TW201905086A - Photosensitive resin composition, resin film, and electronic device - Google Patents

Abstract

This photosensitive resin composition comprises an alkali-soluble resin, a photosensitizer, and a solvent, wherein the solvent contains a urea compound, or, an amide compound having an acyclic structure. The structure of the urea compound is preferably an acyclic structure. In addition, the urea compound is preferably tetramethylurea. Furthermore, the amide compound having an acyclic structure is preferably, for example, 3-methoxy-N,N-dimethylpropanamide. In addition, the alkali-soluble resin is preferably a polyamide resin.

Description

Photosensitive resin composition, resin film, and electronic device

The present invention relates to a photosensitive resin composition, a resin film, and an electronic device.

In the field of the photosensitive resin composition, various techniques have been developed so far for the purpose of obtaining a photosensitive resin composition capable of forming a non-fragile and heat-resistant cured film even when cured at a low temperature. Examples of such a technique include those described in Patent Document 1. According to Patent Document 1, it is described that a film obtained by applying a resin composition containing a compound having a phenolic hydroxyl group to a polyamide having a specific structure and curing at 200 ° C. or lower shows a high elongation at break.

Patent Document 1: Japanese Patent Application Laid-Open No. 2007-213032

When using the photosensitive resin composition described in Patent Document 1 as a permanent film of an electronic device, the inventors of the present invention provided copper (Cu) as an aluminum (Al) pad and a circuit provided as input and output of a substrate of the electronic device. ) Study the tightness between the circuit and the permanent film. The so-called permanent film is a cured film obtained by pre-baking, exposing, and developing a photosensitive resin composition to produce a resin film patterned into a desired shape, and then curing the resin film by post-baking. . As a result of the above studies, it is determined that the cured film formed using the photosensitive resin composition described in Patent Document 1 has insufficient adhesion with respect to Al pads and Cu circuits. Therefore, an object of the present invention is to improve the adhesion between a cured film obtained by post-baking a photosensitive resin composition and metals such as Al and Cu.

The present inventors studied the raw material components of the photosensitive resin composition in order to improve the adhesion between the cured film of the post-baking photosensitive resin composition and metals such as Al and Cu. As a result, it was found that by including a specific solvent as a raw material component, the adhesion between the cured film of the post-baking photosensitive resin composition and metals such as Al and Cu can be improved, and the present invention has been completed.

According to the present invention, there is provided a photosensitive resin composition including: an alkali-soluble resin; a photosensitizer; and a solvent, wherein the solvent includes a urea compound or an amidine compound having a non-cyclic structure.

Also, according to the present invention, a resin film obtained by curing the photosensitive resin composition can be provided.

Also, according to the present invention, an electronic device including the resin film can be provided.

The present invention provides a photosensitive resin composition that improves the adhesion between a cured film obtained by post-baking the photosensitive resin composition and metals such as Al and Cu.

The above-mentioned objects and other objects, features, and advantages will be made clearer by the preferred embodiments described below and the accompanying drawings.

Hereinafter, this embodiment will be described using drawings as appropriate. In all drawings, the same constituent elements are denoted by the same reference numerals, and descriptions thereof are omitted.

The photosensitive resin composition according to this embodiment includes an alkali-soluble resin, a sensitizer, and a solvent, and the solvent includes a urea compound or an amidine compound having a non-cyclic structure.

In recent years, with the miniaturization of electronic devices, there has been a tendency for metal members such as Al pads and copper circuits of electronic devices to become smaller. Here, when the metal member becomes smaller, the adhesion between the cured film of the photosensitive resin composition formed by laminating the metal member and the metal member is low, and the cured film is peeled. When the cured film is peeled off, a leakage current or the like is generated from a part where the peeling occurs, and there is a disadvantage that the electrical reliability of the electronic device is reduced.

The present inventors have studied a raw material component of a photosensitive resin composition that can improve the adhesion between a cured film of a post-bake photosensitive resin composition and metals such as Al pads and copper circuits. As a result, it was found that adhesiveness can be improved by using a urea compound or a fluorene compound having a non-cyclic structure as a solvent for the photosensitive resin composition. Although the detailed mechanism that can improve the adhesion is not clear, it can be estimated as follows. As a mechanism for improving the adhesion, firstly, it is thought that the lone electron pair included in the urea compound and the amidine compound having a non-cyclic structure forms a strong coordination bond with a metal atom such as Al or Cu. From this, it is considered that the varnish-containing component of the photosensitive resin composition before drying is stretched by the coordination bond formed by the solvent and is strongly bonded to metals such as Al and Cu. Thereafter, when the photosensitive resin composition is pre-baked, exposed, and developed to produce a resin film patterned into a desired shape, and then the resin film is post-baked to harden, thereby producing a cured film, It is estimated that the molecular coordination of the contained components other than the solvent of the photosensitive resin composition can be frozen in a state where the contained components other than the solvent of the photosensitive resin composition and metal atoms are strongly bonded. Therefore, it is considered that the adhesion between the post-bake cured film and metals such as Al and Cu can be improved. In addition, it is presumed that the urea compound and the amidine compound having an acyclic structure have different mechanisms for forming the aforementioned strong coordination bond. First, as a premise, it is known that a photosensitive resin composition uses a cyclic amidine compound such as N-methylpyrrolidone (NMP) as a solvent. A urea compound has two or more nitrogen atoms having a lone electron pair in its molecular structure due to a urea bond. As a result, it is presumed that the coordination bond becomes stronger in proportion to the number of lone electron pairs. Therefore, when a urea compound is used, it is thought that a strong coordination bond can be formed compared with the compound used for the solvent of the conventional photosensitive resin composition. In addition, it is presumed that the amidine compound having a non-cyclic structure is easier to form a coordination bond than the amidine compound having a cyclic structure used in a conventional photosensitive resin composition. This is considered to be because the amidine compound having a non-cyclic structure has fewer restrictions on molecular motion than the amidine compound having a cyclic structure, and further has a large degree of freedom in deformation of the molecular structure. Therefore, when a fluorene compound having a non-cyclic structure is used, it is considered that a stronger coordination bond can be formed than a compound used in a solvent of a conventional photosensitive resin composition. From the above, it is presumed that the photosensitive resin composition of the present embodiment contains a specific compound as a solvent, whereby the adhesion between the post-bake cured film and metals such as Al and Cu can be improved.

Furthermore, in addition to the improvement in adhesion between the post-bake cured film and metals such as Al and Cu, urea compounds have less adverse effects on the human body than solvents used in conventional photosensitive resin compositions. The consideration of perspective is also beneficial. The cyclic amidine compounds, such as N-methylpyrrolidone, which have been used in the past, have various adverse effects such as impaired reproductive functions as they enter the human body. In consideration of safety, production of photosensitive resin compositions is required Steps to study. However, since the urea compound has a small adverse effect on the human body, it is advantageous in terms of studies that do not require production steps. Examples of the urea compound having less adverse effects on the human body include tetramethylurea.

First, each raw material component of the photosensitive resin composition of this embodiment is demonstrated.

(Alkali-soluble resin) The alkali-soluble resin is not limited, and can be selected according to physical properties such as mechanical properties and optical properties required for the resin film. Specific examples of the alkali-soluble resin include polyamine resin, polybenzoxazole resin, phenol resin, and hydroxystyrene resin. As the alkali-soluble resin, in the above-mentioned specific examples, for example, a polyfluorene resin or a polybenzoxazole resin is preferably used. From this, it is considered that strong interactions such as hydrogen bonding can be formed between the amidine bond of the polyamide resin and the urea compound or the amidine compound having a non-cyclic structure. Therefore, when the photosensitive resin composition is used as a cured film, it is considered that the molecular structure can be frozen by the coordination in which the alkali-soluble resin and metal molecules are more strongly bonded. The alkali-soluble resin may include one or two or more of the specific examples described above.

<Polyamide resin, polybenzoxazole resin> As the polyamide resin, for example, an aromatic polyamine containing an aromatic ring in the structural unit of polyamine is preferably used, and contains the following formula (PA1) The structural unit shown is more preferred. Thereby, the molecular chains of the polyamide resin are hydrogen-bonded with each other via the amidine bond, and then the aromatic ring part is closely arranged in a molecular arrangement, whereby the alkali-soluble resin and the metal molecule can be more strongly bonded. Coordination to freeze molecular structure. When the solvent contains tetramethylurea as a urea compound, this coordination is more suitable for improving adhesion. Therefore, from the viewpoint of improving the adhesiveness, it is preferable to include a polyamine resin as the alkali-soluble resin and the solvent to include tetramethylurea as the urea compound. In the present embodiment, the term "aromatic ring" means a benzene ring; a condensed aromatic ring such as a naphthalene ring, an anthracene ring, a fluorene ring; a heteroaromatic ring such as a pyridine ring or a pyrrole ring; From the viewpoint of forming the above-mentioned compact structure, it is preferable that the polyamidoamine resin of the present embodiment contains a benzene ring as an aromatic ring.

A precursor of a polyfluorene resin-based polybenzoxazole resin containing a structural unit represented by the formula (PA1). The polyamide resin containing the structural unit represented by the above formula (PA1) can be subjected to heat treatment at a temperature of 150 ° C or higher and 380 ° C or lower for 30 minutes or longer and 50 hours or shorter, thereby dehydrating and closing the ring to form a polymer. Benzoxazole resin. Here, the structural unit of the above formula (PA1) becomes a structural unit represented by the following formula (PBO1) by dehydration closed loop. In the case where the alkali-soluble resin of this embodiment is a polyamide resin containing the structural unit represented by the formula (PA1), for example, the photosensitive resin composition may be subjected to the above-mentioned heat treatment to dehydrate and close the ring to form a polymer. Benzoxazole resin. That is, the photosensitive resin composition subjected to the heat treatment includes a polybenzoxazole resin as an alkali-soluble resin. In the case where the alkali-soluble resin is a polyamide resin containing a structural unit represented by the formula (PA1), the above-mentioned heat treatment may be performed after the resin film and electronic device described later are manufactured, thereby dehydrating and closing the ring to form polybenzene. And oxazole resin. When a polybenzoxazole resin is formed by dehydrating and ring-opening a polyfluorene resin, the tensile elongation at break and the glass transition temperature can be increased. Thereby, it is advantageous from a viewpoint that the strength and heat resistance of a resin film and an electronic device can be improved.

