JP6566150B2 - Photosensitive resin composition, resin film and electronic device - Google Patents

Description

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

Until now, in the field of photosensitive resin compositions, various techniques have been developed for the purpose of obtaining a photosensitive resin composition that can form a cured film that is not brittle and has high heat resistance even when cured at low temperatures. ing. As this type of technology, the technology described in Patent Document 1 can be cited.
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 less exhibits a high elongation at break. Has been.

JP 2007-213032 A

In the case where the photosensitive resin composition described in Patent Document 1 is used as a permanent film of an electronic device, the present inventors have provided an aluminum (Al) pad provided for input / output of a substrate of an electronic device and copper as an electric circuit. The adhesion between the (Cu) circuit and the permanent film was examined. The permanent film is obtained by pre-baking, exposing and developing the photosensitive resin composition, producing a resin film patterned into a desired shape, and then curing the resin film by post-baking. The cured film obtained.
As a result of the above studies, it has been found that the cured film formed using the photosensitive resin composition described in Patent Document 1 has insufficient adhesion to Al pads and Cu circuits.
Then, this invention makes it a subject to improve the adhesiveness of the cured film obtained by post-baking the photosensitive resin composition, and metals, such as Al and Cu.

  In order to improve the adhesiveness between the cured film of the photosensitive resin composition after post-baking and a metal such as Al or Cu, the present inventors have examined the raw material components of the photosensitive resin composition. As a result, it has been found that the inclusion of a specific solvent as a raw material component can improve the adhesion between the cured film of the photosensitive resin composition after post-baking and a metal such as Al or Cu, and the present invention has been completed. .

According to the present invention, an alkali-soluble resin;
A photosensitizer,
A solvent,
The alkali-soluble resin is a polyamide resin containing structural units represented by the following general formula (PA2) and the following general formula (PA3),
The solvent includes a urea compound,
The structure of the urea compound is an acyclic structure,
The photosensitive resin composition in which the content of the urea compound in 100 parts by mass of the solvent is 30 parts by mass or more is provided. However, the organic group having 1 to 30 carbon atoms of R ^{12 to} R ¹⁹ in the general formula (PA3) is an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, a cycloalkyl group, or an alkaryl group. Any one selected from the group consisting of

  Moreover, according to this invention, the resin film formed by hardening | curing the said photosensitive resin composition is provided.

  Moreover, according to this invention, an electronic apparatus provided with the said resin film is 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 a metal such as Al or Cu.

  The above-described object and other objects, features, and advantages will become more apparent from the preferred embodiments described below and the accompanying drawings.

It is sectional drawing which shows an example of the electronic device which concerns on this embodiment.

  Hereinafter, the present embodiment will be described with reference to the drawings as appropriate. In all the drawings, the same symbols are attached to the same components, and the description thereof is omitted.

  The photosensitive resin composition according to this embodiment includes an alkali-soluble resin, a photosensitive agent, and a solvent, and the solvent includes a urea compound or an amide compound having an acyclic structure.

  In recent years, with miniaturization of electronic devices, metal members such as Al pads and copper circuits of electronic devices tend to be smaller. Here, when a metal member becomes small, the adhesive force 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 off. In the case where the cured film is peeled off, there is a problem in that a leakage current or the like is generated from the place where the peeling occurs and the electrical reliability of the electronic device is lowered.

The present inventors examined the raw material components of the photosensitive resin composition that can improve the adhesion between the cured film of the photosensitive resin composition after post-baking and a metal such as an Al pad and a copper circuit. As a result, it has been found that the adhesion can be improved by including a urea compound or an amide compound having an acyclic structure as a solvent of the photosensitive resin composition.
Although the detailed mechanism which can improve adhesiveness is not certain, it estimates as follows. As a mechanism for improving the adhesion, first, the lone electron pair provided in the urea compound and the amide compound having an acyclic structure and a metal atom such as Al and Cu form a strong coordinate bond. Conceivable. Thereby, it is thought that the varnish-containing component of the photosensitive resin composition before drying is strongly bound to a metal such as Al and Cu by being pulled by the coordinate bond formed by the solvent. After that, when the photosensitive resin composition is pre-baked, exposed and developed to produce a resin film patterned into a desired shape, and then cured by post-baking the resin film to produce a cured film It is presumed that the molecular coordination of the components other than the solvent of the photosensitive resin composition can be frozen while the coordination of the components other than the solvent of the photosensitive resin composition and the metal atoms are strongly linked. Therefore, it is considered that the adhesion between the post-baked cured film and a metal such as Al or Cu can be improved.
In addition, it is estimated that the mechanism which forms the strong coordinate bond mentioned above differs between a urea compound and the amide compound of an acyclic structure. First, as a premise, in a conventional photosensitive resin composition, an amide compound having a cyclic structure such as N-methylpyrrolidone (NMP) was used as a solvent. The urea compound has two or more nitrogen atoms having a lone electron pair in the molecular structure due to a urea bond. Thus, it is presumed that the coordination bond becomes stronger in proportion to the number of lone pairs. Therefore, when a urea compound is used, it is thought that a strong coordinate bond can be formed compared with the compound used for the solvent of the conventional photosensitive resin composition. Moreover, it is estimated that the amide compound of a non-cyclic structure is easy to form a coordinate bond compared with the amide compound of the cyclic structure used for the conventional photosensitive resin composition. This is presumably because an amide compound having an acyclic structure has less molecular movement constraints and a greater degree of freedom in deformation of the molecular structure than an amide compound having a cyclic structure. Therefore, it is considered that when an amide compound having an acyclic structure is used, a stronger coordinate bond can be formed as compared with a compound used as a solvent for a conventional photosensitive resin composition.
As mentioned above, it is estimated that the photosensitive resin composition which concerns on this embodiment can improve the adhesiveness of the post-baking cured film and metals, such as Al and Cu, by including a specific compound as a solvent.

In addition to the improvement in adhesion between the cured film after post-baking and the metal such as Al and Cu, the urea compound is more effective for the human body than the solvent used in the conventional photosensitive resin composition. It is also convenient from the viewpoint that there are few adverse effects. Conventionally used cyclic structure amide compounds such as N-methylpyrrolidone have various adverse effects such as impaired reproductive function when taken into the human body, and the production process of the photosensitive resin composition is considered in consideration of safety. It was necessary to devise. However, urea compounds are advantageous in that no detrimental effects on the production process are required because the adverse effects on the human body are slight.
Examples of urea compounds that have little adverse effect on the human body include tetramethylurea.

  First, each raw material component of the photosensitive resin composition according to the present embodiment will be described.

(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 polyamide resin, polybenzoxazole resin, phenol resin, and hydroxystyrene resin. Among the above specific examples, for example, polyamide resin or polybenzoxazole resin is preferably used as the alkali-soluble resin. Thereby, it is considered that a strong interaction such as a hydrogen bond can be formed between the amide bond of the polyamide resin and the urea compound or the amide compound having an acyclic 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 the metal molecule are more strongly bound. In addition, as alkali-soluble resin, 1 type (s) or 2 or more types can be included among the said specific examples.

<Polyamide resin, polybenzoxazole resin>
As the polyamide resin, for example, an aromatic polyamide containing an aromatic ring in the polyamide structural unit is preferably used, and one containing a structural unit represented by the following formula (PA1) is more preferable. As a result, the molecular chains of the polyamide resin are hydrogen-bonded via amide bonds, and the aromatic ring portion is closely molecularly aligned, so that the alkali-soluble resin and the metal molecule are more strongly linked. Freeze molecular structure. This coordination is more suitable for improving adhesion when the solvent contains tetramethylurea as a urea compound. Therefore, it is preferable from the viewpoint of improving adhesion that the polyamide resin is used as the alkali-soluble resin and the solvent contains tetramethylurea as the urea compound.
In the present embodiment, the aromatic ring refers to a benzene ring; a condensed aromatic ring such as a naphthalene ring, an anthracene ring, or a pyrene ring; a heteroaromatic ring such as a pyridine ring or a pyrrole ring. The polyamide resin of this embodiment preferably contains a benzene ring as an aromatic ring from the viewpoint of forming the dense structure.

The polyamide resin containing the structural unit represented by the above formula (PA1) is a precursor of a polybenzoxazole resin. The polyamide resin containing the structural unit represented by the above formula (PA1) is subjected to dehydration and ring closure by heat treatment at a temperature of 150 ° C. or higher and 380 ° C. or lower for 30 minutes to 50 hours, for example. It can be an oxazole resin. Here, the structural unit of the above formula (PA1) becomes a structural unit represented by the following formula (PBO1) by dehydration ring closure.
When the alkali-soluble resin according to this embodiment is a polyamide resin containing the structural unit represented by the above formula (PA1), for example, the heat treatment is performed on the photosensitive resin composition to perform dehydration and cyclization to form a polybenzoxazole resin. It is good. That is, the heat-treated photosensitive resin composition includes a polybenzoxazole resin that is an alkali-soluble resin.
In addition, when the alkali-soluble resin is a polyamide resin containing a structural unit represented by the above formula (PA1), a resin film and an electronic device to be described later are manufactured, and then the heat treatment is performed to perform dehydration and ring closure. Oxazole resin may be used. When a polybenzoxazole resin is obtained by dehydrating and opening a polyamide resin, the tensile elongation at break and the glass transition temperature can be increased. This is convenient from the viewpoint of improving the strength and heat resistance of the resin film and the electronic device.

