mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Example 9> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photoradical initiator, 0.081g of IRGACURE [registered trademark] OXE01, 0.049g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.), and 0.024g of IRGANOX [registered trademark] 3114 are mixed. After dissolving, it was filtered using a polypropylene filter with a pore diameter of 5 μm, thereby preparing a negative photosensitive resin composition.

<Example 10> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. IRGACURE [registered trademark] OXE01 0.081g as a photoradical initiator, and CBT-SG (a mixture of 4-carboxybenzotriazole and 5-carboxybenzotriazole, manufactured by Seongbuk Chemical Industry Co., Ltd.) 0.024 g was mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a negative photosensitive resin composition.

<Example 11> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. IRGACURE [registered trademark] OXE01 0.081g as a photoradical initiator, and CBT-SG (a mixture of 4-carboxybenzotriazole and 5-carboxybenzotriazole, manufactured by Seongbuk Chemical Industry Co., Ltd.) 0.049 g was mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a negative photosensitive resin composition.

<Example 12> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photoradical initiator, 0.081g of IRGACURE [registered trademark] OXE01 and 0.024g of CBT-5 (5-carboxybenzotriazole, manufactured by Seonghoku Chemical Industry Co., Ltd.) were mixed and dissolved before use. A negative photosensitive resin composition was prepared by filtering through a polypropylene filter with a pore size of 5 μm.

<Example 13> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photoradical initiator, 0.081g of IRGACURE [registered trademark] OXE01 and 0.049g of CBT-5 (5-carboxybenzotriazole, manufactured by Seonghoku Chemical Industry Co., Ltd.) were mixed and dissolved before use. A negative photosensitive resin composition was prepared by filtering through a polypropylene filter with a pore size of 5 μm.

<Example 14> In a solution containing 22.44 g of the polyamide (P-3) obtained in Synthesis Example 3 (solid content concentration: 30% by mass), 2.02 g of NK ESTER A-DOD-N as a cross-linking agent and photoradicals were 0.34 g of the starter IRGACURE [registered trademark] OXE01 and 0.20 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.) were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm. Thereby, a negative photosensitive resin composition is prepared.

<Example 15> 3.70g of the solvent-soluble polyimide (P-5) obtained in Synthesis Example 5, 0.56g of NK ESTER A-DOD-N as the cross-linking agent, and IRGACURE [registered trademark] as the photoradical initiator were used ]OXE01 0.15g, and CBT-SG (a mixture of 4-carboxybenzotriazole and 5-carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.), 0.056g, KBM-5103 (manufactured by Shin-Etsu Chemical Industry Co., Ltd. )0.074g, 0.22g of BMI-689 (manufactured by Designer Molecules Inc.) as a bismaleimide compound, 3.67g of N-ethyl-2-pyrrolidinone, 4.90g of γ-butyrolactone, and cyclohexane After mixing and dissolving 3.67 g of ketone, the mixture was filtered using a polypropylene filter with a pore diameter of 5 μm, thereby preparing a negative photosensitive resin composition.

<Example 16> 6.34 g of the powder of polyamide ester (P-6) obtained in Synthesis Example 6, 16.25 g of N-ethyl-2-pyrrolidinone, and 1.90 g of NK ESTER A-DOD-N as a cross-linking agent were used as 0.317g of IRGACURE [registered trademark] OXE01, a photoradical initiator, and 0.19g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.) were mixed and dissolved, and then a polypropylene filter with a pore size of 5 μm was used. and filtering, thereby preparing a negative photosensitive resin composition.

＜Comparative example 1＞ 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g, and 0.081 g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition.

＜Comparative example 2＞ 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photoradical initiator, 0.081g of IRGACURE [registered trademark] OXE01 and 0.033g of KBM-5103 are mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive Resin composition.

＜Comparative Example 3＞ 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photo radical initiator, IRGACURE [registered trademark] OXE01 0.081g and IRGANOX [registered trademark] 3114 0.024g were mixed and dissolved, and then filtered through a polypropylene filter with a pore size of 5 μm to prepare Negative photosensitive resin composition.