<The manufacturing method of a polyamide resin> The polyamide resin of this embodiment is polymerized as follows, for example. First, polyamine is polymerized by polymerizing a diamine monomer and a dicarboxylic acid monomer in a polymerization step (S1). Next, a low molecular weight component is removed in a low molecular weight component removal step (S2), and a polyamide resin containing polyamine as a main component is obtained.

(Polymerization Step (S1)) In the polymerization step (S1), a diamine monomer and a dicarboxylic acid monomer are polycondensed. The polycondensation method for polymerizing polyamine is not limited, and specific examples include melt polycondensation, chlorination, and direct polycondensation. Further, instead of the dicarboxylic acid monomer, a compound selected from the group consisting of tetracarboxylic dianhydride, 1,2,4-benzenetricarboxylic anhydride, dichlorinated dicarboxylic acid, or an active ester type dicarboxylic acid may be used. . Specific examples of a method for obtaining an active ester-type dicarboxylic acid include a method of reacting a dicarboxylic acid with 1-hydroxy-1,2,3-benzotriazole and the like.

The diamine monomer and the dicarboxylic acid monomer used in the polymerization of the polyamide resin are described below. In addition, one type of diamine monomer and one dicarboxylic acid monomer may be separately prepared, or two or more types may be used in combination.

<Diamine monomer> The diamine monomer used for polymerization is not limited. For example, a diamine monomer containing an aromatic ring in the structure is preferred, and a diamine monomer containing a phenolic hydroxyl group in the structure is more preferred. good. Here, as a diamine monomer containing a phenolic hydroxyl group in a structure, it is preferable that it is represented by the following general formula (DA1), for example. By using the diamine monomer as a raw material to manufacture a polyamide resin and controlling the configuration of the polyamide resin, the molecular chains of the polyamide resin can form a tighter structure with each other. Therefore, the molecular structure can be frozen and the adhesion can be improved by the coordination in which the alkali-soluble resin and the metal molecule are more strongly bonded. When a diamine monomer represented by the following general formula (DA1) is used, for example, the polyamide resin contains a structural unit represented by the following general formula (PA2). That is, it is preferable that the polyamide resin of this embodiment contains a structural unit represented by the following general formula (PA2), for example.

(In the general formula (DA1), R ⁴ is selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. A group formed by one or two or more kinds of atoms. R ⁵ to R ¹⁰ each independently represent hydrogen or an organic group having 1 to 30 carbon atoms.)

(In the general formula (PA2), R ⁴ and R ⁵ to R ¹⁰ are the same as the general formula (DA1).)

R ^{4 in} the general formulae (DA1) and (PA2) is selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. A radical formed by one or more atoms in a group. R ⁴ is a divalent radical. Here, the divalent radical means an atomic valence. In other words, there are two bond bonds showing that R ⁴ is bonded to other atoms.

When R ⁴ in the general formulae (DA1) and (PA2) contains a carbon atom, R ^{4 is,} for example, a group having 1 to 30 carbon atoms, and a group having 1 to 10 carbon atoms is preferred. Carbon A group having a number of 1 to 5 is more preferred, and a group having a number of 1 to 3 is more preferred.

R in the general formula (DAl) and (PA2) contained in the case ⁴ carbon atoms, as R ^4, specifically include alkylene, arylene, substituted alkylene group of halo, substituted by halogen Zhifang aryl and so on. The alkylene group may be, for example, a linear alkylene group or a branched alkylene group. Specific examples of the linear alkylene group include methylene, ethylidene, propylidene, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and xylenyl. Decyl, trimethylene, tetramethylene, pentamethylene, hexamethylene and the like. Specific examples of the branched alkylene group include -C (CH ₃ ) _2- , -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) ₂ -and other alkyl methylene groups; -CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2- , -C (CH ₂ CH ₃ ) ₂ -CH _2- , etc. Ethyl etc. Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthyl group, an anthracene group, and two or more arylenyl groups bonded to each other. As the halogen-substituted alkylene group and the halogen-substituted alkylene group, specifically, a hydrogen atom in the alkylene group and the alkylene group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom. Winner. Among these, it is more preferable to use one obtained by replacing a hydrogen atom with a fluorine atom.

When R ⁴ in the general formulae (DA1) and (PA2) does not include a carbon atom, specific examples of R ⁴ include a group consisting of an oxygen atom or a sulfur atom.

R ⁵ to R ^{10 in} the general formulae (DA1) and (PA2) are each independently hydrogen or an organic group having 1 to 30 carbon atoms. For example, hydrogen or an organic group having 1 to 10 carbon atoms is preferred. Preferably, hydrogen or an organic group having 1 or more and 5 or less carbon is more preferable, hydrogen or an organic group having 1 or more and 3 or less is more preferable, and hydrogen or an organic group having 1 or more and 2 or less is further Better. This allows the aromatic rings of the polyamide resin to be closely aligned with each other. Therefore, the molecular structure can be frozen by the coordination formed by the alkali-soluble resin and the metal molecule being more strongly bonded, and the adhesion can be improved.

Specific examples of the organic group having 1 to 30 carbon atoms in R ⁵ to R ¹⁰ in the general formulae (DA1) and (PA2) include methyl, ethyl, n-propyl, isopropyl, and n- Butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and other alkyl groups; allyl, pentenyl, ethylene Alkenyl groups such as ethynyl; alkynyl groups such as ethynyl; alkylene groups such as methine, ethylene; aryl groups such as tolyl, xylyl, phenyl, naphthyl, and anthracenyl; aromatic groups such as benzyl, phenethyl Alkyl; cycloalkyl such as adamantyl, cyclopentyl, cyclohexyl, cyclooctyl; alkylaryl such as tolyl, xylyl, and the like.

Specific examples of the diamine monomer represented by the general formula (DA1) include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-methylene Bis (2-amino-3,6-dimethylphenol), 4,4'-methylenebis (2-aminophenol), 1,1-bis (3-amino-4-hydroxyphenyl) ) Ethane, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, etc. By using these diamine monomers, the aromatic rings of the polyamide resin can be closely aligned with each other. Therefore, the molecular structure can be frozen by the coordination formed by the alkali-soluble resin and the metal molecule being more strongly bonded, and the adhesion can be improved. Furthermore, as the diamine monomer, one of the above specific examples can be used or two or more of them can be used in combination. The structural formula of these diamine monomers is shown below.

<Dicarboxylic acid monomer> There is no limitation as a dicarboxylic acid monomer used for polymerization, For example, it is preferable to use the dicarboxylic acid monomer which contains an aromatic ring in a structure. As the dicarboxylic acid monomer containing an aromatic ring, it is preferable to use, for example, one represented by the following general formula (DC1). When a dicarboxylic acid monomer represented by the following general formula (DC1) is used, for example, the polyamide resin includes a structural unit represented by the following general formula (PA3). That is, it is preferable that the polyamide resin of this embodiment contains a structural unit represented by the following general formula (DC1), for example. This allows the aromatic rings of the polyamide resin to be closely aligned with each other. Therefore, the molecular structure can be frozen by the coordination formed by the alkali-soluble resin and the metal molecule being more strongly bonded, and the adhesion can be improved.

(In the general formula (DC1), R ¹¹ is selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. A group formed by one or two or more kinds of atoms. R ¹² to R ¹⁹ each independently represent hydrogen or an organic group having 1 to 30 carbon atoms.)

(In the general formula (PA3), R ¹¹ and R ¹² to R ¹⁹ are the same as the general formula (DC1).)

R ^{11 in} the general formulae (DC1) and (PA3) is selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. A radical formed by one or more atoms in a group. R ¹¹ is a divalent radical. Here, the divalent radical means an atomic valence. In other words, there are two bond bonds showing that R ¹¹ is bonded to other atoms.

When R ¹¹ in the general formulae (DC1) and (PA3) contains a carbon atom, R ^{11 is,} for example, a group having 1 to 30 carbon atoms, and a group having 1 to 10 carbon atoms is preferred. Carbon Groups having a number of 1 to 5 are more preferred, and groups having a carbon number of 1 to 3 are more preferred.

R in the general formula (DC1) and (PA3) contains ¹¹ carbon atoms in the case, as R ^11, specifically include alkylene, arylene, substituted alkylene group of halo, substituted by halogen Zhifang aryl and so on. The alkylene group may be, for example, a linear alkylene group or a branched alkylene group. Specific examples of the linear alkylene group include methylene, ethylidene, propylidene, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and xylenyl. Decyl, trimethylene, tetramethylene, pentamethylene, hexamethylene and the like. Specific examples of branched alkylene include -C (CH ₃ ) _2- , -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) ₂ -and other alkyl methylene groups; -CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2- , -C (CH ₂ CH ₃ ) ₂ -CH _2- , etc. Ethyl etc. Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthyl group, an anthracene group, and two or more arylenyl groups bonded to each other. As the halogen-substituted alkylene and halogen-substituted alkylene, specifically, a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom can be used instead of a hydrogen atom in the alkylene group or the alkylene group. By. Among these, it is preferable to use a fluorine atom instead of a hydrogen atom.

When R ¹¹ in the general formulae (DC1) and (PA3) does not include a carbon atom, examples of R ¹¹ include a group consisting of an oxygen atom or a sulfur atom.

R ¹² to R ^{19 in} the general formulae (DC1) and (PA3) are each independently hydrogen or an organic group having 1 to 30 carbon atoms. For example, hydrogen or an organic group having 1 to 10 carbon atoms is preferred. Preferably, hydrogen or an organic group having 1 or more and 5 or less carbon is more preferred, hydrogen or an organic group having 1 or more and 3 or less carbon is further preferred, and hydrogen is still more preferred.