<Production method of polyamide resin>
The polyamide resin according to this embodiment is polymerized as follows, for example.
First, polyamide is polymerized by polycondensation of a diamine monomer and a dicarboxylic acid monomer in the polymerization step (S1). Next, in the low molecular weight component removing step (S2), the low molecular weight component is removed to obtain a polyamide resin mainly composed of polyamide.

(Polymerization step (S1))
In the polymerization step (S1), a diamine monomer and a dicarboxylic acid monomer are polycondensed. The polycondensation method for polymerizing polyamide is not limited, and specific examples include melt polycondensation, acid chloride method, and direct polycondensation.
Instead of the dicarboxylic acid monomer, a compound selected from the group consisting of tetracarboxylic dianhydride, trimellitic anhydride, dicarboxylic acid dichloride, or active ester type dicarboxylic acid may be used. Specific examples of a method for obtaining an active ester dicarboxylic acid include a method in which a dicarboxylic acid is reacted with 1-hydroxy-1,2,3-benzotriazole or the like.

  The diamine monomer and dicarboxylic acid monomer used for the polymerization of the polyamide resin will be described below. One diamine monomer and one dicarboxylic acid monomer may be prepared, or two or more diamine monomers may be used in combination.

<Diamine monomer>
It does not limit as a diamine monomer used for superposition | polymerization, For example, it is preferable to use the diamine monomer which contains an aromatic ring in a structure, and it is more preferable to use the diamine monomer which contains a phenolic hydroxyl group in a structure. Here, as a diamine monomer containing a phenolic hydroxyl group in the structure, for example, a product represented by the following general formula (DA1) is preferable. By producing a polyamide resin using such a diamine monomer as a raw material, the conformation of the polyamide resin can be controlled, and the molecular chains of the polyamide resin can form a denser structure. 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 bound.
For example, when a diamine monomer represented by the following general formula (DA1) is used, the polyamide resin includes a structural unit represented by the following general formula (PA2). That is, the polyamide resin according to the present embodiment preferably includes, for example, a structural unit represented by the following general formula (PA2).

（上記一般式（ＤＡ１）において、Ｒ^４は、水素原子、炭素原子、酸素原子、窒素原子、硫黄原子、リン原子、ケイ素原子、塩素原子、フッ素原子、臭素原子からなる群より選択される１種または２種以上の原子によって形成される基である。Ｒ^５−Ｒ^１０は、それぞれ独立して、水素または炭素数１以上３０以下の有機基を表す。）

(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. And a group formed by two or more kinds of atoms, R ^{5 to} R ¹⁰ each independently represents hydrogen or an organic group having 1 to 30 carbon atoms.)

（上記一般式（ＰＡ２）において、Ｒ^４、Ｒ^５−Ｒ^１０は、上記一般式（ＤＡ１）と同様である。）

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

R ⁴ in the general formulas (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 group formed by one or more atoms.
R ⁴ is a divalent group. Here, the divalent group indicates a valence. That is, R ⁴ has two bonds that are bonded to other atoms.

When R ⁴ in the general formulas (DA1) and (PA2) includes a carbon atom, R ⁴ is, for example, a group having 1 to 30 carbon atoms, and preferably a group having 1 to 10 carbon atoms, A group having 1 to 5 carbon atoms is more preferable, and a group having 1 to 3 carbon atoms is more preferable.

When R ⁴ in the general formulas (DA1) and (PA2) contains a carbon atom, specific examples of R ⁴ include an alkylene group, an arylene group, a halogen-substituted alkylene group, and a halogen-substituted arylene group.
The alkylene group may be, for example, a linear alkylene group or a branched alkylene group. Specific examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decanylene group, a trimethylene group, and a tetramethylene group. , Pentamethylene group, hexamethylene group and the like. Specific examples of the branched alkylene group include —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ) (CH ₂ ). _{CH 3) -, - C (} CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - alkyl methylene group, such _{as; -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 - alkyl, such as ethylene Group and the like.
Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a group in which two or more arylene groups are bonded to each other.
Specifically, as the halogen-substituted alkylene group and halogen-substituted arylene group, those obtained by substituting hydrogen atoms in the above-described alkylene group and arylene group with halogen atoms such as fluorine atom, chlorine atom and bromine atom, respectively, should be used. Can do. Among these, what uses what substituted the hydrogen atom by the fluorine atom is preferable.

When R ⁴ in the above general formulas (DA1) and (PA2) does not contain a carbon atom, specifically, R ⁴ includes a group consisting of an oxygen atom or a sulfur atom.

R ⁵ -R ¹⁰ in the general formulas (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. It is preferably hydrogen or an organic group having 1 to 5 carbon atoms, more preferably hydrogen or an organic group having 1 to 3 carbon atoms, hydrogen or 1 to 2 carbon atoms. The organic group is more preferable. Thereby, the aromatic rings of a polyamide resin can be arranged closely. 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 bound.

Specific examples of the organic group having 1 to 30 carbon atoms of R ^{5 to} R ¹⁰ in the general formulas (DA1) and (PA2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Alkyl groups such as isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group; alkenyl groups such as allyl group, pentenyl group and vinyl group Group; alkynyl group such as ethynyl group; alkylidene group such as methylidene group and ethylidene group; aryl group such as tolyl group, xylyl group, phenyl group, naphthyl group and anthracenyl group; aralkyl group such as benzyl group and phenethyl group; adamantyl group , Cyclopentyl group, cyclohexyl group, cyclooctyl group and other cycloalkyl groups Tolyl group, and alkaryl groups, such as xylyl group.

Specific examples of the diamine monomer represented by the general formula (DA1) include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4,4′-methylenebis (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 densely arranged. 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 bound. In addition, as a diamine monomer, it can use 1 type or in combination of 2 or more types among the said specific examples.
The structural formulas of these diamine monomers are shown below.

<Dicarboxylic acid monomer>
The dicarboxylic acid monomer used for the polymerization is not limited. For example, it is preferable to use a dicarboxylic acid monomer having an aromatic ring in the structure.
As the dicarboxylic acid monomer containing an aromatic ring, for example, a monomer represented by the following general formula (DC1) is preferably used.
For example, when a dicarboxylic acid monomer represented by the following general formula (DC1) is used, the polyamide resin includes a structural unit represented by the following general formula (PA3). That is, the polyamide resin according to the present embodiment preferably includes, for example, a structural unit represented by the following general formula (DC1). Thereby, the aromatic rings of a polyamide resin can be arranged closely. 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 bound.

（上記一般式（ＤＣ１）において、Ｒ^１１は、水素原子、炭素原子、酸素原子、窒素原子、硫黄原子、リン原子、ケイ素原子、塩素原子、フッ素原子、臭素原子からなる群より選択される１種または２種以上の原子によって形成される基である。Ｒ^１２−Ｒ^１９は、それぞれ独立して、水素または炭素数１以上３０以下の有機基を表す。）

(In the above 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. And a group formed by two or more kinds of atoms, R ^{12 to} R ¹⁹ each independently represents hydrogen or an organic group having 1 to 30 carbon atoms.)

（上記一般式（ＰＡ３）において、Ｒ^１１、Ｒ^１２−Ｒ^１９は、上記一般式（ＤＣ１）と同様である。）

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

R ¹¹ in the general formulas (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 group formed by one or more atoms.
R ¹¹ is a divalent group. Here, the divalent group indicates a valence. That is, R ¹¹ has two bonds that bond to other atoms.

When R ¹¹ in the general formulas (DC1) and (PA3) contains a carbon atom, R ¹¹ is, for example, a group having 1 to 30 carbon atoms, and preferably a group having 1 to 10 carbon atoms, A group having 1 to 5 carbon atoms is more preferable, and a group having 1 to 3 carbon atoms is more preferable.

When R ¹¹ in the general formulas (DC1) and (PA3) contains a carbon atom, specific examples of R ¹¹ include an alkylene group, an arylene group, a halogen-substituted alkylene group, and a halogen-substituted arylene group.
The alkylene group may be, for example, a linear alkylene group or a branched alkylene group. Specific examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decanylene group, a trimethylene group, and a tetramethylene group. , Pentamethylene group, hexamethylene group and the like. Specific examples of the branched alkylene group include —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ) (CH ₂ ). _{CH 3) -, - C (} CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - alkyl methylene group, such _{as; -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 - alkyl, such as ethylene Group and the like.
Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a group in which two or more arylene groups are bonded to each other.
Specifically, as the halogen-substituted alkylene group and halogen-substituted arylene group, those obtained by substituting hydrogen atoms in the above-described alkylene group and arylene group with halogen atoms such as fluorine atom, chlorine atom and bromine atom, respectively, should be used. Can do. Among these, what uses what substituted the hydrogen atom by the fluorine atom is preferable.