＜Comparative Example 4＞ 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photoradical initiator, 0.081g of IRGACURE [registered trademark] OXE01 and 0.024g of 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed and dissolved before use. A negative photosensitive resin composition was prepared by filtering through a polypropylene filter with a pore size of 5 μm.

＜Comparative Example 5＞ 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As a photoradical initiator, 0.081g of IRGACURE [registered trademark] OXE01 and 0.049g of 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed and dissolved before use. A negative photosensitive resin composition was prepared by filtering through a polypropylene filter with a pore size of 5 μm.

<Comparative Example 6> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As photoradical initiators, IRGACURE [registered trademark] OXE01 0.081g, 5-methyl-1H-benzotriazole (made by Tokyo Chemical Industry Co., Ltd.) 0.024g, and IRGANOX [registered trademark] 3114 0.24 g After mixing and dissolving, the mixture was filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a negative photosensitive resin composition.

<Comparative Example 7> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. As photoradical initiators, IRGACURE [registered trademark] OXE01 0.081g, 5-methyl-1H-benzotriazole (made by Tokyo Chemical Industry Co., Ltd.) 0.049g, and IRGANOX [registered trademark] 3114 0.24 g After mixing and dissolving, the mixture was filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a negative photosensitive resin composition.

＜Comparative Example 8＞ 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. IRGACURE [registered trademark] OXE01 0.081g as a photoradical initiator, and 2,4-diamino-6-butylamino-1,3,5-trifluoroethylene (Tokyo Chemical Industry Co., Ltd.) 0.024 g of the mixture was mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a negative photosensitive resin composition.

<Comparative Example 9> 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. IRGACURE [registered trademark] OXE01 0.081g as a photoradical initiator, and 2,4-diamino-6-diallylamino-1,3,5-trifluoroethylene (Tokyo Chemical Industry (Tokyo Chemical Industry) Co., Ltd.) 0.024 g was mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a negative photosensitive resin composition.

＜Comparative Example 10＞ 1.63g of the powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N 0.49 as a cross-linking agent were prepared. g. IRGACURE [registered trademark] OXE01 0.081g as a photoradical initiator, and 6-(dibutylamino)-1,3,5-tris-2,4-dithiol (Tokyo Chemical Industry (manufactured by Co., Ltd.), 0.024 g was mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm, thereby preparing a negative photosensitive resin composition.

[Evaluation of Adhesion Strength] An 8-inch silicon wafer with Cu evaporated to a thickness of 1.5 μm was cut into 1 cm × 1 cm. The silicon wafer was washed with 10% sulfuric acid for 1 minute, washed with pure water for 30 seconds and then dried, and then coated with the negative photosensitive resin composition prepared in Examples 1 to 16 and Comparative Examples 1 to 10. things. A photosensitive resin film of 22 μm was formed on the substrate (silicon wafer on which Cu was vapor-deposited) by temporarily firing at 115° C. for 270 seconds. Next, an i-beam aligner (PLA-501, manufactured by Canon Co., Ltd.) was used to expose the entire surface at 500 mJ/cm ² , and then a high-temperature clean oven (CLH-21CD(V)-S, manufactured by Koyo Thermo Systems Co., Ltd.) was used. Fire at 230°C for 2 hours in a nitrogen atmosphere. Next, the reliability test was performed at 125°C for 24 hours and 30°C at 60% humidity for 168 hours in the air. Then, three times of 260°C for 1 second including temperature rise in a nitrogen environment were performed as a reflow process. Finally, a high temperature test was performed. Accelerated life test (EHS-212MD, manufactured by ESPEC Co., Ltd.) was performed at 130°C, humidity 85%, vapor pressure 230kPa, and 192 hours. After that, the Stud Pin with epoxy adhesive was bonded to the surface of the resin film, and the Stud Pull peel strength measurement was performed using ROMURUS V (Quad Group Company, USA) to evaluate the adhesion between the Cu surface and the resin film. In addition, a substrate that was not subjected to the reliability test (a substrate with a resin film formed on it) was also prepared, and the Stud Pull peel strength measurement was performed in the same manner. Observe the peeling interface after the test. If the epoxy adhesive peels off due to aggregation failure before and after the reliability test, or if the epoxy adhesive peels off at the interface between the epoxy adhesive and the resin film surface, it is considered that the adhesion force is good. Mark "O"; the case where peeling occurs at the interface between the photosensitive resin film and Cu before and after the reliability test is regarded as poor adhesion and marked "×". The results are shown in Table 1-1 and Table 1-2.

