WO2020080266A1 - Photosensitive resin composition, cured film, electronic device provided with cured film, and method for manufacturing said device - Google Patents

Abstract

This photosensitive resin composition for forming a permanent film contains an alkali-soluble resin (A), a photosensitizer, and a solvent (C), and also contains a solvent (C-1) having a water-soluble glycol ether structure of which the boiling point is 130°C or greater.

Description

Photosensitive resin composition, cured film, electronic device including cured film, and method of manufacturing the same

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

Until now, various techniques have been developed in the field of photosensitive resin compositions, and for example, techniques for uniformly coating a photosensitive composition on a substrate have been studied. For example, Patent Document 1 includes an alkali-soluble resin, a quinonediazide compound, a surfactant and a solvent, and the surfactant is an organic fluorine compound, a predetermined first silicone compound, a predetermined second silicone compound. It has been disclosed that a photosensitive resin composition containing the above is disclosed. According to the photosensitive resin composition, unevenness during coating is reduced and coating with a uniform film thickness is possible.

JP 2006-184908 A

However, according to the studies by the inventors, the photosensitive resin composition described in Patent Document 1 may not spread evenly on a substrate containing an inorganic material, and a coating film having a uniform thickness may not be formed in some cases. It has been found that there is room for improvement in terms of reduction in wettability with respect to a substrate containing an inorganic material, occurrence of dents in the coating film, and exposure of the underlayer.

The present inventor diligently studied a photosensitive resin composition. As a result, by using a solvent having a glycol ether structure, which is water-soluble and has a boiling point of 130 ° C. or higher, as a component contained in the photosensitive resin composition, the wettability with respect to the substrate containing the inorganic material is improved, and the coating film The present invention has been completed by finding that it is possible to suppress the occurrence of dents, underlayer exposure, etc.

According to the invention,
Alkali-soluble resin (A),
Including a photosensitizer (B) and a solvent (C),
There is provided a photosensitive resin composition for forming a permanent film, wherein the solvent contains a solvent (C-1) having a glycol ether structure which is water-soluble and has a boiling point of 130 ° C. or higher.

Further, according to the present invention, a cured film obtained by curing the photosensitive resin composition is provided.

Further, according to the present invention, there is provided an electronic device including the cured film.

According to the invention,
A step of providing an electronic component on one surface of the substrate,
A coating film forming step of coating a photosensitive resin composition containing an alkali-soluble resin (A), a photosensitive material (B), and a solvent (C) on one surface of the substrate to form a coating film;
An exposure step of exposing the formed coating film,
A developing step of developing the exposed coating film, and a heating step of heating the coating film remaining after the development to cure the coating film to form a permanent film,
A method of manufacturing an electronic device including a cured film of the photosensitive resin composition, comprising:
There is provided a method for manufacturing an electronic device, wherein the solvent includes a solvent (C-1) having a glycol ether structure, which is water-soluble and has a boiling point of 130 ° C. or higher.

According to the present invention, a photosensitive resin having excellent wettability with respect to a substrate containing an inorganic material and capable of stably forming a coating film in which the occurrence of dents, undercoat exposure, etc. in the coating film is suppressed A composition is provided. Further, a cured film obtained by curing the photosensitive resin composition, and an electronic device provided with the cured film are provided.

The present embodiment will be described below.
The notation “ab” in the description of the numerical range means a or more and b or less, unless otherwise specified. For example, “1 to 5 mass%” means “1 mass% or more and 5 mass% or less”.
In the present specification, the term "electronic device" means a semiconductor chip, a semiconductor element, a printed wiring board, an electric circuit display device, an information communication terminal, a light emitting diode, a physical battery, a chemical battery, or the like to which an electronic technology is applied. , Device, final product, etc.

The photosensitive resin composition for forming a permanent film of the present invention contains an alkali-soluble resin (A), a photosensitizer (B), and a solvent (C), and the solvent (C) is water-soluble and has a boiling point of 130 ° C. or higher. A solvent (C-1) having a glycol ether structure is included.

In the field of electronic devices, it is common practice to coat the surface of a substrate including semiconductor elements with an organic film called a buffer coat to protect the semiconductor from external stress and contamination. In addition, especially in recent years, a package called a wafer level package (Wafer Level Package) that is processed at the wafer level up to the final process of the package and completed, or a panel-level package (Panel Level Packaging: PLP), which is a larger panel-shaped substrate With the addition of a technology such as a package that is manufactured in a batch using, the needs for forming an insulating layer having a uniform film thickness and spreading evenly on a substrate having a large area are increasing. However, in the conventional photosensitive resin composition, when a coating film is formed on the surface of a substrate containing an inorganic material, in particular, a dent may be seen in the formed coating film or a part of the underlying layer may be exposed, resulting in uniform coating. It may be difficult to form a resin film having a uniform thickness.