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

R ^{12 to} R ¹⁹ in the general formulas (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. It is preferably hydrogen or an organic group having 1 to 5 carbon atoms, more preferably hydrogen or an organic group having 1 to 3 carbon atoms, and even more preferably hydrogen.

Specific examples of the organic group having 1 to 30 carbon atoms of R ^{12 to} R ¹⁹ in the general formulas (DC1) and (PA3) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Alkyl groups such as isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group; alkenyl groups such as allyl group, pentenyl group and vinyl group Group; alkynyl group such as ethynyl group; alkylidene group such as methylidene group and ethylidene group; aryl group such as tolyl group, xylyl group, phenyl group, naphthyl group and anthracenyl group; aralkyl group such as benzyl group and phenethyl group; adamantyl group , Cyclopentyl group, cyclohexyl group, cyclooctyl group and other cycloalkyl Tolyl group, and alkaryl groups, such as xylyl group.

  Specific examples of the dicarboxylic acid monomer include diphenyl ether 4,4'-dicarboxylic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, and the like. Of the above specific examples, diphenyl ether 4,4'-dicarboxylic acid or isophthalic acid is preferably used as the dicarboxylic acid monomer, and diphenyl ether 4,4'-dicarboxylic acid is more preferably used. The aromatic rings of the polyamide resin can be closely arranged. 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 bound.

In addition, it is preferable to modify the amino group present at the end of the polyamide resin simultaneously with 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, the polyamide resin according to the present embodiment is preferably formed by modifying the terminal amino group with a specific acid anhydride or a specific monocarboxylic acid. In addition, the said specific acid anhydride and the said specific monocarboxylic acid have 1 or more types of functional groups which consist of a group which consists of an alkenyl group, an alkynyl group, and a hydroxyl group. Moreover, as said specific acid anhydride and specific monocarboxylic acid, what contains a nitrogen atom, for example is preferable. Thereby, the adhesiveness of the photosensitive resin composition after post-baking and metals, such as Al and Cu, can be improved.
Specific examples of the acid anhydride include maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, exo-3. , 6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, itaconic acid anhydride Products, het acid anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride, and the like. As a specific acid anhydride, it can use 1 type or in combination of 2 or more types among the said specific examples.
In addition, when the amino group which exists in the terminal of a polyamide resin is modified with the ring-shaped specific acid anhydride, the ring-shaped specific acid anhydride is opened. Here, after modifying the polyamide resin, a structural unit derived from a specific acid anhydride having a ring shape may be closed to form an imide ring. Examples of the ring closing method include heat treatment.
Specific examples of the specific monocarboxylic acid include 5-norbornene-2-carboxylic acid, 4-hydroxybenzoic acid, and 3-hydroxybenzoic acid. As said specific monocarboxylic acid, 1 type (s) or 2 or more types can be used in combination among the said specific examples.

Moreover, you may modify the carboxyl group which exists in the terminal of a polyamide resin simultaneously with a superposition | polymerization process (S1) or after a superposition | polymerization process (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 according to this embodiment is preferably formed by modifying the terminal carboxyl group with a specific nitrogen atom-containing heteroaromatic compound. The specific nitrogen atom-containing heteroaromatic compound includes 1- (5-1H-triazoyl) methylamino group, 3- (1H-pyrazoyl) amino group, 4- (1H-pyrazoyl) amino group, 5- (1H-pyrazoyl) amino group, 1- (3-1H-pyrazoyl) methylamino group, 1- (4-1H-pyrazoyl) methylamino group, 1- (5-1H-pyrazoyl) methylamino group, (1H- One or more functional groups consisting of the group consisting of tetrazol-5-yl) amino group, 1- (1H-tetrazol-5-yl) methyl-amino group and 3- (1H-tetrazol-5-yl) benz-amino group It has a group. Thereby, the number of lone electron pairs in the photosensitive resin composition can be increased. Therefore, the adhesiveness between the pre-baked and post-baked photosensitive resin composition and a metal such as Al can be improved.
Specific examples of the specific nitrogen atom-containing heteroaromatic compound include 5-aminotetrazole.

(Low molecular weight component removal step (S2))
Subsequent to the polymerization step (S1), a low molecular weight component removal step (S2) is performed to remove the low molecular weight component to obtain a polyamide resin containing a polyamide resin as a main component.
An organic layer containing a mixture of a low molecular weight component and a polyamide resin is concentrated by filtration or the like and then dissolved again in an organic solvent such as water / isopropanol. Thereby, the polyamide resin from which the precipitate was filtered and the 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, those having the structural units of the general formulas (PA2) and (PA3) are preferable, and those having the structural units of the general formulas (PA2) and (PA3) alternately are more preferable.

<Phenolic resin>
Specific examples of the phenol resin include phenol novolac resins, cresol novolac resins, bisphenol novolac resins, phenol-biphenyl novolac resins and other novolac type phenol resins; novolac type phenol resins, resol type phenol resins, cresol novolak resins A reaction product of a compound and an aldehyde compound; a reaction product of a phenol compound such as a phenol aralkyl resin and a dimethanol compound. In addition, as a phenol resin, 1 type (s) or 2 or more types can be included among the said specific examples.

The phenol compound used for the reaction product of the phenol compound and the aldehyde compound or the reaction product of the phenol compound and the dimethanol compound described above is not limited.
Specific examples of such a phenol compound include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2 , 6-xylenol, 3,4-xylenol, xylenols such as 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol; isopropylphenol, butylphenol, p-tert- Examples include alkylphenols such as butylphenol; polyphenols such as resorcinol, catechol, hydroquinone, pyrogallol, and phloroglucinol; and biphenyl phenols such as 4,4′-biphenol. As a phenol compound, 1 type (s) or 2 or more types can be used among the said specific examples.

The aldehyde compound used for the reaction product of the phenol compound and the aldehyde compound described above is not limited as long as it is a compound having an aldehyde group.
Specific examples of such aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, salicylaldehyde, and the like. As an aldehyde compound, 1 type (s) or 2 or more types can be used among the said specific examples.

It is not limited as a dimethanol compound used for the reaction material of a phenol compound and a dimethanol compound mentioned above.
Specific examples of such a dimethanol compound include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4′-biphenyldimethanol, 3,4′-biphenyldimethanol, 3, Dimethanol compounds such as 3′-biphenyldimethanol, 2,6-naphthalenediethanol, 2,6-bis (hydroxymethyl) -p-cresol; 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, methyl 2,6-naphthalenedicarboxylate Bis (alkoxymethyl) compounds such as 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 (hargenoalkyl) compounds such as bis (chloromethyl) biphenyl, 4,4′-bis (bromomethyl) biphenyl, 3,4′-bis (bromomethyl) biphenyl or 3,3′-bis (bromomethyl) biphenyl, And biphenyl aralkyl compounds such as 4,4′-bis (methoxymethyl) biphenyl and 4,4′-bis (methoxymethyl) biphenyl. As a dimethanol compound, 1 type (s) or 2 or more types can be used among the said specific examples.

<Hydroxystyrene resin>
The hydroxystyrene resin is not limited, and specifically, a polymerization reaction product or copolymer obtained by polymerizing or copolymerizing one or more selected from the group consisting of hydroxystyrene, hydroxystyrene derivatives, styrene and styrene derivatives. A polymerization reaction product can be used.
Specific examples of the hydroxystyrene derivative and the styrene derivative include hydroxystyrene and those obtained by substituting a hydrogen atom of an aromatic ring of styrene with a monovalent organic group. Examples of the monovalent organic group for substituting a hydrogen atom include alkyl groups such as methyl group, ethyl group and n-propyl group; alkenyl groups such as allyl group and vinyl group; alkynyl groups such as ethynyl group; An alkylidene group such as an ethylidene group; a cycloalkyl group such as a cyclopropyl group; and a heterocyclic group such as an epoxy group oxetanyl group.

<Cyclic olefin resin>
The cyclic olefin-based resin is not limited, and specifically, a polymerization reaction product or a copolymerization reaction product obtained by polymerizing or copolymerizing one or more selected from the group consisting of norbornene and norbornene derivatives is used. be able to.
Specific examples of the norbornene derivative include those obtained by substituting a hydrogen atom bonded to the norbornene skeleton with a monovalent organic group. Examples of the monovalent organic group for substituting a hydrogen atom include alkyl groups such as methyl group, ethyl group and n-propyl group; alkenyl groups such as allyl group and vinyl group; alkynyl groups such as ethynyl group; An alkylidene group such as an ethylidene group; a cycloalkyl group such as a cyclopropyl group; and a heterocyclic group such as an epoxy group oxetanyl group.

The lower limit of the content of the alkali-soluble resin in the photosensitive resin composition is, for example, preferably 30 parts by mass or more and 40 parts by mass when the total solid content of the photosensitive resin composition is 100 parts by mass. More preferably, it is more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more. Thereby, the alkali-soluble resin in the photosensitive resin composition can preferably interact with the urea compound or the amide compound having an acyclic structure in the solvent. 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 bound.
The upper limit of the content of the alkali-soluble resin in the photosensitive resin composition is preferably 95 parts by mass or less, for example, when the total solid content of the photosensitive resin composition is 100 parts by mass, More preferably, it is less than or equal to part by weight, and even more preferably less than or equal to 85 parts by weight.
In the present embodiment, the total solid content of the photosensitive resin composition indicates the total content of the photosensitive resin composition excluding the solvent.