[Antioxidant ability evaluation] An evaluation test substrate (1cm × 1cm) with a PI (polyimide) base and Cu wiring with a height of 5 μm and a width of 10 μmL/S was washed with 10% sulfuric acid for 1 minute. Wash with pure water for 30 seconds and dry. The negative photosensitive resin composition prepared in Examples 1 to 16 and Comparative Examples 1 to 10 was applied to the substrate under the same conditions as [Adhesion Strength Evaluation], and was temporarily fired at 115°C for 270 seconds. clock, thereby forming a photosensitive resin film. Next, the entire surface was exposed at 500 mJ/cm ² using an i-ray aligner (PLA-501, manufactured by Canon Co., Ltd.). Next, a high-temperature clean oven (CLH-21CD(V)-S, Koyo Thermo Systems Co., Ltd.) was used to bake at 230° C. for 2 hours in a nitrogen atmosphere. Next, the reliability test was performed at 125°C for 24 hours in the air, 30°C at 60% humidity for 168 hours, and the reflow treatment at 260°C for 1 second including temperature rise was carried out three times in a nitrogen environment, and finally high acceleration was used After the life test (EHS-212MD, manufactured by ESPEC Co., Ltd.) and treated at 130°C, humidity 85%, vapor pressure 230kPa, and 192 hours, the Cu of the test substrate for evaluation was measured using FIB-SEM (manufactured by Japan FEI Co., Ltd.). Cut out the wiring and observe the cross section with SEM. If the thickness of the oxide film on the Cu wiring formed by the reliability test is thinner than that of Comparative Example 1 (73.7 nm), it will be marked as "0" as a good result, and if it is thicker, it will be marked as poor. "×". The results are shown in Table 1.

[Evaluation of Electrical Properties] The negative photosensitive resin compositions prepared in Examples 1 to 15 and Comparative Examples 1 to 10 were spin-coated on a 4-inch silicon wafer covered with a 20 μm thick aluminum foil. A photosensitive resin film of approximately 22 μm was formed on the aluminum foil by firing on a hot plate at 115° C. for 270 seconds. An i-ray aligner (PLA-501, manufactured by Canon Co., Ltd.) was used on the obtained photosensitive resin film to fully expose the wafer at 500 mJ/cm ² , and then a high-temperature clean oven (CLH-21CD (V )-S, Koyo Thermo Systems Co., Ltd.), fired at 230°C for 2 hours in a nitrogen atmosphere. Furthermore, the fired aluminum foil was immersed in 6N hydrochloric acid to dissolve the aluminum foil, thereby obtaining a thin film. The obtained film was dried, and the loss tangent at 60 GHz was measured using a split cylinder resonator. The measurement conditions for loss tangent are as follows.・Measurement method: Split cylinder resonator ・Vector network analyzer: FieldFox N9926A (made by Keysight Technologies Co., Ltd.) ・Resonator: CR-760 (made by EM Labs Co., Ltd.) ・Measurement frequency: approximately 60GHz This measurement will be performed The obtained loss tangent value was marked as "0" if it was less than that of Comparative Example 1 (0.0087), and it was marked as "0" as a good result, and it was marked as "×" if it was greater than Comparative Example 1, and it was bad. The results are shown in Table 1-1 and Table 1-2.

[Table 1-1]

[Table 1-2]

From the results of Table 1-1 and Table 1-2, the resin films obtained from the negative photosensitive resin compositions of Examples 1 to 16 all had good adhesion. Furthermore, the Cu wiring of the resin film obtained from the negative photosensitive resin composition of Examples 1 to 16 was formed, and the thickness ratio of the oxide film after the reliability test was the negative photosensitivity of Comparative Example 1. The Cu wiring of the resin film obtained from the resin composition was thinner, and good reliability was confirmed. Furthermore, the films obtained from the negative photosensitive resin compositions of Examples 1 to 15 showed a loss tangent lower than that of the films obtained from the negative photosensitive resin composition of Comparative Example 1.