In the photosensitive resin composition for permanent film formation containing an alkali-soluble resin (A), a photosensitizer (B), and a solvent (C), the present inventors are water-soluble in the solvent and have a boiling point of 130 ° C. or higher. It was found that a solvent (C-1) having a glycol ether structure is contained, so that a photosensitive resin composition having excellent wettability with respect to a metal and capable of forming a uniform resin film thickness can be obtained, and the present invention is achieved. It has been completed.
That is, the conventional photosensitive resin composition has not been compatible with all the various materials existing on the surface of the panel level package or the like. Then, in a manufacturing process of a panel level package or the like, there is a material that repels the photosensitive resin composition when the resin layer is formed by using a method such as slit coating. However, since the photosensitive resin composition according to the present embodiment contains the solvent (C-1) having a glycol ether structure which is water-soluble and has a boiling point of 130 ° C. or higher as a solvent, it is present on the photosensitive resin composition and the substrate surface. It is presumed that the compatibility with a wide variety of materials is improved. Therefore, even if the photosensitive resin composition is, for example, slit-coated, the photosensitive resin composition is not largely repelled, and it is considered that it is possible to form a coating film having a uniform thickness and no dents or underlayers exposed. To be Furthermore, according to the present invention, since the solvent volatilization is appropriately controlled in the drying step after forming the coating film, it is presumed that a resin film with less thickness unevenness is formed.

First, the components contained in the photosensitive resin composition according to this embodiment will be described.
The photosensitive resin composition according to this embodiment includes an alkali-soluble resin (A), a photosensitizer (B), and a solvent (C).

(Alkali-soluble resin)
The alkali-soluble resin is not limited and can be selected according to the physical properties required for the resin film, such as mechanical properties and optical properties. Specific examples of the alkali-soluble resin include polyamide resin, polybenzoxazole resin, polyimide resin, phenol resin, hydroxystyrene resin, and cyclic olefin resin. The alkali-soluble resin preferably contains at least one of the above specific examples. The alkali-soluble resin may be used alone or in combination of two or more. As the alkali-soluble resin, for example, a polyamide resin or a polybenzoxazole resin is preferably used among the above specific examples, and a polybenzoxazole resin is more preferably used. This can improve the dispersibility of the alkali-soluble resin in the photosensitive resin composition. Further, by improving the physical properties such as the mechanical strength of the resin film made of the photosensitive resin composition, the uniformity of the film thickness can be improved and the occurrence of defects can be suppressed, which is also preferable.

(Polyamide resin, polybenzoxazole resin)
As the polyamide resin, for example, it is preferable to use an aromatic polyamide containing an aromatic ring in the structural unit of polyamide, and more preferable one is one containing a structural unit represented by the following formula (PA1). Thereby, physical properties such as mechanical strength of the resin film made of the photosensitive resin composition can be improved. Therefore, it is also preferable from the viewpoint of improving the uniformity of the film thickness and suppressing the occurrence of defects.
In the present embodiment, the aromatic ring means 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. From the viewpoint of mechanical strength and the like, the polyamide resin of the present embodiment preferably contains a benzene ring as an aromatic ring.

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 dehydrated and ring-closed by being heat-treated at a temperature of 150 ° C. or higher and 380 ° C. or lower for 30 minutes or longer and 50 hours or shorter. 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 the present embodiment is a polyamide resin containing a structural unit represented by the above formula (PA1), for example, the photosensitive resin composition is subjected to the heat treatment to dehydrate and ring-close the polybenzoxazole resin. May be That is, the heat-treated photosensitive resin composition contains a polybenzoxazole resin which is an alkali-soluble resin.
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 produced and then subjected to the heat treatment to dehydrate and ring-close the polybenzoate. It may be an oxazole resin. When a polybenzoxazole resin is obtained by subjecting a polyamide resin to ring opening by dehydration, mechanical properties and thermal properties can be improved. This is convenient from the viewpoint of suppressing the deformation of the resin film.