(Photosensitive agent)
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 diaryliodonium salt; a 2-nitrobenzyl ester compound; an N-iminosulfonate compound; an imidesulfonate compound; and 2,6-bis (trichloromethyl) -1,3. 5-triazine compounds; dihydropyridine compounds and the like. Among these, it is preferable to use a photosensitive diazoquinone compound. Thereby, the sensitivity of the photosensitive resin composition can be improved. Therefore, the accuracy of the pattern can be improved and the appearance can be improved. In addition, as a photo-acid generator, 1 type (s) or 2 or more types can be included among the said specific examples.
When the photosensitive resin composition is a positive type, in addition to the above specific examples, triarylsulfonium salts; onium salts such as sulfonium borate salts and the like may be used in combination. Thereby, the sensitivity of the photosensitive resin composition can be further improved.
Specific examples of the diazoquinone compound that can be preferably used as the photosensitizer are shown below.

（ｎは、１以上、５以下の整数である。）

(N is an integer of 1 or more and 5 or less.)

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

The lower limit of the content of the photosensitive agent in the photosensitive resin composition is, for example, preferably 1 part by mass or more and more preferably 3 parts by mass or more when the alkali-soluble resin is 100 parts by mass. More preferably, it is 5 parts by mass or more. Thereby, the photosensitive resin composition can exhibit appropriate sensitivity.
Further, the upper limit of the content of the photosensitive agent in the photosensitive resin composition is preferably 30 parts by mass or less, and preferably 20 parts by mass or less, when the alkali-soluble resin is 100 parts by mass. More preferred. Thereby, the photosensitive resin composition is appropriately cured and can exhibit adhesion to metals such as Al and Cu after pre-baking and post-baking.

(solvent)
The photosensitive resin composition according to the present embodiment contains a urea compound or an amide compound having an acyclic structure as a solvent. As a solvent, it is preferable that a urea compound is included, for example. Thereby, the adhesiveness of the hardened | cured material of the photosensitive resin composition and metals, such as Al and Cu, can be improved more.
In the present specification, a urea compound refers to a compound having a urea bond, that is, a urea bond. An amide compound refers to a compound having an amide bond, that is, an amide. Specific examples of amides include primary amides, secondary amides, and tertiary amides.
In the present embodiment, the non-cyclic structure means that the compound structure does not include a cyclic structure such as a carbocyclic ring, an inorganic ring, or a heterocyclic ring. Examples of the structure of the compound that does not have a cyclic structure include a linear structure and a branched structure.

  As the urea compound and the acyclic amide compound, those having a large number of nitrogen atoms in the molecular structure are preferable. Specifically, the number of nitrogen atoms in the molecular structure is preferably 2 or more. Thereby, the number of lone electron pairs can be increased. Therefore, adhesion with metals such as Al and Cu can be improved.

  Specific examples of the structure of the urea compound include a cyclic structure and an acyclic structure. Of the above specific examples, the structure of the urea compound is preferably an acyclic structure. Thereby, the adhesiveness of the hardened | cured material of the photosensitive resin composition and metals, such as Al and Cu, can be improved. The reason is presumed as follows. It is presumed 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 presumably because a urea compound having an acyclic structure has less molecular movement restraint and a greater degree of freedom in deformation of the molecular structure than a urea compound having a cyclic structure. Therefore, when a urea compound having an acyclic 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′-dimethylpropyleneurea, 1, 3-dimethoxy-1,3-dimethylurea, N, N′-diisopropyl-O-methylisourea, O, N, N′-triisopropylisourea, O-tert-butyl-N, N′-diisopropylisourea, O-ethyl-N, N′-diisopropylisourea, O-benzyl-N, N′-diisopropylisourea and the like can be mentioned. As a urea compound, it can use 1 type or in combination of 2 or more types among the said specific examples. Examples of urea compounds include tetramethylurea (TMU), tetrabutylurea, 1,3-dimethoxy-1,3-dimethylurea, N, N′-diisopropyl-O-methylisourea, O, N among the above specific examples. , N′-triisopropylisourea, O-tert-butyl-N, N′-diisopropylisourea, O-ethyl-N, N′-diisopropylisourea and O-benzyl-N, N′-diisopropylisourea It is preferable to use one or more selected from the group consisting of tetramethylurea (TMU). Thereby, a strong coordination bond can be formed and adhesiveness can be improved.

  Specific examples of the amide compound having an acyclic structure include 3-methoxy-N, N-dimethylpropanamide, N, N-dimethylformamide, N, N-dimethylpropionamide, N, N-diethylacetamide, 3- Examples include butoxy-N, N-dimethylpropanamide and N, N-dibutylformamide.

The photosensitive resin composition according to the present embodiment may include a solvent that does not include a nitrogen atom in addition to a urea compound and an acyclic amide compound as a solvent.
Specific examples of solvents that do not include nitrogen atoms include ether solvents, acetate solvents, alcohol solvents, ketone solvents, lactone solvents, carbonate solvents, sulfone solvents, ester solvents, aromatic hydrocarbons. System solvents and the like. As a solvent which does not have a nitrogen atom, it can use 1 type or in combination of 2 or more types among the said specific examples.
Specific examples of the ether 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, ethylene glycol diethyl ether, and diethylene glycol diethyl ether. , Diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, 1,3-butylene glycol-3-monomethyl ether, and the like.
Specific examples of the acetate solvent include propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, and methyl-1,3-butylene glycol acetate.
Specific examples of the alcohol solvent include tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol, butanediol, isopropyl alcohol, and the like.
Specific examples of the ketone solvent include cyclopentanone, cyclohexanone, diacetone alcohol, and 2-heptanone.
Specific examples of the lactone solvent include γ-butyrolactone (GBL) and γ-valerolactone.
Specific examples of the carbonate solvent include ethylene carbonate and propylene carbonate.
Specific examples of the sulfone solvent include dimethyl sulfoxide (DMSO) and sulfolane.
Specific examples of the ester solvent include methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, and the like.
Specific examples of the aromatic hydrocarbon solvent include mesitylene, toluene, xylene and the like.

As a lower limit of content of the urea compound in a solvent and the amide compound of a non-cyclic structure, when a solvent is 100 mass parts, it is preferable that it is 10 mass parts or more, for example, and it is 20 mass parts or more. More preferably, it is more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, and particularly preferably 70 parts by mass or more. Thereby, the adhesiveness of the hardened | cured material of the photosensitive resin composition and metals, such as Al and Cu, can be improved more.
Moreover, as a lower limit of content of the urea compound in a solvent and the amide compound of an acyclic structure, when a solvent is 100 mass parts, it can be 100 mass parts or less, for example. In the solvent, it is preferable from the viewpoint of improving adhesion that the content of the urea compound and the amide compound having an acyclic structure is large.

The photosensitive resin composition according to the present embodiment further includes additives such as an adhesion assistant, a silane coupling agent, a thermal crosslinking agent, a surfactant, an antioxidant, a dissolution accelerator, a filler, and a sensitizer. May be.
Hereinafter, details of typical additive components will be described.

(Adhesion aid)
The photosensitive resin composition according to the present embodiment may further include an adhesion assistant. Specifically, a triazole compound, an aminosilane, or an imide compound can be used as the adhesion assistant. This further increases the number of lone electron pairs derived from nitrogen atoms. Therefore, contents other than the solvent of the photosensitive resin composition can be coordinated with the metal atom, and the adhesion can be further improved. As the adhesion assistant, either a triazole compound, an aminosilane, or an imide compound may be used, or two or more of a triazole compound, an aminosilane, and an imide 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, 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-me It includes 1,2,4-triazole, such as Le-1,2,4-triazole-3-carboxamide. As a triazole compound, 1 type (s) or 2 or more types can be used in combination in the above specific examples.

  Specific examples of aminosilanes include cyclohexene-1,2-dicarboxylic anhydride and 3-aminopropyltriethoxysilane condensate, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 3 -Condensate of aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (amino Ethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl -3-aminopropyltrimethoxysilane, N, N′bis [3- (trimethoxy Ryl) 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- (trimethoxy Silyl) propyl] ethylenediamine, N, N′-bis [3- (trimethoxysilyl) propyl] diaminopropane, N, N′-bis [3- (trimethoxysilyl) propyl] diaminohexane, N, N′-bis And [3- (trimethoxysilyl) propyl] diethylenetriamine. As aminosilane, 1 type (s) or 2 or more types can be used in combination in the above specific examples.

  Specific examples of the imide compound include compounds exemplified below. These can be used alone or in combination of two or more.