Specific examples of the organic group having 1 to 30 carbon atoms in R ¹² to R ¹⁹ in the general formulae (DC1) and (PA3) include methyl, ethyl, n-propyl, isopropyl, and n-propyl. Butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and other alkyl groups; allyl, pentenyl, ethylene Alkenyl groups such as ethynyl; alkynyl groups such as ethynyl; alkylene groups such as methine, ethylene; aryl groups such as tolyl, xylyl, phenyl, naphthyl, and anthracenyl; aromatic groups such as benzyl, phenethyl Alkyl; cycloalkyl such as adamantyl, cyclopentyl, cyclohexyl, cyclooctyl; alkylaryl such as tolyl, xylyl, and the like.

As the dicarboxylic acid monomer, specifically, diphenyl ether-4,4'-dicarboxylic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, and the like can be used. As the dicarboxylic acid monomer, diphenyl ether-4,4'-dicarboxylic acid or isophthalic acid in the above specific examples is preferred, and diphenyl ether-4,4'-dicarboxylic acid is more preferred. . The aromatic rings of the polyamide resin can be closely aligned with each other. Therefore, the molecular structure can be frozen by the coordination formed by the alkali-soluble resin and the metal molecule being more strongly bonded, and the adhesion can be improved.

Furthermore, it is preferable to modify the amine group existing at the terminal of the polyamide resin at the same time as the polymerization step (S1) or after the polymerization step (S1). The modification can be performed, for example, by reacting a specific acid anhydride or a specific monocarboxylic acid with a diamine monomer or a polyamide resin. Therefore, it is preferred that the amine group at the polyamine resin-based terminal of this embodiment is modified with a specific acid anhydride or a specific monocarboxylic acid. The specific acid anhydride and the specific monocarboxylic acid have one or more functional groups selected from the group consisting of an alkenyl group, an alkynyl group, and a hydroxyl group. The specific acid anhydride and the specific monocarboxylic acid are preferably those containing a nitrogen atom, for example. This can improve the adhesion between the post-baking photosensitive resin composition and metals such as Al and Cu. Specific examples of the specific acid anhydride include maleic anhydride, citraconic anhydride, 2,3-dimethyl maleic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, and exo- 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3- Dicarboxylic anhydride, itaconic anhydride, chlorobridged anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride, etc. As the specific acid anhydride, one of the above specific examples can be used or two or more of them can be used in combination. When the amine group present at the terminal of the polyamide resin is modified with a specific acid anhydride having a ring shape, the specific acid anhydride having a ring shape undergoes ring opening. Here, after modifying the polyamidamine resin, the structural unit derived from a specific acid anhydride derived from a ring may be closed to form a fluoreneimine ring. Examples of the method for performing the closed loop include heat treatment and the like. Moreover, as said specific monocarboxylic acid, 5-norbornene-2-carboxylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, etc. are mentioned specifically ,. As the specific monocarboxylic acid, one of the specific examples described above can be used or two or more of them can be used in combination.

The carboxyl group existing at the terminal of the polyamide resin may be modified at the same time as the polymerization step (S1) or after the polymerization step (S1). The modification can be performed, for example, by reacting a specific nitrogen atom-containing heteroaromatic compound with a dicarboxylic acid monomer or a polyamide resin. Therefore, the polyamide resin of the present embodiment is preferably formed by modifying a terminal carboxyl group with a specific nitrogen atom-containing heteroaromatic compound. The specific nitrogen atom-containing heteroaromatic compound is selected from the group consisting of 1- (5-1H-triazolyl) methylamino, 3- (1H-pyrazolyl) amino, and 4- (1H -Pyrazolyl) amino, 5- (1H-pyrazolyl) amino, 1- (3-1H-pyrazolyl) methylamino, 1- (4-1H-pyrazolyl) methylamine Base, 1- (5-1H-pyrazolyl) methylamino, (1H-tetrazol-5-yl) amino, 1- (1H-tetrazol-5-yl) methyl-amino, and 3 -(1H-tetrazol-5-yl) benzene-amine group having one or more functional groups. This makes it possible to increase the number of lone electron pairs in the photosensitive resin composition. Therefore, it is possible to improve the adhesion between the photosensitive resin composition after prebaking and after baking, and a metal such as Al. Examples of the specific nitrogen atom-containing heteroaromatic compound include 5-aminotetrazole and the like.

(Low-molecular-weight component removal step (S2)) Following the above-mentioned polymerization step (S1), a low-molecular-weight component removal step (S2) is performed, and low-molecular-weight components are removed to obtain a polyamide resin containing a polyamide resin as a main component. The organic layer containing the mixture of the low molecular weight component and the polyamide resin is concentrated by filtration or the like, and then dissolved in an organic solvent such as water / isopropanol again. Thereby, a precipitate can be filtered, and the polyamine resin from which a low molecular weight component was removed can be obtained.

As the polyamide resin, for example, one obtained by condensing a diamine monomer represented by the general formula (DA1) and a dicarboxylic acid monomer represented by the general formula (DC1) is preferable. That is, as the polyamide resin, it is preferable to include the structural units of the general formulae (PA2) and (PA3), and it is more preferable to provide the structural units of the general formulae (PA2) and (PA3) alternately.

<Phenol resin> Specific examples of the phenol resin include phenol novolac resin, cresol novolac resin, bisphenol novolac resin, phenol-biphenol novolac resin, and other novolac phenol resins; novolac phenol resins, Reactants of phenol compounds such as soluble phenol resin type phenol resin and cresol novolac resin type with aldehyde compound; reactants of phenol compound such as phenol aralkyl resin and dimethanol compound, etc. The phenol resin may include one, two or more of the specific examples described above.

The phenol compound used as a reactant of a phenol compound and an aldehyde compound or a reactant of a phenol compound and a dimethanol compound is not limited. Specific examples of such phenol compounds include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, and 2,5-diphenol Xylenols such as cresol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol Class; alkylphenols such as isopropylphenol, butylphenol, p-tertiary butylphenol; polyphenols such as resorcinol, catechol, hydroquinone, gallophenol, resorcinol; 4 , 4'-biphenol and other biphenyl phenols. As the phenol compound, one or two or more of the above specific examples can be used.

The aldehyde compound described above as a reactant for a phenol compound and an aldehyde compound is not limited as long as it is a compound having an aldehyde group. Specific examples of such an aldehyde compound include formaldehyde, polyformaldehyde, acetaldehyde, benzaldehyde, and salaldehyde. As the aldehyde compound, one, two or more of the above specific examples can be used.

The above-mentioned dimethanol compound as a reactant for a phenol compound and a dimethanol compound is not limited. Specific examples of such dimethanol compounds include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4'-biphenyldimethanol, 3,4'-biphenyldimethanol, 3, 3'-biphenyldimethanol, 2,6-naphthalenedimethanol, 2,6-bis (hydroxymethyl) -p-cresol, and other dimethanol compounds; 1,4-bis (methoxymethyl) benzene, 1 , 3-bis (methoxymethyl) benzene, 4,4'-bis (methoxymethyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl, 3,3'- Bis (methoxymethyl) biphenyl, bis (alkoxymethyl) compounds such as methyl 2,6-naphthalene dicarboxylate, or 1,4-bis (chloromethyl) benzene, 1,3-bis (Chloromethyl) benzene, 1,4-bis (bromomethyl) benzene, 1,3-bis (bromomethyl) benzene, 4,4'-bis (chloromethyl) biphenyl, 3,4'- Bis (chloromethyl) biphenyl, 3,3'-bis (chloromethyl) biphenyl, 4,4'-bis (bromomethyl) biphenyl, 3,4'-bis (bromomethyl) biphenyl Or bis (haloalkyl) compounds such as 3,3'-bis (bromomethyl) biphenyl, 4,4'-bis (methoxymethyl) biphenyl, 4,4'-bis (methoxymethyl) ) Biphenyl aralkyl compounds such as biphenyl. As the dimethanol compound, one or two or more of the above specific examples can be used.

<Hydroxystyrene resin> The hydroxystyrene resin is not limited. Specifically, one or two or more selected from the group consisting of hydroxystyrene, a hydroxystyrene derivative, styrene, and a styrene derivative can be used. Polymerization or copolymerization reactants formed by polymerization or copolymerization. Moreover, as a hydroxystyrene derivative and a styrene derivative, the thing which substituted the hydrogen atom which the aromatic ring of hydroxystyrene and styrene has with the monovalent organic group specifically is mentioned. Examples of the monovalent organic group substituted for a hydrogen atom include alkyl groups such as methyl, ethyl, and n-propyl; alkenyl groups such as allyl and vinyl; alkynyl groups such as ethynyl; methine and ethylene And other alkylene groups; cycloalkyl groups such as cyclopropyl groups; heterocyclic groups such as epoxy groups and oxetanyl groups.

<Cyclic olefin-based resin> The cyclic olefin-based resin is not limited. Specifically, one or two or more selected from the group consisting of norbornene and norbornene derivatives can be polymerized or copolymerized. Polymerization or copolymerization reactants. Further, as the norbornene derivative, specifically, a hydrogen atom bonded to a norbornene skeleton by a monovalent organic group may be mentioned. Examples of the monovalent organic group substituted for a hydrogen atom include alkyl groups such as methyl, ethyl, and n-propyl; alkenyl groups such as allyl and vinyl; alkynyl groups such as ethynyl; methine and ethylene And other alkylene groups; cycloalkyl groups such as cyclopropyl groups; heterocyclic groups such as epoxy groups and oxocyclobutane groups.