Claims (23)

A resin composition comprising at least one resin selected from the group consisting of polyimide, polybenzoethazole and these precursors, a compound represented by the following formula (A), and a solvent, In formula (A), R _a represents a hydrogen atom, a hydroxyl group, a hydroxymethyl group, or an alkyl group having 1 to 30 carbon atoms; R _b represents an alkyl group having 1 to 30 carbon atoms; m represents an integer of 0 to 3, n represents an integer from 1 to 4, and the maximum sum of m and n is 4. The resin composition of claim 1, wherein the resin is at least one resin selected from the group consisting of polyimide and its precursors. The resin composition of claim 1, wherein the resin is a polyimide having structural units represented by the following formula (1-a) and the following formula (1-b-1) or having the following formula (3) and a polyimide precursor having a structural unit represented by the following formula (1-b-2), In formula (1-a) and formula (1-b-1), Ar ₁ represents a tetravalent organic group, and X ₁₁ represents a divalent organic group having a photopolymerizable group; Formula (3) and formula (1-b- In 2), Ar ₃ represents a tetravalent organic group, L ₁ and L ₂ each independently represent a univalent organic group, X ₁₂ represents a divalent organic group, and at least one of L ₁ , L ₂ and X ₁₂ has a photopolymerizable group . The resin composition of claim 1, wherein the resin has a divalent organic group represented by the following formula (9-a), In formula (9-a), V ₁ represents a direct bond, ether bond, ester bond, amide bond, urethane bond, or urea bond, W ₁ represents an oxygen atom or an NH group, and R ₁₅ represents a direct bond. Knot, or an alkylene group with 2 to 6 carbon atoms that can also be substituted by a hydroxyl group, R ₁₆ represents a hydrogen atom or a methyl group, and * represents a bond. The resin composition of claim 4, wherein V ₁ in the formula (9-a) represents an ester bond, and W ₁ further represents an oxygen atom. The resin composition of claim 4, wherein R ₁₅ in the formula (9-a) represents 1,2-ethylidene group. The resin composition of claim 1, wherein R _a in the formula (A) represents a hydrogen atom. The resin composition of claim 1, wherein m in the formula (A) represents 0. The resin composition of claim 1, wherein the compound represented by formula (A) contains at least one of 1H-benzotriazole-5-carboxylic acid and 1H-benzotriazole-4-carboxylic acid. The resin composition of claim 1, further comprising a photoradical polymerization initiator. The resin composition of claim 1, further comprising a crosslinking compound. The resin composition of claim 1 is used for forming an insulating film. The resin composition of claim 1 is a photosensitive resin composition. The resin composition of claim 1 is a negative photosensitive resin composition. A resin film which is a fired product of a coating film of the resin composition according to any one of claims 1 to 14. The resin film of claim 15 is an insulating film. A photosensitive photoresist film, which has a base film, a photosensitive resin layer formed of the resin composition of claim 13 or 14, and a cover film. A method of manufacturing a substrate with a hardened relief pattern, which includes the following steps: (1) The step of coating the resin composition of claim 13 or 14 on a substrate and forming a photosensitive resin layer on the substrate; (2) The step of exposing the photosensitive resin layer; (3) The step of developing the exposed photosensitive resin layer to form a relief pattern; and (4) The step of heating the relief pattern to form a hardened relief pattern. The method of manufacturing a substrate with a hardened relief pattern as claimed in claim 18, wherein in the (1) step, the resin composition is coated on the substrate having metal wiring on the surface. The method of manufacturing a substrate with a hardened relief pattern as claimed in claim 18, wherein the developer used for the development is an organic solvent. A substrate with a hardened relief pattern, which is manufactured by the manufacturing method of a substrate with a hardened relief pattern according to claim 18. A semiconductor device including a semiconductor element and a cured film provided on an upper or lower portion of the semiconductor element, wherein the cured film is a cured film formed of the resin composition according to any one of claims 1 to 14. The semiconductor device of claim 22, wherein the resin composition is a photosensitive resin composition, The cured film is a cured relief pattern formed by the photosensitive resin composition.