The lower limit value of the content of the adhesion assistant in the photosensitive resin composition is, for example, preferably 0.1 parts by mass or more, and 1.0 parts by mass or more with respect to 100 parts by mass of the alkali-soluble resin. More preferably, it is more preferably 2.0 parts by mass or more, and still more preferably 3.0 parts by mass or more. Thereby, the adhesive force can be sufficiently increased.
Moreover, it is preferable that it is 10 mass parts or less with respect to 100 mass parts of alkali-soluble resin, for example, and the upper limit of content of the adhesion | attachment adjuvant in the photosensitive resin composition is 7 mass parts or less. More preferred is 5 parts by mass or less. Thereby, the adhesion assistant is suitably dispersed in the photosensitive resin composition, and the adhesion can be improved.

(Silane coupling agent)
The photosensitive resin composition according to the present embodiment may further include a silane coupling agent. Examples of the silane coupling agent include those other than aminosilanes exemplified as the adhesion assistant.
Specific examples of the silane coupling agent having a structure different from that of the silane compound described above include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3 -Epoxy silanes such as glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; p-styryltrimethoxysilane Such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. Acrylic silane such as 3-acryloxypropyltrimethoxysilane; isocyanurate silane; alkyl silane; ureido silane such as 3-ureidopropyltrialkoxysilane; 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Mercaptosilanes of the above; isocyanate silanes such as 3-isocyanatopropyltriethoxysilane; titanium compounds; aluminum chelates; aluminum / zirconium compounds. As a silane coupling agent, 1 type (s) or 2 or more types can be mix | blended among the said specific examples.

(Thermal crosslinking agent)
The photosensitive resin composition according to the present embodiment may include a thermal crosslinking agent that can react with an alkali-soluble resin by heat. Thereby, about the hardened | cured material which post-baked the photosensitive resin composition, mechanical characteristics, such as tensile elongation at break, can be improved. Moreover, it is convenient also from a viewpoint which can improve the sensitivity of the resin film formed with the photosensitive resin composition.
Specific examples of the thermal crosslinking agent include 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol (paraxylene glycol), 1,3,5-benzenetrimethanol, Methylol groups such as 4,4-biphenyldimethanol, 2,6-pyridinedimethanol, 2,6-bis (hydroxymethyl) -p-cresol, 4,4′-methylenebis (2,6-dialkoxymethylphenol) A compound having a phenol; phenols such as phloroglucid; 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, methyl 2,6-naphthalenedicarboxylate , Compounds having an alkoxymethyl group such as 4,4′-methylenebis (2,6-dimethoxymethylphenol); methylol melamine compounds represented by hexamethylol melamine, hexabutanol melamine and the like; alkoxy melamine compounds such as hexamethoxy melamine; Alkoxymethylglycoluril compounds such as tetramethoxymethylglycoluril; methylolurea compounds such as methylolbenzoguanamine compounds and dimethylolethyleneurea; cyano compounds such as dicyanoaniline, dicyanophenol and cyanophenylsulfonic acid; 1,4-phenylene diisocyanate , 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate compounds; ethylene glycol diglycidyl ether; Epoxy group-containing compounds such as phenol A diglycidyl ether, triglycidyl isocyanurate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenol novolak resin type epoxy resin; N, N ′ And maleimide compounds such as -1,3-phenylene dimaleimide and N, N′-methylene dimaleimide. As the thermal crosslinking agent, one or more of the above specific examples can be used.

The upper limit of the content of the thermal crosslinking agent in the photosensitive resin composition is, for example, preferably 20 parts by mass or less and more preferably 15 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin. , More preferably 12 parts by mass or less, and still more preferably 10 parts by mass or less. Thereby, even when a thermal crosslinking agent is provided with the functional group which solvates, such as a phenolic hydroxyl group, it can suppress that the chemical resistance after post-baking falls.
Moreover, it is preferable that it is 0.1 mass part or more with respect to 100 mass parts of alkali-soluble resin, and, as for the lower limit of content of the thermal crosslinking agent in the photosensitive resin composition, it is 1 mass part or more. More preferably, it is more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and particularly preferably 8 parts by mass or more.

(Surfactant)
The photosensitive resin composition according to this embodiment may further contain a surfactant.
The surfactant is not limited, and specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Ftop EF301, Ftop EF303, Ftop EF352 (Manufactured by Shin-Akita Kasei Co., Ltd.), Megafuck F171, Megafuck F172, Megafuck F173, Megafuck F177, Megafuck F444, Megafuck F 70, Megafuck F471, Megafuck F475, Megafuck F482, Megafuck F477 (manufactured by DIC), Florard FC-430, Florard FC-431, Novec FC4430, Novec FC4432 (manufactured by 3M Japan), Surflon S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (AGC Seimi Chemical Co., Ltd.) Fluorosurfactants commercially available under names such as; organosiloxane copolymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth) acrylic acid copolymer polyflow no. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

  Among these, it is preferable to use a fluorosurfactant having a perfluoroalkyl group. Among the above specific examples, the fluorosurfactant having a perfluoroalkyl group is MegaFuck F171, MegaFuck F173, MegaFuck F444, MegaFuck F470, MegaFuck F471, MegaFuck F475, MegaFuck F482, MegaFuck One or more selected from F477 (manufactured by DIC), Surflon S-381, Surflon S-383, Surflon S-393 (manufactured by AGC Seimi Chemical), Novec FC4430 and Novec FC4432 (manufactured by 3M Japan) Is preferably used.

  As the surfactant, a silicone-based surfactant (for example, polyether-modified dimethylsiloxane) can be preferably used. Specific examples of silicone surfactants include SH series, SD series and ST series from Toray Dow Corning, BYK series from Big Chemie Japan, KP series from Shin-Etsu Chemical Co., Ltd. (Registered trademark) series, TSF series of Toshiba Silicone, and the like.

The upper limit of the content of the surfactant in the photosensitive resin composition is preferably 1% by mass (10000 ppm) or less with respect to the entire photosensitive resin composition (including the solvent), and 0.5% by mass. % (5000 ppm) or less, more preferably 0.1 mass% (1000 ppm) or less.
Further, the lower limit of the content of the surfactant in the photosensitive resin composition is not particularly limited, but from the viewpoint of sufficiently obtaining the effect of the surfactant, for example, the entire photosensitive resin composition (the solvent is used). 0.001% by mass (10 ppm) or more.
By appropriately adjusting the amount of the surfactant, it is possible to improve the coatability and the uniformity of the coating film while maintaining other performances.

(Antioxidant)
The photosensitive resin composition according to the present embodiment may further contain an antioxidant. As the antioxidant, one or more selected from phenol-based antioxidants, phosphorus-based antioxidants and thioether-based antioxidants can be used. The antioxidant can suppress oxidation of the resin film formed by the photosensitive resin composition.
Examples of phenolic antioxidants include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} 2,4,8,10-tetraoxaspiro [5,5] undecane, octadecyl-3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,6-di-t-butyl-4-methylphenol, 2,6-di- -Butyl-4-ethylphenol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-t-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-t -Butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-t-butyl-m-cresol) 2-octylthio-4,6-di (3,5-di-t-butyl-4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-t-butyl-6- Butylphenol), 2, -2'-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3- -Butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (6-t-butyl-m-cresol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2, 2′-ethylidenebis (4-s-butyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-t- Butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t- Butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3 , 5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 2-t -Butyl-4-methyl-6- (2-acryloyloxy-3-t-butyl-5-methylbenzyl) phenol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4- 8,10-tetraoxaspiro [5,5] undecane-bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], triethyleneglycolbis [β- (3-t- Butyl-4-hydroxy-5-methylphenyl) propionate], 1,1′-bis (4-hydroxyphenyl) cyclohexane, 2,2′-methylene (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (6- (1-methylcyclohexyl) -4-methyl Phenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis (2- (3-tert-butyl-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-t-butyl-4-hydroxybenzyl) sulfide, 4,4′-thiobis (6-t-butyl-2-methylphenol), 2,5-di-t-butylhydroquinone, 2,5-di t-amylhydroquinone, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-dimethyl-6- (1-methylcyclohexyl), Examples include styrene phenol, 2,4-bis ((octylthio) methyl) -5-methylphenol, and the like.
Phosphorus antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenylphosphite), tetrakis (2 , 4-Di-tert-butyl-5-methylphenyl) -4,4′-biphenylenediphosphonite, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis- (2,6 -Dicumylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, Tris (mixed mono and di-nonylphenyl phosphite), bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methoxycal Bonylethyl-phenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-octadecyloxycarbonylethylphenyl) pentaerythritol diphosphite, and the like.
Examples of thioether antioxidants include dilauryl-3,3′-thiodipropionate, bis (2-methyl-4- (3-n-dodecyl) thiopropionyloxy) -5-tert-butylphenyl) sulfide. , Distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis (3-lauryl) thiopropionate, and the like.

(Filler)
The photosensitive resin composition according to the present embodiment may further contain a filler. As the filler, an appropriate filler can be selected according to mechanical properties and thermal properties required for the resin film made of the photosensitive resin composition.
Specific examples of the filler include inorganic fillers and organic fillers.
Specific examples of the inorganic filler include silica such as fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, and finely divided silica; alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, and silicon carbide. And metal compounds such as aluminum hydroxide, magnesium hydroxide and titanium white; talc; clay; mica; glass fiber. As an inorganic filler, it can use 1 type or in combination of 2 or more types among the said specific examples.
Specific examples of the organic filler include organosilicone powder and polyethylene powder. As an organic filler, it can use 1 type or in combination of 2 or more types among the said specific examples.