For example, when the total solid content of the photosensitive resin composition is 100 parts by mass, the lower limit of the content of the alkali-soluble resin in the photosensitive resin composition is preferably 30 parts by mass or more, and more preferably 40 parts by mass or more. 50 mass parts or more is further preferred, 60 mass parts or more is further preferred, and 70 mass parts or more is particularly preferred. This allows the alkali-soluble resin in the photosensitive resin composition to appropriately interact with the urea compound or the amidine compound having a non-cyclic structure in the solvent. Therefore, the molecular structure can be frozen by the coordination formed by the alkali-soluble resin and the metal molecule being more strongly bonded, and the adhesion can be improved. For example, when the total solid content of the photosensitive resin composition is 100 parts by mass, the upper limit value of the content of the alkali-soluble resin in the photosensitive resin composition is preferably 95 parts by mass or less, and 90 parts by mass or less. More preferably, 85 parts by mass or less is more preferable. In addition, in this embodiment, the total solid content of the photosensitive resin composition means the total of the content of the photosensitive resin composition other than the solvent.

(Photosensitizer) As the photosensitizer, a photoacid generator that generates an acid by absorbing light energy can be used. Specific examples of the photoacid generator include a diazoquinone compound; a diarylsulfonium salt; a 2-nitrobenzyl ester compound; an N-iminosulfonate compound; and a pyrimidate sulfonate Compounds; 2,6-bis (trichloromethyl) -1,3,5-three well compounds; dihydropyridine compounds, etc. Among these, it is preferable to use a photosensitive diazoquinone compound. This can improve the sensitivity of the photosensitive resin composition. Therefore, the accuracy of the pattern can be improved, and the appearance can be improved. The photoacid generator can include one or two or more of the specific examples described above. When the photosensitive resin composition is of the positive type, in addition to the specific examples described above, as the photosensitizer, a triarylsulfonium salt, an onium salt such as fluorene-borate, or the like may be used in combination. This can further improve the sensitivity of the photosensitive resin composition. Specific examples of the diazoquinone compound that can be preferably used as a photosensitizer are shown below.

(N is an integer from 1 to 5.)

In each of the above diazoquinone compounds, Q is a structure or a hydrogen atom represented by the following formula (a), (b), and (c). Among them, at least one of Q of each diazoquinone compound has a structure represented by the following formula (a), (b), and (c). The Q of the diazoquinone compound preferably contains the following formula (a) or (b). This can improve the transparency of the photosensitive resin composition. Therefore, the appearance of the photosensitive resin composition can be improved.

When the alkali-soluble resin is 100 parts by mass, the lower limit value of the content of the photosensitizer in the photosensitive resin composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and 5 parts by mass or more. Better. Thereby, the photosensitive resin composition can exhibit appropriate sensitivity. When the alkali-soluble resin is 100 parts by mass, the upper limit of the content of the photosensitizer in the photosensitive resin composition is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less. Thereby, the photosensitive resin composition is appropriately hardened, and adhesion to metals such as Al and Cu can be exhibited after pre-baking and after-baking.

(Solvent) The photosensitive resin composition of this embodiment contains a urea compound or an amidine compound having a non-cyclic structure as a solvent. As the solvent, for example, a urea compound is preferably contained. Thereby, the adhesiveness between the hardened | cured material of a photosensitive resin composition and metals, such as Al and Cu, can be improved further. In addition, in this specification, a urea compound means the compound which has a urea bond, ie, a urea bond. The amidine compound refers to a compound having an amidine bond, that is, amidine. Furthermore, the amidines specifically include first-grade amidines, second-grade amidines, and third-grade amidines. In the present embodiment, the acyclic structure refers to a compound that does not include a cyclic structure such as a carbocyclic ring, an inorganic ring, or a heterocyclic ring. Examples of the structure of a compound having no cyclic structure include a linear structure and a branched structure.

As the urea compound and the amidine compound having a non-cyclic structure, it is preferable that the number of nitrogen atoms in the molecular structure is large. Specifically, the number of nitrogen atoms in the molecular structure is preferably two or more. Thereby, the number of lone electron pairs can be increased. Therefore, it is possible to improve the adhesion with metals such as Al and Cu.

Specific examples of the structure of the urea compound include a cyclic structure and an acyclic structure. The structure of the urea compound is preferably a non-cyclic structure in the above specific examples. Thereby, the adhesiveness between the hardened | cured material of a photosensitive resin composition and metals, such as Al and Cu, can be improved. The reason is presumed as follows. It is estimated that a urea compound having an acyclic structure is more likely to form a coordination bond than a urea compound having a cyclic structure. This is considered to be because the urea compound having a non-cyclic structure has fewer restrictions on molecular motion than the urea compound having a cyclic structure, and further has a large degree of freedom in deforming the molecular structure. Therefore, when a urea compound having a non-cyclic structure is used, a strong coordination bond can be formed, and adhesion can be improved.

Specific examples of the urea compound include tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone, N, N-dimethylacetamide, tetrabutylurea, N, N '-Dimethacryl urea, 1,3-dimethoxy-1,3-dimethylurea, N, N'-diisopropyl-O-methylisourea, O, N, N'- Triisopropylisourea, O-tertiary butyl-N, N'-diisopropylisourea, O-ethyl-N, N'-diisopropylisourea, O-benzyl-N, N'-diisopropylisourea and the like. As the urea compound, one of the above specific examples may be used or two or more of them may be used in combination. As the urea compound, for example, a compound selected from tetramethylurea (TMU), tetrabutylurea, 1,3-dimethoxy-1,3-dimethylurea, N, N'-di Isopropyl-O-methylisourea, O, N, N'-triisopropylisourea, O-tertiary butyl-N, N'-diisopropylisourea, O-ethyl-N One or two or more of the group consisting of, N'-diisopropylisourea and O-benzyl-N, N'-diisopropylisourea are preferred. The use of tetramethylurea (TMU) is Better. Thereby, a strong coordination bond can be formed, and adhesiveness can be improved.

Specific examples of the amidine compound having a non-cyclic structure include 3-methoxy-N, N-dimethylpropanamide, N, N-dimethylformamide, and N, N-dimethyl Propamide, N, N-diethylacetamide, 3-butoxy-N, N-dimethylpropanamide, N, N-dibutylformamide, and the like.

The photosensitive resin composition according to this embodiment may contain, as a solvent, a solvent having no nitrogen atom in addition to a urea compound and a fluorene compound having a non-cyclic structure. Specific examples of the solvent having no nitrogen atom include ether-based solvents, acetate-based solvents, alcohol-based solvents, ketone-based solvents, lactone-based solvents, carbonate-based solvents, fluorene-based solvents, ester-based solvents, and aromatic solvents. Group hydrocarbon solvents and the like. As the solvent having no nitrogen atom, one of the above specific examples can be used or two or more of them can be used in combination. Specific examples of the ether-based solvent include propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, and ethylene glycol. Diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, 1,3-butanediol-3-monomethyl ether, and the like. Specific examples of the acetate-based solvent include propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butanediol acetate, and the like. . Specific examples of the alcohol-based solvent include tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol, butanediol, and isopropanol. Specific examples of the ketone-based solvent include cyclopentanone, cyclohexanone, diacetone alcohol, and 2-heptanone. Specific examples of the lactone-based solvent include γ-butyrolactone (GBL) and γ-valerolactone. Specific examples of the carbonate-based solvent include ethyl carbonate and propylene carbonate. Specific examples of the fluorene-based solvent include dimethyl fluorene (DMSO), cyclobutane, and the like. Specific examples of the ester-based solvent include methyl pyruvate, ethyl pyruvate, and methyl-3-methoxypropionate. Specific examples of the aromatic hydrocarbon-based solvent include symmetric xylene, toluene, and xylene.

When the solvent is 100 parts by mass, the lower limit of the content of the urea compound and the acyclic amine compound in the solvent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and 30. It is more preferable that it is more than mass part, it is more preferable that it is 50 mass part or more, and it is more preferable that it is 70 mass part or more. Thereby, the adhesiveness between the hardened | cured material of a photosensitive resin composition and metals, such as Al and Cu, can be improved further. When the solvent is 100 parts by mass, the lower limit of the content of the urea compound and the acyclic amine compound in the solvent can be, for example, 100 parts by mass or less. In the solvent, from the viewpoint of improving the adhesion, the content of the urea compound and the amidine compound having a non-cyclic structure is more preferable.

The photosensitive resin composition of this embodiment may further be added with additives such as adhesion aids, silane coupling agents, thermal crosslinking agents, surfactants, antioxidants, dissolution accelerators, fillers, and sensitizers. Hereinafter, representative additive components will be described in detail.

(Adhesion Aid) The photosensitive resin composition of this embodiment may further include an adhesion aid. As the adhesion adjuvant, specifically, a triazole compound, an aminosilane, or a sulfonimine compound can be used. Thereby, the number of lone electron pairs derived from a nitrogen atom can be further increased. Therefore, the content other than the solvent of the photosensitive resin composition can be coordinated with the metal atom, and adhesion can be further improved. As the adhesion adjuvant, any one of a triazole compound, an aminosilane, or a sulfonimine compound may be used, or two or more of a triazole compound, an aminosilane, and a sulfonimine compound may be used in combination.

Specific examples of the triazole compound include 4-amino-1,2,4-triazole, 4H-1,2,4-triazole-3-amine, and 4-amino-3,5-di- 2-pyridyl-4H-1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-methyl-4H-1,2,4- Triazole-3-amine, 3,4-diamino-4H-1,2,4-triazole, 3,5-diamino-4H-1,2,4-triazole, 1,2,4 -Triazole-3,4,5-triamine, 3-pyridyl-4H-1,2,4-triazole, 4H-1,2,4-triazole-3-carboxamide, 3,5- Diamino-4-methyl-1,2,4-triazole, 3-pyridyl-4-methyl-1,2,4-triazole, 4-methyl-1,2,4-triazole 1,2,4-triazole such as 3-formamidine. As the triazole compound, one of the above specific examples can be used or two or more can be used in combination.