(Preparation of photosensitive resin composition)
The method for preparing the photosensitive resin composition in the present 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 be prepared by mixing and dissolving each of the above components in a solvent. Thereby, the photosensitive resin composition used as the varnish can be obtained.

(Photosensitive resin composition)
The photosensitive resin composition according to the present embodiment is applied to the surface provided with a metal such as Al and Cu, and then dried by pre-baking to form a resin film. Next, 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.
In addition, when producing the said permanent film | membrane, as prebaking conditions, it can be set as the heat processing for 30 second or more and 1 hour or less at the temperature of 90 to 130 degreeC, for example. Moreover, as conditions for post-baking, for example, a heat treatment can be performed at a temperature of 150 ° C. to 350 ° C. for 30 minutes to 10 hours.

The viscosity of the photosensitive resin composition according to the present embodiment can be appropriately set according to the desired thickness of the resin film. Adjustment of the viscosity of the photosensitive resin composition can be performed by adding a solvent. In the adjustment, it is necessary to keep the contents of the urea compound and the acyclic amide compound in the solvent constant.
The upper limit of the viscosity of the photosensitive resin composition according to the present embodiment may be, for example, 2000 mPa · s or less, 1800 mPa · s or less, or 1500 mPa · s or less. Moreover, the lower limit of the viscosity of the photosensitive resin composition according to the present embodiment may be, for example, 10 mPa · s or more, or 50 mPa · s or more, depending on the desired thickness of the resin film.
In the present embodiment, the viscosity of the photosensitive resin composition can be measured with an E-type viscometer, for example, at a temperature of 25 ° C. and 300 seconds after the start of rotation.

The photosensitive resin composition according to the present embodiment was adjusted by an E-type viscometer so that the viscosity measured after rotation at a rotation frequency of 100 rpm, a temperature of 25 ° C. and 300 seconds was 50 mPa · s, and a temperature of 25 ° C. Then, the upper limit of the contact angle 10 seconds after dropping 2 ml onto the copper foil is, for example, preferably 71 ° or less, more preferably 69 ° or less, still more preferably 65 ° or less, More preferably, it is 62 ° or less, and particularly preferably 57 ° or less. When the contact angle is less than or equal to the above numerical range, the familiarity between the varnish of the photosensitive resin composition and a metal such as Cu is improved, and the photosensitive resin composition is placed in a fine gap formed on the metal surface such as Cu. Can invade. Thereby, when the photosensitive resin composition is used as a cured film, an anchor effect is exhibited between the cured film and a metal such as Cu, and the adhesion can be improved.
Further, the viscosity was adjusted by an E-type viscometer so that the viscosity measured after rotation at a rotational frequency of 100 rpm, a temperature of 25 ° C. for 300 seconds was 50 mPa · s, and 2 ml was dropped onto the copper foil at a temperature of 25 ° C. for 10 seconds. The lower limit value of the subsequent contact angle may be, for example, 40 ° or more, or 45 ° or more.

The photosensitive resin composition according to the present embodiment was adjusted by an E-type viscometer so that the viscosity measured after rotation at a rotation frequency of 100 rpm, a temperature of 25 ° C. and 300 seconds was 50 mPa · s, and a temperature of 25 ° C. Thus, the upper limit of the contact angle after 10 seconds after dropping 2 ml of the aluminum foil is, for example, preferably 14 ° or less, more preferably 13 ° or less, and further preferably 12 ° or less, 11 More preferably, it is not more than °. When the contact angle is not more than the above numerical range, the familiarity between the varnish of the photosensitive resin composition and a metal such as Al is improved, and the photosensitive resin composition is placed in a fine gap generated on the metal surface such as Al. Can invade. Thereby, when the photosensitive resin composition is used as a cured film, an anchor effect is exhibited between the cured film and a metal such as Al, and the adhesion can be improved.
Further, with an E-type viscometer, the viscosity was adjusted so that the viscosity measured after rotating at a rotation frequency of 100 rpm, a temperature of 25 ° C. for 300 seconds was 50 mPa · s, and 2 ml was dropped on the aluminum foil at a temperature of 25 ° C. for 10 seconds. The lower limit value of the subsequent contact angle may be, for example, 1 ° or more, or 5 ° or more.

It supplements about the viscosity adjustment at the time of the measurement of the above-mentioned contact angle.
About the photosensitive resin composition whose viscosity by the measuring method by said E type | mold viscosity meter is larger than 50 mPa * s, the viscosity is adjusted to 50 mPa * s using the same solvent as the solvent which the said photosensitive resin composition contains. To measure the contact angle. In addition, when the said photosensitive resin composition contains a mixed solvent, a viscosity is adjusted with the mixed solvent.
Moreover, about the photosensitive resin composition whose viscosity by the said measuring method is smaller than 50 mPa * s, the contact angle by the viscosity equivalent to 50 mPa * s can be calculated | required as follows.
For example, it is assumed that there is a photosensitive resin composition having a viscosity of 40 mPa · s by the above measurement method. This is further diluted using 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. Then, the relationship between the viscosity and the contact angle of the photosensitive resin composition having a viscosity of 10 to 40 mPa · s is plotted, a straight line is drawn by the least square method, and the contact angle corresponding to the viscosity of 50 mPa · s is extrapolated. . Note that plotting is performed at a minimum of 2 points, preferably 3 points or 4 points.
Incidentally, as a knowledge of the present inventors, in a low viscosity region of 50 mPa · s or less, there is almost no difference in contact angle between 30 mPa · s and 50 mPa · s, for example.

As a result of studying the method of bringing the contact angle with respect to the copper foil and the aluminum foil into the above numerical range for the varnish of the photosensitive resin composition, the present inventor has found that the urea compound contained in the solvent and the amide compound having an acyclic structure are included. It has been found that it is important to appropriately control the structure and the contents of urea compounds and acyclic amide compounds in the solvent.
As the structure of the urea compound and the amide compound having an acyclic structure contained in the solvent, those having more resonance structures are preferable. Specifically, a urea bond of a urea compound or an amide bond of an amide compound having a non-cyclic structure preferably has a large number of resonance structures formed by a lone electron pair of a nitrogen atom and a ketone moiety C═O. . The number of resonance structures of the urea compound and the amide compound having an acyclic structure is, for example, preferably 2 or more, and more preferably 3 or more. Thereby, the electron cloud of a urea compound and an amide compound of a non-cyclic structure spreads, and an electronic state is stabilized. Therefore, it is considered that the surface free energy of the urea compound and the amide compound having an acyclic structure is reduced, and the wettability with respect to Cu can be improved. An example is given as the number of resonance structures. For example, the number of resonance structures of a urea compound such as tetramethylurea (TMU) is three.
In addition, the content of the urea compound and the amide compound having an acyclic structure in the solvent depends on the structure described above. For example, when the solvent is 100 parts by mass, the content is preferably 30 parts by mass or more, More preferably, it is more than 70 mass parts, More preferably, it is more preferably 100 mass parts. Thereby, the electronic state in a solvent can be stabilized and a contact angle can be made into the said numerical range.

(Use)
The photosensitive resin composition of this embodiment is used for forming a resin film for an electronic device such as a permanent film or a resist. Among these, the photosensitive resin composition after pre-baking and the photosensitive resin composition after post-baking from the standpoint of improving the adhesion between the photosensitive resin composition and Al pad after pre-baking and the suppression of the generation of residues of the photosensitive resin composition during development. From the viewpoint of improving the adhesion between the cured film of the composition and the metal, and in addition to improving the chemical resistance of the photosensitive resin composition after post-baking, it is preferably used for applications using a permanent film. .
In the present embodiment, the resin film is a dry film or a cured film of the photosensitive resin composition. That is, the resin film according to the present embodiment is obtained by drying or curing the photosensitive resin composition.

  The permanent film is composed of a resin film obtained by pre-baking, exposing and developing the photosensitive resin composition, patterning it into a desired shape, and curing it by post-baking. The permanent film can be used for a protective film of an electronic device, an interlayer film, a dam material, and the like.

  The resist is, for example, coated with a photosensitive resin composition on an object to be masked by the resist by a method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, and the like. It is comprised with the resin film obtained by removing a solvent from.

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

  The electronic device 100 is, for example, a semiconductor chip. In this case, for example, a semiconductor package can be obtained by mounting the electronic device 100 on the wiring board via the bumps 52. 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 in the uppermost layer of the multilayer wiring layer. The uppermost layer wiring 34 is made of, for example, aluminum Al. Further, a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34. An opening through which the uppermost layer wiring 34 is exposed is provided in a part of the passivation film 32.

  A rewiring 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, an insulating layer 44 provided on the insulating layer 42 and the rewiring 46, Have An opening connected to the uppermost layer wiring 34 is formed in the insulating layer 42. The rewiring 46 is formed on the insulating layer 42 and in an opening provided in the insulating layer 42, and is connected to the uppermost layer wiring 34. The insulating layer 44 is provided with an opening connected to the rewiring 46.

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

It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
Hereinafter, examples of the reference form will be added.
1.
An alkali-soluble resin;
A photosensitizer,
A solvent,
The solvent is a photosensitive resin composition containing a urea compound or an amide compound having an acyclic structure.
2.
1. The photosensitive resin composition according to claim 1,
The photosensitive resin composition is used to form a permanent film,
The said permanent film is a photosensitive resin composition which is an interlayer film, a surface protective film, or a dam material.
3.
1. Or 2. The photosensitive resin composition according to claim 1,
Content of the said urea compound in the said solvent and the amide compound of the said acyclic structure is a photosensitive resin composition which is 10 mass parts or more and 100 mass parts or less with respect to 100 mass parts of said solvents.
4).
1. To 3. It is the photosensitive resin composition as described in any one of these, Comprising:
The solvent includes the urea compound;
The structure of the urea compound is a photosensitive resin composition having an acyclic structure.
5.
4). The photosensitive resin composition according to claim 1,
The photosensitive resin composition, wherein the urea compound is tetramethylurea.
6).
1. To 5. It is the photosensitive resin composition as described in any one of these, Comprising:
The alkali-soluble resin is a photosensitive resin composition that is at least one selected from the group consisting of a polyamide resin, a polybenzoxazole resin, a polyimide resin, a phenol resin, a hydroxystyrene resin, and a cyclic olefin resin.
7).
6). The photosensitive resin composition according to claim 1,
The alkali-soluble resin includes the polyamide resin,
The polyamide resin is a photosensitive resin composition containing a structural unit represented by the above formula (PA1).
8).
7). The photosensitive resin composition according to claim 1,
The said polyamide resin is a photosensitive resin composition containing the structural unit represented by the above-mentioned general formula (PA2) and the above-mentioned general formula (PA3).
9.
1. To 8. It is the photosensitive resin composition as described in any one of these, Comprising:
The content of the alkali-soluble resin in the photosensitive resin composition is 30 parts by mass or more and 95 parts by mass or less when the total solid content of the photosensitive resin composition is 100 parts by mass. .
10.
1. To 9. It is the photosensitive resin composition as described in any one of these, Comprising:
The photosensitive resin composition, wherein the photosensitive agent is a diazoquinone compound.
11.
1. To 10. It is the photosensitive resin composition as described in any one of these, Comprising:
The photosensitive resin composition further includes an adhesion assistant,
The adhesion assistant is a photosensitive resin composition, which is a triazole compound, an aminosilane, or an imide compound.
12
1. To 11. It is the photosensitive resin composition as described in any one of these, Comprising:
The photosensitive resin composition was adjusted with an E-type viscometer so that the viscosity measured after rotating at a rotation frequency of 100 rpm, a temperature of 25 ° C. and for 300 seconds was 50 mPa · s, at a temperature of 25 ° C. and a copper A photosensitive resin composition having a contact angle of 70 ° or less 10 seconds after dropping 2 ml of the foil.
13.
1. To 12. It is the photosensitive resin composition as described in any one of these, Comprising:
The photosensitive resin composition whose viscosity of the said photosensitive resin composition 300 seconds after a rotation start at the temperature of 25 degreeC measured using an E-type viscosity meter is 50 mPa * s or more and 2000 mPa * s or less.
14
1. To 13. A resin film obtained by curing the photosensitive resin composition according to any one of the above.
15.
14 An electronic device comprising the resin film.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to description of these Examples at all.
In addition, Examples 7-12 shall be read as a reference example.

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

<Alkali-soluble resin>
First, the details of the alkali-soluble resin used in each example and each comparative example will be described.

(Alkali-soluble resin 1)
The alkali-soluble resin 1 which is a polyamide resin was synthesized by the following procedure.
In a four-necked glass separable flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet tube, 206.58 g of diphenyl ether-4,4′-dicarboxylic acid represented by the following formula (DC2) (0.800 mol) and 170.20 g of a mixture of dicarboxylic acid derivatives obtained by reacting 1-hydroxy-1,2,3-benzotriazole monohydrate (216.19 g, 1.600 mol) (0 .346 mol), 4.01 g (0.047 mol) of 5-aminotetrazole, 45.22 g (0.196 mol) of 4,4′-methylenebis (2-aminophenol) represented by the following formula (DA2), 56.24 g (0.196 mol) of 4,4′-methylenebis (2-amino-3,6 dimethylphenol) represented by the following formula (DA3) It was. Thereafter, 578.3 g of N-methyl-2-pyrrolidone was added into the separable flask to dissolve each raw material component. Next, it was made to react at 90 degreeC for 5 hours using the oil bath. Next, 24.34 g (0.141 mol) of 4-ethynylphthalic anhydride and 121.7 g of N-methyl-2-pyrrolidone were added to the above separable flask and reacted while stirring at 90 ° C. for 2 hours. Then, the reaction was terminated by 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 filtered off, sufficiently washed with water, and then dried under vacuum to obtain an alkali-soluble resin 1. The obtained alkali-soluble resin 1 had a weight average molecular weight Mw of 18081.

<Photosensitive agent>
Next, details of the photosensitizers used in the respective examples and comparative examples will be described.

(Photosensitive agent 1)
Photosensitive agent 1 which is a diazoquinone compound was synthesized by the following procedure.
In a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 11.04 g (0.026 mol) of phenol represented by the following formula (P-1), 2-Naphthoquinone-2-diazide-5-sulfonyl chloride 18.81 g (0.070 mol) and acetone 170 g were added and stirred to dissolve.
Next, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C. After reacting for 3 hours at room temperature, 1.05 g (0.017 mol) of acetic acid was added and reacted for another 30 minutes. The reaction mixture was then filtered, and the filtrate was poured into a mixed solution of water / acetic acid (990 mL / 10 mL). Next, the precipitate was collected by filtration, thoroughly 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>
The following solvent 1-3 was used as the solvent.
Solvent 1: tetramethylurea (TMU), which is a linear urea compound
Solvent 2: γ-butyrolactone (GBL)
Solvent 3: N-methylpyrrolidone (NMP) which is a cyclic amide compound

<Adhesion aid>
The following adhesion assistant 1-3 was used as the adhesion assistant.
Adhesion aid 1: N, N′-bis [3- (trimethoxysilyl) propyl] ethane-1,2-diamine (X-) manufactured by Shin-Etsu Chemical Co., which is an aminosilane represented by the following formula (S1) 12-5263HP)
Adhesion aid 2: Condensation product of carboxylic acid anhydride and 3-aminopropyltriethoxysilane, which is an aminosilane synthesized by the method described below and represented by the following formula (S2)

Below, the synthesis | combining method of the adhesion | attachment adjuvant 2 which is a condensate of a carboxylic acid anhydride and 3-aminopropyl triethoxysilane is demonstrated in detail.
In a suitably sized reaction vessel equipped with a stirrer and a condenser, cyclohexene-1,2-dicarboxylic anhydride (45.6 g, 300 mmol) was dissolved in N-methyl-2-pyrrolidone (970 g) and a thermostatic bath. To 30 ° C. Subsequently, 3-aminopropyltriethoxysilane (62 g, 280 mmol) was charged into the dropping funnel and dropped into the solution over 60 minutes. After completion of dropping, the mixture was stirred under conditions of 30 ° C. for 18 hours to obtain an adhesion aid 2 represented by the following formula (S2).

<Thermal crosslinking agent>
The following thermal crosslinking agent 1 was used as the thermal crosslinking agent.
-Thermal crosslinking agent 1: Paraxylene glycol (manufactured by Ihara Nikkei, PXG)

<Surfactant>
The following surfactant 1 was used as the surfactant.
Surfactant 1: Fluorosurfactant (manufactured by 3M Japan, FC4430)

(Preparation of photosensitive resin compositions of Examples and Comparative Examples)
The photosensitive resin compositions of Example 1-3 and Comparative Example 1 were prepared as follows.
First, each raw material component mentioned above was prepared. Subsequently, about what uses 2 or more types of solvents, the solvent was mixed according to the mixture ratio shown in the following Table 1, and the mixed solvent was produced. Next, each raw material other than the solvent is added to the solvent or the mixed solvent, stirred, and then filtered through a PTFE membrane filter having a pore size of 0.2 μm, so that the varnish of the photosensitive resin composition of each example and each comparative example is obtained. Got.
In addition, the mixture ratio of each raw material shown in following Table 1 is described in a mass part.

  The following evaluation was performed on the photosensitive resin compositions of Example 1-3 and Comparative Example 1.