Specific examples of the aminosilane include a condensate of cyclohexene-1,2-dicarboxylic anhydride and 3-aminopropyltriethoxysilane, and 3,3 ', 4,4'-diphenyl. Ketotetracarboxylic dianhydride and 3-aminopropyltriethoxysilane condensate, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane Silyl, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, N-phenyl-3-amino Propyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N, N'-bis (3-triethoxysilylpropyl) Ethylenediamine, N, N'-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N'-bis [3- (methyldiethoxysilyl) ) Propyl] ethylenediamine, N, N'-bis [3- (dimethylmethoxysilyl) propyl] ethylenediamine, N- [3- (methyldimethoxysilyl) ) Propyl] -N '-[3- (trimethoxysilyl) propyl] ethylenediamine, N, N'-bis [3- (trimethyl Oxysilyl) propyl] diaminopropane, N, N'-bis [3- (trimethoxysilyl) propyl] diaminohexane, N, N'-bis [3- ( Trimethoxysilyl) propyl] diethylenetriamine and the like. As the aminosilane, one of the above specific examples can be used or two or more of them can be used in combination.

Specific examples of the fluorene imine compound include the compounds exemplified below. These can be used singly or in combination of two or more.

The lower limit value of the content of the adhesion promoter in the photosensitive resin composition is, for example, preferably 0.1 parts by mass or more relative to 100 parts by mass of the alkali-soluble resin, more preferably 1.0 parts by mass or more, and 2.0 parts by mass or more. Preferably, 3.0 parts by mass or more is further preferred. Thereby, the close contact force can be fully improved. The upper limit of the content of the adhesion assistant in the photosensitive resin composition is, for example, 100 parts by mass of the alkali-soluble resin. Is even better. Accordingly, the adhesion assistant is appropriately dispersed in the photosensitive resin composition, and the adhesion can be improved.

(Silane coupling agent) The photosensitive resin composition of this embodiment may further contain a silane coupling agent. Examples of the silane coupling agent include those other than the amine silanes exemplified as the adhesion assistant. Specific examples of the silane coupling agent having a structure different from that of the above-mentioned silane compound include vinylsilane such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethyl Siloxane such as oxysilane, 3-glycidoxypropyltriethoxysilane; Styrylsilane such as p-styryltrimethoxysilane; 3-Methacryloxypropylmethyldi Methoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethyl Silanes such as methacrylic acid; acrylic silanes such as 3-propenyloxypropyltrimethoxysilane; triisocyanate silane; alkylsilanes; urea-based silane such as 3-ureidopropyltrialkoxysilane; Mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane; 3-isocyanatepropyltriethoxysilane Silane isocyanate; titanium compound; aluminum chelate; aluminum / zirconium compounds. As the silane coupling agent, one or two or more of the specific examples described above can be blended.

(Thermal Crosslinking Agent) The photosensitive resin composition of this embodiment may include a thermal crosslinking agent capable of reacting with an alkali-soluble resin by heat. Thereby, the hardened | cured material after post-baking the photosensitive resin composition can improve the mechanical characteristic of tensile elongation at break. It is also advantageous from the viewpoint of improving the sensitivity of a resin film formed from a photosensitive resin composition. Specific examples of the thermal crosslinking agent include 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol (p-xylylene glycol), and 1,3,5-benzene Trimethanol, 4,4-biphenyldimethanol, 2,6-pyridinedimethanol, 2,6-bis (hydroxymethyl) -p-cresol, 4,4'-methylenebis (2,6-dimethyl Alkoxymethylphenol) and other compounds with methylol groups; phenols such as pentahydroxybiphenyl (phloroglucide); 1,4-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) Group) benzene, 4,4'-bis (methoxymethyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl, 3,3'-bis (methoxymethyl) biphenyl Compounds with alkoxymethyl groups such as benzene, methyl 2,6-naphthalenedicarboxylate, 4,4'-methylenebis (2,6-dimethoxymethylphenol); hexamethylol Methylol melamine compounds such as melamine and hexabutanol melamine; alkoxymelamine compounds such as hexamethoxymelamine; alkoxymethyl acetylene urea compounds such as tetramethoxymethyl acetylene urea; hydroxymethyl benzo Hydroxymethyl urea compounds such as guanamine compounds, dimethylol vinyl urea; dicyanoanilines, dicyanobenzenes And cyano compounds such as cyanobenzenesulfonic acid; 1,4-phenylene diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate and other isocyanate compounds; ethylene glycol bicyclic Oxypropyl ether, bisphenol A diglycidyl ether, triglycidyl isocyanurate, bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, biphenyl Epoxy-containing compounds such as epoxy resins, phenol novolac resin epoxy resins; N, N'-1,3-phenylene dicis-butene difluorene imine, N, N'-methylene A maleimide compound such as a maleimide diimide and the like. As the thermal crosslinking agent, one of the above-mentioned specific examples can be used or two or more kinds can be used in combination.

The upper limit of the content of the thermal crosslinking agent in the photosensitive resin composition is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and 12 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin. Preferably, 10 parts by mass or less is more preferable. Accordingly, even when the thermal cross-linking agent includes a solvated functional group such as a phenolic hydroxyl group, it is possible to suppress a decrease in chemical resistance after the post-baking. The lower limit of the content of the thermal crosslinking agent in the photosensitive resin composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and 3 parts by mass or more with respect to 100 parts by mass of the alkali-soluble resin. To be more preferable, 5 parts by mass or more is further preferable, and 8 parts by mass or more is particularly preferable.

(Surfactant) The photosensitive resin composition of this embodiment may further contain a surfactant. The surfactant is not limited, and specific examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl Polyoxyethylene aryl ethers such as phenyl ether and polyoxyethylene nonylphenyl ether; non-ionic systems such as polyoxyethylene dilaurate and polyoxyethylene distearate surfactant; to EFTOP EF301, EFTOP EF303, EFTOP EF352 (manufactured Shin-Akita Chemical company), MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACE F444, MEGAFACE F470, MEGAFACE F471, MEGAFACE F475, MEGAFACE F482, MEGAFACE F477 (manufactured by DIC), FLUORAD FC-430, FLUORAD FC-431, NOVEC FC4430, NOVEC FC4432 (manufactured by 3M Japan), SURFLON S-381, SURFLON S-382, SURFLON S-383, SURFLON S-393, SURFLON Commercially available fluorine-based surfactants such as SC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106, (manufactured by AGC SEIMI CHEMICAL); organic silicon oxygen KP341 Shin-Etsu Chemical Co., Ltd.); (meth) acrylic copolymer Polyflow No.57,95 (KYOEISHA CHEMICAL Co., Ltd.).

Among these, it is preferable to use a fluorine-based surfactant having a perfluoroalkyl group. As the fluorine-based surfactant having a perfluoroalkyl group, the above-mentioned specific examples are selected from the group consisting of MEGAFACE F171, MEGAFACE F173, MEGAFACE F444, MEGAFACE F470, MEGAFACE F471, MEGAFACE F475, MEGAFACE F482, MEGAFACE F477 (manufactured by DIC Corporation), One or two or more of SURFLON S-381, SURFLON S-383, SURFLON S-393 (manufactured by AGC SEIMI CHEMICAL), NOVEC FC4430, and NOVEC FC4432 (manufactured by 3M Japan) are preferred.

In addition, as the surfactant, a polysiloxane-based surfactant (for example, polyether modified dimethylsiloxane) can be preferably used. Specific examples of the polysiloxane surfactant include SH series, SD series and ST series of Dow Corning Toray, BYK series of BYK Japan, KP series of Shin-Etsu Chemical Co., Ltd., and NOF Co., Ltd. DISFOAM (registered trademark) series, Toshiba Silicones Co., Ltd. TSF series and so on.

The upper limit of the content of the surfactant in the photosensitive resin composition is preferably 1% by mass (10000ppm) or less, and more preferably 0.5% by mass (5000ppm) with respect to the entire photosensitive resin composition (including the solvent). It is more preferable that it is 0.1 mass% (1000 ppm) or less. The lower limit value of the content of the surfactant in the photosensitive resin composition is not particularly limited, but from the viewpoint of sufficiently obtaining the effect based on the surfactant, for example, with respect to the entire photosensitive resin composition (including the solvent) , Above 0.001% by mass (10ppm). By appropriately adjusting the amount of the surfactant, it is possible to maintain other properties and improve coating properties, uniformity of the coating film, and the like.

(Antioxidant) The photosensitive resin composition of this embodiment may further contain an antioxidant. As the antioxidant, one or more selected from the group consisting of a phenol-based antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant can be used. The antioxidant can suppress the oxidation of the resin film formed of the photosensitive resin composition. Examples of the phenolic antioxidant include neopentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3 -(3-tertiarybutyl-4-hydroxy-5-methylphenyl) propanyloxy] -1,1-dimethylethyl} 2,4,8,10-tetraoxaspiro [5 , 5] undecane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tri (3,5-di-tert-butyl- 4-hydroxybenzyl) benzene, 2,6-di-tertiary-butyl-4-methylphenol, 2,6-di-tertiary-butyl-4-ethylphenol, 2,6-diphenyl- 4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl- 4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-di-tertiarybutyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6 -Tertiary butyl-m-cresol), 2-octylthio-4,6-bis (3,5-di-tertiary butyl-4-hydroxyphenoxy)-symmetrical three wells, 2,2 ' -Methylenebis (4-methyl-6-tertiarybutyl-6-butylphenol), 2, -2'-methylenebis (4- -6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butanoic acid] ethylene glycol ester, 4,4'-butylene bis (6 -Tertiary butyl-m-cresol), 2,2'-ethylenebis (4,6-di-tertiary butylphenol), 2,2'-ethylenebis (4-second butyl) -6-tertiary-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tertiary-butylphenyl) butane, bis [2-tertiary-butyl-4- Methyl-6- (2-hydroxy-3-tertiarybutyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl- 3-hydroxy-4-tertiary-butylbenzyl) trimeric isocyanate, 1,3,5-tris (3,5-di-tertiary-butyl-4-hydroxybenzyl) -2,4,6-tris Methylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] trimeric isocyanate, tetrakis [methylene-3- ( 3,5-di-tertiary butyl-4-hydroxyphenyl) propionate] methane, 2-tertiary butyl-4-methyl-6- (2-propenyloxy-3-tertiary butyl 5-methylbenzyl) phenol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] deca Monoalkane-bis [β- (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propionate], triethylene glycol bis [Β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 1,1'-bis (4-hydroxyphenyl) cyclohexane, 2,2'-sub Methylbis (4-methyl-6-tertiary-butylphenol), 2,2'-methylenebis (4-ethyl-6-tertiary-butylphenol), 2,2'-methylene Bis (6- (1-methylcyclohexyl) -4-methylphenol), 4,4'-butylene bis (3-methyl-6-tertiary butylphenol), 3,9-bis (2 -(3-tertiarybutyl-4-hydroxy-5-methylphenylpropionyloxy) 1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5, 5) Undecane, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-bis (3,5-di-tert-butyl-4-hydroxy Benzyl) sulfide, 4,4'-thiobis (6-tertiarybutyl-2-methylphenol), 2,5-di-tertiary butylhydroquinone, 2,5-di-tertiary Amylhydroquinone, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2,4-dimethyl -6- (1-methylcyclohexyl), styrenated phenol, 2,4-bis ((octylthio) methyl) -5-methylphenol, and the like. Examples of the phosphorus-based antioxidant include bis (2,6-di-tert-butyl-4-methylphenyl) neopentaerythritol diphosphite and tris (2,4-di-tert-butylbenzene). Diphosphite), tetra (2,4-di-tertiarybutyl-5-methylphenyl) -4,4'-biphenylphenyl phosphite, 3,5-di-tertiary butyl 4-hydroxybenzyl phosphate-diethyl ester, bis- (2,6-dicumylphenyl) neopentaerythritol diphosphite, 2,2-methylenebis (4, 6-di-tertiary butylphenyl) octyl phosphate, tri (mixed mono and di-nonylphenyl phosphite), bis (2,4-di-tertiary butylphenyl) neopentyl Alcohol diphosphite, bis (2,6-di-tertiary butyl-4-methoxycarbonylethyl-phenyl) neopentyl tetraol diphosphite, bis (2,6-di-tertiary Butyl-4-octadecyloxycarbonylethylphenyl) neopentaerythritol diphosphite and the like. Examples of the thioether-based antioxidant include 3,3'-thiodipropionate dilauryl and bis (2-methyl-4- (3-n-dodecyl) thiopropionyloxy) -5 -Tertiary butylphenyl) sulfide, 3,3'-thiodipropionate, neopentaerythritol-tetrakis (3-lauryl) thiopropionate, and the like.

(Filler) The photosensitive resin composition of this embodiment may further contain a filler. As the filler, an appropriate filler can be selected according to the mechanical characteristics and thermal characteristics required for a resin film made of a photosensitive resin composition. Specific examples of the filler include inorganic fillers and organic fillers. Specific examples of the inorganic filler include silicon dioxide such as fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, and finely divided silica; alumina, nitride Silicon, aluminum nitride, boron nitride, titanium oxide, silicon carbide, aluminum hydroxide, magnesium hydroxide, titanium white and other metal compounds; talc; clay; mica; glass fiber, etc. As the inorganic filler, one of the above specific examples can be used or two or more of them can be used in combination. Specific examples of the organic filler include organic polysiloxane powder and polyethylene powder. As the organic filler, one of the above specific examples can be used or two or more of them can be used in combination.

(Preparation of photosensitive resin composition) The method for preparing the photosensitive resin composition in this embodiment is not limited, and a known method can be used depending on the components contained in the photosensitive resin composition. For example, it can prepare by mixing each said component with a solvent, and making it melt | dissolve. Thereby, a photosensitive resin composition as a varnish can be obtained.

(Photosensitive resin composition) The photosensitive resin composition of this embodiment can be used by applying the varnish of the photosensitive resin composition to a surface provided with a metal such as Al, Cu, and the like, and then performing The resin film is dried to form a resin film, and then the resin film is patterned into a desired shape by exposure and development, and then the resin film is cured by post-baking to form a cured film. When the permanent film is produced, the pre-baking condition can be, for example, a heat treatment at a temperature of 90 ° C. or higher and 130 ° C. or lower and 30 seconds or longer and 1 hour or shorter. The post-baking condition can be, for example, a heat treatment at a temperature of 150 ° C. or higher and 350 ° C. or lower and 30 minutes or longer and 10 hours or shorter.

The viscosity of the photosensitive resin composition of this embodiment can be appropriately set according to the thickness of a desired resin film. The viscosity of the photosensitive resin composition can be adjusted by adding a solvent. In addition, when adjusting, it is necessary to keep the content of the urea compound and the acyclic amine compound in the solvent constant. The upper limit of the viscosity of the photosensitive resin composition of this embodiment may be, for example, 2000 mPa ･ s or less, 1800 mPa ･ s or less, or 1500 mPa ･ s or less. In addition, depending on the thickness of the desired resin film, the lower limit value of the viscosity of the photosensitive resin composition of this embodiment may be, for example, 10 mPa ･ s or more, and may be 50 mPa ･ s or more. In addition, in this embodiment, the viscosity of the photosensitive resin composition can be measured, for example, by using an E-type viscometer at a temperature of 25 ° C. for 300 seconds after the rotation is started.

The viscosity of the photosensitive resin composition of this embodiment is adjusted by a E-type viscometer so that the measured viscosity becomes 50 mPa ･ s after rotating at a rotation frequency of 100 rpm and a temperature of 25 ° C for 300 seconds, and 2 mL is added dropwise at a temperature of 25 ° C The upper limit value of the contact angle after 10 seconds from the copper foil is preferably 71 ° or less, more preferably 69 ° or less, more preferably 65 ° or less, even more preferably 62 ° or less, and 57 ° or less. Especially good. When the contact angle is below the above numerical range, the affinity between the varnish of the photosensitive resin composition and metals such as Cu is improved, and the photosensitive resin composition can penetrate into the fine gaps generated by the surface of the metal such as Cu. Accordingly, when the photosensitive resin composition is used as a cured film, an anchoring effect can be exhibited between the cured film and a metal such as Cu, and adhesion can be improved. In addition, with an E-type viscometer, the viscosity was adjusted so that the measured viscosity became 50 mPa ･ s after rotating at a rotation frequency of 100 rpm and a temperature of 25 ° C for 300 seconds, and 2 mL was added dropwise to a copper foil at a temperature of 25 ° C for 10 seconds. The lower limit value of the contact angle may be, for example, 40 ° or more, or 45 ° or more.

The viscosity of the photosensitive resin composition of this embodiment is adjusted by a E-type viscometer so that the measured viscosity becomes 50 mPa ･ s after rotating at a rotation frequency of 100 rpm and a temperature of 25 ° C for 300 seconds, and 2 mL is added dropwise at a temperature of 25 ° C The upper limit value of the contact angle after 10 seconds from the aluminum foil is, for example, preferably 14 ° or less, more preferably 13 ° or less, even more preferably 12 ° or less, and even more preferably 11 ° or less. When the contact angle is below the above-mentioned numerical range, the affinity between the varnish of the photosensitive resin composition and metal such as Al is improved, and the photosensitive resin composition can penetrate into the fine gaps generated by the surface of metal such as Al. Accordingly, when the photosensitive resin composition is used as a cured film, an anchor effect can be exhibited between the cured film and a metal such as Al, and adhesion can be improved. In addition, with an E-type viscometer, the viscosity was adjusted such that the measured viscosity became 50 mPa ･ s after rotating at a rotation frequency of 100 rpm and a temperature of 25 ° C for 300 seconds, and 2 mL was added dropwise to the aluminum foil at 25 ° C for 10 seconds. The lower limit value of the contact angle may be, for example, 1 ° or more, or 5 ° or more.

Supplementary explanation will be given for viscosity adjustment when measuring the above-mentioned contact angle. For the photosensitive resin composition having a viscosity of more than 50 mPa ･ s in the above-mentioned measuring method based on the E-type viscometer, the same solvent as the solvent contained in the photosensitive resin composition was used to adjust the viscosity to 50 mPa ･ s to measure the contact angle. When the photosensitive resin composition contains a mixed solvent, the viscosity is adjusted by the mixed solvent. In addition, for a photosensitive resin composition having a viscosity of less than 50 mPa ･ s based on the above-mentioned measurement method, a contact angle corresponding to a viscosity of 50 mPa ･ s can be obtained as follows. For example, it is assumed that there is a photosensitive resin composition having a viscosity of 40 mPa 基于 s based on the above-mentioned measurement method. The photosensitive resin composition is further diluted with the same solvent as the solvent contained in the photosensitive resin composition to prepare a photosensitive resin composition having a viscosity of 30, 20, 10 mPa ･ s, or the like. In addition, the relationship between the viscosity of the photosensitive resin composition with a viscosity of 10 to 40 mPa ･ s and the contact angle is plotted, and a straight line is drawn by the least square method, and the contact angle equivalent to the viscosity of 50 mPa ･ s is calculated. Out. Furthermore, the plotting is performed at the lowest 2 points, preferably at 3 or 4 points. Incidentally, as the findings of the present inventors, there is almost no difference in contact angle in a low viscosity region below 50 mPa50s, for example, 30 mPa ･ s and 50 mPa ･ s.

The inventors have studied the method of setting the contact angle with copper foil and aluminum foil to the above-mentioned numerical range with respect to the varnish of the photosensitive resin composition, and found that the urea compound and the acyclic compound contained in the solvent are appropriately controlled. The structure of the amidine compound having a crystalline structure, and the content of the urea compound and the acyclic amidine compound in the solvent are important. As the structure of the urea compound and the amidine compound having a non-cyclic structure contained in the solvent, more resonance structures are preferred. Specifically, the urea bond of the urea compound or the amidine bond of the amidine compound having a non-cyclic structure is preferably one having a large number of resonance structures formed by a lone electron pair of a nitrogen atom and a ketone site C = 0. The number of resonance structures of the urea compound and the amidine compound having a non-cyclic structure is, for example, preferably two or more, and more preferably three or more. Thereby, the electron cloud of the urea compound and the amidine compound having a non-cyclic structure is diffused, and the electronic state is stabilized. Therefore, it is considered that the surface free energy of the urea compound and the amidine compound having an acyclic structure is reduced, and the wettability to Cu can be improved. An example is given as the number of resonance structures. For example, the number of resonance structures of urea compounds such as tetramethylurea (TMU) is three. The content of the urea compound and the acyclic amine compound in the solvent also depends on the structure. For example, when the solvent is 100 parts by mass, it is preferably 30 parts by mass or more, and 50 parts by mass or more. More preferably, 70 parts by mass or more is further preferred, and 100 parts by mass is further preferred. Thereby, the state of the electrons in the solvent can be stabilized, and the contact angle can be set within the above-mentioned numerical range.