(viscosity)
About the varnish of the photosensitive resin composition of Example 1-3 and Comparative Example 1, with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., TVE-22H), the rotation frequency was 100 rpm, the temperature was 25 ° C., and the viscosity was measured after 300 seconds of rotation. It was 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 Example 1-3 and Comparative Example 1, the contact angle of the varnish was evaluated as follows.
First, a smooth copper foil was prepared as a substrate. Next, at a temperature of 25 ° C., 2 ml of the varnish of the photosensitive resin composition was deposited on the substrate, and the contact angle after 10 seconds was evaluated by a droplet method. In addition, the measurement was performed using the contact angle meter (the Kyowa Interface Science company make, DROPMASTER-501).
Moreover, it replaced with the said smooth copper foil as a base material, and evaluated also about what used the smooth aluminum foil.
The respective evaluation results are shown in Table 1 below. Here, the unit of the contact angle is °. Here, in Table 1 below, the description “−” indicates that evaluation is not performed.
In addition, the viscosity of the varnish of each photosensitive resin composition of Example 1-3 and Comparative Example 1 is 50 mPa · s when measured with an E-type viscometer after rotating at a rotation frequency of 100 rpm, a temperature of 25 ° C. for 300 seconds. there were.

(Adhesion)
Using the photosensitive resin composition of Example 1-3 and Comparative Example 1, the adhesion between the post-baking photosensitive resin composition and aluminum (Al) was evaluated as follows.
First, a silicon wafer was prepared as a base material. Next, after coating the base material with titanium (Ti) to a thickness of 0.05 μm (500 mm), Al is sputtered to a thickness of 0.3 μm (3000 mm) on Ti, and then Al The varnish of the photosensitive resin composition was coated on the top using a spin coater. Next, after prebaking at a temperature of 120 ° C. for 4 minutes using a hot plate, it was further post-baked at a temperature of 220 ° C. for 1 hour in a nitrogen atmosphere to obtain a cured film having a thickness of 7 μm. Here, the cured film is in close contact with Al. That is, the laminated structure formed by laminating the base material, Ti, Al, and the cured film in this order was obtained. Using this laminated structure, adhesion was evaluated based on JIS D 0202. Specifically, the cured film and Al were scratched from the surface where the cured film was present in the laminated structure so that 100 squares of 1 mm square could be formed and separated into pieces. A cellophane adhesive tape was then attached to the cured film. One minute after the attachment, the cellophane adhesive 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 peeled squares were counted, and this was regarded as an evaluation result of 0h in the PCT process. The PCT process 0h indicates that an acceleration test is not performed. The evaluation results are shown in Table 1 below. Table 1 shows the number of peeled squares.
In the above, the cellophane pressure-sensitive adhesive tape was attached to the cured film and allowed to stand at a temperature of 125 ° C., a humidity of 100%, and an atmospheric pressure of 2.3 atm for a specific time, and then the cellophane pressure-sensitive adhesive 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 peeled squares were counted. This was the evaluation result for a specific time by the PCT process. As the PCT process time, each of 48h, 100h, 150h, 200h, and 300h was evaluated. The evaluation results are shown in Table 1 below. Table 1 shows the number of peeled squares.
Furthermore, the adhesiveness of the photosensitive resin composition and copper (Cu) after post-baking was evaluated. Specifically, instead of sputtering Al with a thickness of 0.05 μm (500 mm) on Ti, except that copper (Cu) was sputtered with a thickness of 0.5 μm (300 mm), The adhesiveness of the photosensitive resin composition and aluminum (Al) described above was evaluated by the same method as the evaluation. The evaluation results are shown in Table 1 below.
In addition, as for the evaluation result of adhesiveness, all show that the value is small, ie, the adhesiveness of a cured film, Al, and Cu is so high that there are few squares which peeled.
The PCT process is intended for an accelerated test, and was performed in order to evaluate the long-term adhesion between the post-baking photosensitive resin composition and Al and Cu.

  As shown in Table 1 above, it was confirmed that the photosensitive resin composition of each example had a small contact angle with respect to a metal such as Cu and Al, and the familiarity as compared with the photosensitive resin composition of Comparative Example 1. . Moreover, 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. It was confirmed that the adhesion was improved.

Moreover, in addition to the above Example 1-3, the photosensitive resin composition with a small amount of the solvent can be applied suitably, and the adhesion is improved as in Example 1-3. In order to confirm this, the photosensitive resin composition of Example 4-7 was prepared. The method for preparing the photosensitive resin composition of Example 4-7 was the same as that of Example 1-3 described above. The blending ratio of Example 4-7 is shown in Table 2 below.
In addition, the mixture ratio of each raw material shown in following Table 2 is described in a mass part.
About the prepared photosensitive resin composition of Example 4-7, evaluation of a viscosity and adhesiveness was performed by the method similar to Example 1-3 mentioned above. Here, the coating could be performed without any problem as in Example 1-3. The evaluation results are shown in Table 2 below.

  As mentioned above, although the photosensitive resin composition of Example 4-7 was a thing with few compounding quantities of a solvent compared with the photosensitive resin composition of Example 1-3, it should coat without a problem. It was confirmed that the adhesiveness to metals such as Cu and Al after post-baking was developed similarly to the photosensitive resin composition of Example 1-3.

Furthermore, the following Examples 8-13 and Comparative Example 2 were evaluated. Examples 8-13 include an amide compound having an acyclic structure as a solvent.
First, each raw material component shown in Table 3 was prepared. Subsequently, about what uses 2 or more types of solvents, the solvent was mixed according to the compounding ratio shown by following Table 3, and the mixed solvent was produced.
Subsequently, each raw material other than the solvent was added to the solvent or the mixed solvent, stirred, and filtered through a PTFE membrane filter having a pore size of 0.2 μm to obtain a varnish of the photosensitive resin composition.
In addition, the mixture ratio of each raw material of Table 3 is a mass part.

Among the raw material components shown in Table 3, the solvent 4 is as follows. Other raw material components are the same as those described in Table 1 or Table 2.
Solvent 4: 3-methoxy-N, N-dimethylpropanamide, which is an acyclic amide compound

About the photosensitive resin composition of Table 3, evaluation of a viscosity and adhesiveness was performed by the method similar to Example 1-3. Here, the coating could be performed without any problem as in Example 1-3.
Moreover, about Example 11-13, the contact angle was measured by the method similar to Example 1-3.
The evaluation results are shown in Table 3.

  As shown in Table 3, even when an amide compound having an acyclic structure was used as the solvent, the adhesion to metals such as Cu and Al after post-baking was remarkably good.

  This application claims the priority on the basis of Japanese application Japanese Patent Application No. 2017-129670 for which it applied on June 30, 2017, and takes in those the indications of all here.

Claims (11)

An alkali-soluble resin;
A photosensitizer,
A solvent,
The alkali-soluble resin is a polyamide resin containing structural units represented by the following general formula (PA2) and the following general formula (PA3),
The solvent includes a urea compound,
The structure of the urea compound is an acyclic structure,
Content of the said urea compound in 100 mass parts of said solvents is a photosensitive resin composition which is 30 mass parts or more.

(In the general formula (PA2), 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. And a group formed by two or more kinds of atoms, R ^{5 to} R ¹⁰ each independently represents hydrogen or an organic group having 1 to 30 carbon atoms.)

(In the above general formula (PA3), 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. R ^{12 to} R ¹⁹ each independently represent hydrogen or an organic group having 1 to 30 carbon atoms, and the organic group is an alkyl group, alkenyl group, or a group formed by two or more types of atoms. And any one selected from the group consisting of a group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, a cycloalkyl group, and an alkaryl group.) The photosensitive resin composition according to claim 1,
The photosensitive resin composition is used to form a permanent film,
The said permanent film is a photosensitive resin composition which is an interlayer film, a surface protective film, or a dam material. The photosensitive resin composition according to claim 1 or 2,
Content of the said urea compound in the said solvent is the photosensitive resin composition which is 50 to 100 mass parts with respect to 100 mass parts of said solvents. The photosensitive resin composition according to claim 3 ,
The photosensitive resin composition, wherein the urea compound is tetramethylurea. It is the photosensitive resin composition of any one of Claim 1 to 4 , Comprising:
The content of the alkali-soluble resin in the photosensitive resin composition is 30 parts by mass or more and 95 parts by mass or less when the total solid content of the photosensitive resin composition is 100 parts by mass. . It is the photosensitive resin composition of any one of Claim 1 to 5 , Comprising:
The photosensitive resin composition, wherein the photosensitive agent is a diazoquinone compound. It is the photosensitive resin composition of any one of Claim 1 to 6 , Comprising:
The photosensitive resin composition further includes an adhesion assistant,
The adhesion assistant is a photosensitive resin composition, which is a triazole compound, an aminosilane, or an imide compound. It is the photosensitive resin composition of any one of Claim 1 to 7 , Comprising:
The photosensitive resin composition was adjusted with an E-type viscometer so that the viscosity measured after rotation at a rotation frequency of 100 rpm, a temperature of 25 ° C. and 300 seconds was 50 mPa · s, and the temperature was 25 ° C. A photosensitive resin composition having a contact angle of 70 ° or less 10 seconds after dropping 2 ml of the foil. It is the photosensitive resin composition of any one of Claim 1 to 8 , Comprising:
The photosensitive resin composition whose viscosity of the said photosensitive resin composition 300 seconds after a rotation start at the temperature of 25 degreeC measured using an E-type viscosity meter is 50 mPa * s or more and 2000 mPa * s or less. The resin film formed by curing the photosensitive resin composition according to any one of claims 1 to 9. An electronic device comprising the resin film according to claim 10 .

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