(Application) The photosensitive resin composition of this embodiment is used to form a resin film for electronic devices such as a permanent film and a resist. Among these, from the viewpoints of improving the adhesion between the photosensitive resin composition after pre-baking and the Al pad and suppressing the generation of residues of the photosensitive resin composition during development in a good balance, the sensitivity after post-baking is improved. From the viewpoint of the adhesion between the cured film of the flexible resin composition and the metal, and from the viewpoint of improving the chemical resistance of the photosensitive resin composition after post-baking, it is preferably used for applications using a permanent film. In addition, in this embodiment, a resin film means the dry film or hardened film of a photosensitive resin composition. That is, the resin film of this embodiment refers to a product obtained by drying or curing the photosensitive resin composition.

The permanent film is made of a resin film obtained by pre-baking, exposing and developing a photosensitive resin composition, patterning it into a desired shape, and then post-baking to harden it. The permanent film can be used for protective films, interlayer films, dam materials, and the like of electronic devices.

The above-mentioned resist is made of, for example, a resin film obtained by applying a photosensitive resin composition to the resist by a method such as spin coating, roll coating, flow coating, dip coating, spray coating, and blade coating. The solvent is removed from the photosensitive resin composition on the object covered by the agent.

An example of the electronic device of this embodiment is shown in FIG. The electronic device 100 according to this embodiment can be an electronic device including the resin film. Specifically, one or more of the group consisting of the passivation film 32, the insulating layer 42 and the insulating layer 44 in the electronic device 100 can be a resin film. Here, the resin film is preferably the permanent film.

The electronic device 100 is, for example, a semiconductor wafer. In this case, for example, the electronic device 100 is mounted on a wiring substrate via the bumps 52 to obtain a semiconductor package. The electronic device 100 includes a semiconductor substrate provided with a semiconductor element such as a transistor, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. An interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided on the uppermost layer of the multilayer wiring layers. The uppermost layer wiring 34 is made of, for example, aluminum Al. A passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34. An opening for exposing the uppermost layer wiring 34 is provided in a part of the passivation film 32.

A redistribution layer 40 is provided on the passivation film 32. The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and the rewiring 46. An opening is formed in the insulating layer 42 to be connected to the uppermost wiring 34. The rewiring 46 is formed on the insulating layer 42 and provided in the opening of the insulating layer 42, and is connected to the uppermost wiring 34. An opening connected to the redistribution wiring 46 is provided in the insulating layer 44.

In the opening provided in the insulating layer 44, for example, a bump 52 is formed through an UBM (Under Bump Metallurgy) layer 50. The electronic device 100 is connected to a wiring board or the like via a bump 52, for example.

In addition, the present invention is not limited to the aforementioned embodiments, and modifications, improvements, and the like within a range where the object of the present invention can be achieved are included by the inventor. [Example]

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited in any way by the examples.

First, the raw materials used in Examples and Comparative Examples will be described in detail.

<Alkali-soluble resin> First, the alkali-soluble resin used in each Example and each comparative example is demonstrated in detail.

(Alkali-soluble resin 1) The alkali-soluble resin 1 as a polyamide resin was synthesized by the following steps. In a four-necked glass separable flask equipped with a thermometer, a stirrer, a raw material input port, and a dry nitrogen introduction tube, diphenyl ether-4,4'-dicarboxylic acid 206.58 represented by the following formula (DC2) was placed. 170.20 g (0.346 mol) of dicarboxylic acid derivative mixture obtained by reacting g (0.800 mol) with 216.19 g (1.600 mol) of 1-hydroxy-1,2,3-benzotriazole hydrazone monohydrate, 5 -4.01 g (0.047 mol) of aminotetrazole, 45.22 g (0.196 mol) of 4,4'-methylenebis (2-aminophenol) represented by the following formula (DA2) and the following formula (DA3) The indicated 4,4'-methylenebis (2-amino-3,6-dimethylphenol) is 56.24 g (0.196 mol). Thereafter, 578.3 g of N-methyl-2-pyrrolidone was placed in the separable flask to dissolve each raw material component. Then, it was made to react at 90 degreeC for 5 hours using the oil bath. Next, in the separable flask, 24.34 g (0.141 mol) of 4-ethynylphthalic anhydride and 121.7 g of N-methyl-2-pyrrolidone were added, and stirred at 90 ° C for 2 hours while simultaneously After the reaction, the reaction was terminated after cooling to 23 ° C. The filtrate obtained by filtering the reaction mixture in the separable flask was put into a solution of water / isopropanol = 7/4 (volume ratio). Thereafter, the precipitate was collected by filtration, sufficiently washed with water, and then dried under vacuum, thereby obtaining an alkali-soluble resin 1. The weight-average molecular weight Mw of the obtained alkali-soluble resin 1 was 18,081.

<Photosensitizer> Next, the photosensitizer used in each Example and a comparative example is demonstrated in detail.

(Photosensitizer 1) Photosensitizer 1 as a diazoquinone compound was synthesized by the following steps. In a four-neck separable flask equipped with a thermometer, a stirrer, a raw material input port, and a dry nitrogen introduction tube, 11.04 g (0.026 mol) of phenol represented by the following formula (P-1) and 1,2-naphthoquinone- 18.81 g (0.070 mol) of 2-diazide-5-sulfosulfonyl chloride and 170 g of acetone were stirred to dissolve these. Next, while cooling the flask by a water bath so that the temperature of the reaction solution does not become 35 ° C or higher, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise at the same time. After reacting at room temperature for 3 hours in this state, 1.05 g (0.017 mol) of acetic acid was added, and the reaction was further performed for 30 minutes. Next, after filtering the reaction mixture, the filtrate was poured into a mixed solution of water / acetic acid (990 mL / 10 mL). Next, the precipitate was collected by filtration and sufficiently washed with water, and then dried under vacuum. Thereby, the photosensitive agent 1 represented by the structure of following formula (Q-1) was obtained.

<Solvent> As the solvent, the following solvents 1 to 3 were used. ･ Solvent 1: Tetramethylurea (TMU) as a linear urea compound ･ Solvent 2: Gamma-butyrolactone (GBL) ･ Solvent 3: N-methylpyrrolidine as a cyclic amidine compound Ketone (NMP)

<Adhesion aid> As the adhesion aid, the following adhesion aids 1 to 3 were used. Adhesion Adhesion Aid: N, N'-bis [3- (trimethoxysilyl) propyl] ethane-1,2-diamine (aminosilane) represented by the following formula (S1): X-12-5263HP manufactured by Shin-Etsu Chemical Co., Ltd.) Adhesion Adhesion Aid 2: Synthesized by the method described below and used as the carboxylic anhydride and 3-aminopropyl amine silane represented by the following formula (S2) Triethoxysilane

Hereinafter, the synthesis method of the adhesion promoter 2 which is a condensation product of a carboxylic acid anhydride and 3-aminopropyltriethoxysilane is demonstrated in detail. In an appropriately sized reaction vessel equipped with a stirrer and a cooling tube, cyclohexene-1,2-dicarboxylic anhydride (45.6 g, 300 mmol) was dissolved in N-methyl-2-pyrrolidone (970 g), and Adjust to 30 ° C in a thermostatic bath. Next, a dropping funnel was charged with 3-aminopropyltriethoxysilane (62 g, 280 mmol), and the solution was added dropwise over 60 minutes. After completion of the dropwise addition, stirring was performed under the conditions of 30 ° C. and 18 hours to obtain the adhesion promoter 2 represented by the following formula (S2).

<Thermal Crosslinking Agent> As the thermal crosslinking agent, the following thermal crosslinking agent 1 was used. ･ Heat crosslinker 1: P-xylene glycol (PXG manufactured by IHARANIKKEI CHEMICAL INDUSTRY)

<Surfactant> As the surfactant, the following surfactant 1 was used. ･ Surfactant 1: Fluorine surfactant (FC4430 manufactured by 3M Japan)

(Preparation of photosensitive resin composition of each Example and each comparative example) The photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 were prepared as follows. First, each of the above raw material components is prepared. Next, for those who use two or more solvents, the solvents are mixed according to the blending ratio shown in Table 1 below to prepare a mixed solvent. Next, each raw material other than the solvent was added to a solvent or a mixed solvent and stirred, and then filtered through a PTFE membrane filter having a pore size of 0.2 μm to obtain the photosensitive resin composition of each example and each comparative example. Varnish. The blending ratio of each raw material shown in Table 1 below is described in parts by mass.

The photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 were evaluated as follows.

(Viscosity) The varnishes of the photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 were rotated at a rotation frequency of 100 rpm and a temperature of 25 ° C. for 300 seconds using an E-type viscometer (TVE-22H manufactured by Toki Sangyo). The viscosity was then measured. The evaluation results are shown in Table 1 below. Here, the unit of viscosity is mPa ･ s.

(Contact Angle) Using the varnish of the photosensitive resin composition of Examples 1 to 3 and Comparative Example 1, the contact angle of the varnish was evaluated as follows. First, a smooth copper foil is prepared as a base material. Next, the contact angle after 10 seconds after 2 mL of the varnish of the photosensitive resin composition was dripped on a base material at the temperature of 25 degreeC by the droplet method was evaluated. The measurement was performed using a contact angle meter (DROPMASTER-501 manufactured by Kyowa Interface Science). In addition, those who used a smooth aluminum foil as a substrate instead of the smooth copper foil were also evaluated. The evaluation results are shown in Table 1 below. Here, the unit of the contact angle is °. Here, in Table 1 below, the description of ｢-｣ indicates that the evaluation was not performed. In addition, when measured by an E-type viscometer at a rotation frequency of 100 rpm and a temperature of 25 ° C. for 300 seconds, the viscosity of the varnish of each photosensitive resin composition of Examples 1 to 3 and Comparative Example 1 was 50 mPams. .

(Adhesiveness) Using the photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1, the adhesion between the post-baking photosensitive resin composition and aluminum (Al) was evaluated as follows. First, a silicon wafer is prepared as a base material. Next, titanium (Ti) was coated on the substrate so as to have a thickness of 0.05 μm (500 Å), and then Al was sputtered onto Ti so as to have a thickness of 0.3 μm (3000 Å). Next, a spin coater was used to apply The varnish of the photosensitive resin composition is applied on Al. Next, using a hot plate, pre-baking at a temperature of 120 ° C. for 4 minutes, and then using an oven under a nitrogen atmosphere at a temperature of 220 ° C. for 1 hour to obtain a cured film having a thickness of 7 μm. Here, the cured film is in close contact with Al. That is, a laminated structure in which a base material, Ti, Al, and a cured film are sequentially laminated is obtained. Using this laminated structure, the adhesion was evaluated in accordance with JIS D 0202. Specifically, the hardened film and Al were scratched from the surface where the hardened film in the laminated structure existed so as to form 100 squares of 1 mm square and singulated. Next, a cellophane tape was attached to the cured film. After 1 minute of adhesion, the cellophane tape was peeled from the cured film. After peeling, among the 100 squares, the number of squares remaining after the cured film and Al were not peeled and the number of squares after peeling were calculated, and this was used as the evaluation result of the PCT program at 0h. The so-called PCT program 0h means that no accelerated test has been performed. The evaluation results are shown in Table 1 below. Table 1 shows the number of squares after peeling. In the above, after the cellophane tape is adhered to the cured film, the cellophane tape is peeled from the cured film after being left at a temperature of 125 ° C., a humidity of 100%, and an air pressure of 2.3 atm for a specific time. After peeling, among the 100 squares, the number of squares remaining after the cured film and Al were not peeled and the number of squares after peeling were counted. Take this as the result of the PCT procedure evaluation at a specific time. As the time of the PCT procedure, 48h, 100h, 150h, 200h, and 300h were evaluated. The evaluation results are shown in Table 1 below. Table 1 shows the number of squares after peeling. The adhesiveness of the post-baking photosensitive resin composition and copper (Cu) was further evaluated. Specifically, instead of sputtering Al to a thickness of 0.05 μm (500 Å) on Ti, and sputtering copper (Cu) to a thickness of 0.5 μm (300 Å), the same procedure was used except for the sputtering. The method evaluated the adhesion of the photosensitive resin composition and aluminum (Al). The evaluation results are shown in Table 1 below. In addition, the evaluation results of the adhesion are all small, that is, the smaller the number of squares after peeling, the higher the adhesion between the cured film and Al and Cu. The PCT program is intended to accelerate the tester and is used to evaluate the long-term adhesion between the photosensitive resin composition after post-baking and Al and Cu.

[Table 1]

As shown in Table 1 above, it was confirmed that the photosensitive resin composition of each Example has a smaller contact angle with metals such as Cu and Al than the photosensitive resin composition of Comparative Example 1 and good affinity. In addition, it was confirmed that the cured film obtained by post-baking the photosensitive resin composition of each example is more resistant to metals such as Cu and Al than the cured film obtained by post-baking the photosensitive resin composition of each comparative example. The tightness is improved.

In addition, it was confirmed that, in addition to the above Examples 1 to 3, a photosensitive resin composition having a small blending amount of the solvent can be appropriately applied. As in Examples 1 to 3, the adhesiveness is improved, and therefore the preparation is performed. The photosensitive resin composition of Examples 4-7. The preparation method of the photosensitive resin composition of Examples 4-7 is the same as that of the said Examples 1-3. The blending ratios of Examples 4 to 7 are shown in Table 2 below. In addition, the blending ratio of each raw material shown in the following Table 2 is described in mass parts. With respect to the prepared photosensitive resin compositions of Examples 4 to 7, the same methods as those of Examples 1 to 3 were used to evaluate the viscosity and adhesion. Here, coating can be performed without any problems in the same manner as in Examples 1 to 3. The evaluation results are shown in Table 2 below.

[Table 2]

As described above, it was confirmed that the photosensitive resin composition of Examples 4 to 7 has a smaller blending amount of the solvent than the photosensitive resin composition of Examples 1 to 3, but can be applied without any problems. In the same manner as the photosensitive resin composition of Examples 1 to 3, it exhibited adhesion to metals such as Cu and Al after post-baking.

The evaluations of Examples 8 to 13 and Comparative Example 2 below were further performed. Examples 8 to 13 are those containing an amidamine compound having a non-cyclic structure as a solvent. First, each raw material component shown in Table 3 was prepared. Next, for those who use two or more solvents, the solvents are mixed according to the blending ratios shown in Table 3 below, and mixed solvents are prepared. Next, each raw material other than the solvent was added to a solvent or a mixed solvent and stirred, and then filtered through a PTFE membrane filter having a pore size of 0.2 μm to obtain a varnish of a photosensitive resin composition. In addition, the blending ratio of each raw material in Table 3 is a mass part.

Among the raw material components shown in Table 3, the solvent 4 is the following. The other raw material components are the same as those described in Table 1 or Table 2. ･ Solvent 4: 3-methoxy-N, N-dimethylpropanamide as a fluorene compound having a non-cyclic structure

About the photosensitive resin composition of Table 3, the viscosity and adhesiveness were evaluated by the same method as Examples 1-3. Here, coating can be performed without any problems in the same manner as in Examples 1 to 3. In addition, for Examples 11 to 13, the contact angle was measured by the same method as in Examples 1 to 3. The evaluation results are shown in Table 3.

[table 3]

As shown in Table 3, even when the amidine compound having a non-cyclic structure is used as a solvent, the adhesion to metals such as Cu and Al after post-baking is remarkably good.

This application claims the priority based on Japanese Patent Application No. 2017-129670 filed on June 30, 2017, and incorporates the entire disclosure thereof into this document.

30‧‧‧ interlayer insulation film

32‧‧‧ passivation film

34‧‧‧ Top-level wiring

40‧‧‧ redistribution layer

42‧‧‧ Insulation

44‧‧‧ Insulation

46‧‧‧Re-wiring

50‧‧‧UBM floor

52‧‧‧ bump

100‧‧‧ electronic device

FIG. 1 is a cross-sectional view showing an example of an electronic device according to this embodiment.

Claims (15)

A photosensitive resin composition comprising: an alkali-soluble resin; a photosensitizer; and a solvent, wherein the solvent includes a urea compound or an amidine compound having a non-cyclic structure. For example, the photosensitive resin composition of the first patent application range, wherein the photosensitive resin composition is used to form a permanent film, the permanent film is an interlayer film, a surface protection film, or a dam material. For example, the photosensitive resin composition according to item 1 or 2 of the patent application range, wherein the content of the urea compound and the acyclic amine compound in the solvent is 10 parts by mass or more with respect to 100 parts by mass of the solvent and 100 parts by mass or less. For example, the photosensitive resin composition according to claim 1 or 2, wherein the solvent contains the urea compound, and the structure of the urea compound is an acyclic structure. For example, the photosensitive resin composition according to claim 4 of the application, wherein the urea compound is tetramethylurea. For example, the photosensitive resin composition of claim 1 or 2, wherein the alkali-soluble resin is selected from the group consisting of polyamide resin, polybenzoxazole resin, polyimide resin, phenol resin, and hydroxystyrene resin. And one or more of the group consisting of a cyclic olefin resin. For example, the photosensitive resin composition of claim 6 in which the alkali-soluble resin includes the polyamide resin, and the polyamide resin includes a structural unit represented by the following formula (PA1), . For example, the photosensitive resin composition of the seventh scope of the application for a patent, wherein the polyamide resin includes structural units represented by the following general formula (PA2) and the following general formula (PA3), In the general formula (PA2), R ⁴ is one selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. Or a group formed by two or more kinds of atoms; R ⁵ to R ¹⁰ each independently represent hydrogen or an organic group having 1 to 30 carbon atoms, In the general formula (PA3), R ¹¹ is one selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. Or a group formed by two or more kinds of atoms; R ¹² to R ¹⁹ each independently represent hydrogen or an organic group having 1 to 30 carbon atoms. For example, when the photosensitive resin composition of the first or second patent application scope is applied, and the total solid content of the photosensitive resin composition is 100 parts by mass, the content of the alkali-soluble resin in the photosensitive resin composition is 30 mass parts or more and 95 mass parts or less. For example, the photosensitive resin composition according to claim 1 or 2, wherein the photosensitive agent is a diazoquinone compound. For example, the photosensitive resin composition according to item 1 or 2 of the patent application scope, wherein the photosensitive resin composition further includes an adhesion assistant, and the adhesion assistant is a triazole compound, an aminosilane, or a sulfonimide compound. For example, the photosensitive resin composition in the scope of patent application No. 1 or 2, in which the viscosity is measured by an E-type viscometer so that the viscosity measured after rotating at a rotation frequency of 100 rpm and a temperature of 25 ° C for 300 seconds becomes 50 mPa ･ s. The contact angle of the photosensitive resin composition obtained by adjusting the viscosity of the copper foil at a temperature of 25 ° C. for 10 seconds was 70 ° or less. For example, the photosensitive resin composition of the first or second patent application scope, in which the viscosity of the photosensitive resin composition measured with an E-type viscometer after the rotation starts at a temperature of 25 ° C for 300 seconds is 50 mPa ･ s or more and Below 2000mPa ･ s. A resin film is obtained by curing the photosensitive resin composition according to any one of claims 1 to 13. An electronic device includes a resin film with a scope of application for item 14 of the patent.