(Polyamide resin, polyimide resin)
Moreover, as the polyamide resin, for example, a resin containing a structural unit represented by the following general formula (PA2) may be used.
The polyamide resin containing the structural unit represented by the following general formula (PA2) is a precursor of the polyimide resin. The polyamide resin containing the structural unit represented by the following general formula (PA2) is dehydrated and ring-closed by being heat-treated at a temperature of 150 ° C. or higher and 380 ° C. or lower for 30 minutes or longer and 50 hours or shorter. It can be a resin. Here, the structural unit of the following formula (PA2) becomes a structural unit of the following formula (PI1) by dehydration ring closure.
When the alkali-soluble resin according to this embodiment is a polyamide resin containing a structural unit represented by the following formula (PA2), the photosensitive resin composition may be dehydrated and ring-closed by heat treatment to obtain a polyimide resin. That is, the heat-treated photosensitive resin composition contains a polyimide resin which is an alkali-soluble resin.
Further, when the alkali-soluble resin is a polyamide resin containing a structural unit represented by the following formula (PA2), dehydration ring closure and polyimide resin are performed by performing the above heat treatment after producing a resin film and an electronic device described later. May be

In formula (PA2), R ^B and R ^C are each independently an organic group having 1 to 30 carbon atoms.

In the general formula (PI1), R ^B and R ^C are the same as those in the general formula (PA2).

Specifically, R ^B and R ^C in the general formula (PA2) and the general formula (PI1) are preferably organic groups having an aromatic ring.
As the organic group having an aromatic ring, specifically, a group containing a benzene ring, a naphthalene ring or an anthracene ring is preferable, and a group containing a benzene ring is more preferable. As a result, the dispersibility of the alkali-soluble resin can be improved and the contact angle with respect to various materials can be kept within a desired numerical range.

(Method for producing polyamide resin)
The polyamide resin according to this embodiment is polymerized as follows, for example.
First, in a polymerization step (S1), a polyamide is polymerized by polycondensing a diamine monomer and a dicarboxylic acid monomer. Then, in the low molecular weight component removing step (S2), the low molecular weight component is removed to obtain a polyamide resin containing polyamide as a main component.

(Polymerization step (S1))
In the polymerization step (S1), a diamine monomer and a dicarboxylic acid monomer are polycondensed. The polycondensation method for polymerizing the polyamide is not limited, and specific examples thereof 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 the method for obtaining the active ester type dicarboxylic acid include a method in which the dicarboxylic acid is reacted with 1-hydroxy-1,2,3-benzotriazole or the like.

The diamine monomer and dicarboxylic acid monomer used for polymerizing the polyamide resin will be described below. The diamine monomer and the dicarboxylic acid monomer may be used each alone, or two or more diamine monomers and / or two or more dicarboxylic acid monomers may be used.

(Diamine monomer)
The diamine monomer used for the polymerization is not limited, and for example, a diamine monomer having an aromatic ring in the structure is preferably used, and a diamine monomer having a phenolic hydroxyl group in the structure is more preferably used. 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 dispersibility of the composition can be further improved.

Here, as the diamine monomer having a phenolic hydroxyl group in the structure, for example, a compound 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, it is considered that the molecular structure can be frozen by the coordination in which the molecule of the alkali-soluble resin and the metal molecule are more strongly bound, and the adhesion to the substrate can be improved.
In addition, for example, when a diamine monomer represented by the following general formula (DA1) is used, the polyamide resin contains a structural unit represented by the following general formula (PA2). That is, the polyamide resin according to the present embodiment preferably contains, for example, a structural unit represented by the following general formula (PA2).

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

In the general formula (PA2), R ⁴ and R ⁵ to 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 hydrogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, chlorine atom, fluorine atom and bromine atom. A group formed by one or more atoms.
R ⁴ is a divalent group. Here, the divalent group means valence. That is, it indicates that R ⁴ has two bonds to bond to another atom.

When R ⁴ in the general formulas (DA1) and (PA2) contains 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. The group having a number of 1 or more and 5 or less is more preferable, and the group having a carbon number of 1 or more and 3 or less 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. As the linear alkylene group, specifically, 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, 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 An alkylmethylene group such as CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2- ; -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 Groups 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.
As the halogen-substituted alkylene group and the halogen-substituted arylene group, specifically, those in which the hydrogen atom in the above-mentioned alkylene group and arylene group is substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom are used. You can Among these, it is preferable to use one in which a hydrogen atom is replaced by a fluorine atom.

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

R ^{5 to} R ¹⁰ in formulas (DA1) and (PA2) are each independently hydrogen or an organic group having 1 to 30 carbon atoms, such as hydrogen or an organic group having 1 to 10 carbon atoms. It is preferable that hydrogen or an organic group having 1 to 5 carbon atoms is more preferable, hydrogen or an organic group having 1 to 3 carbon atoms is further preferable, and hydrogen or an organic group having 1 to 2 carbon atoms is preferable. More preferably, it is an organic group. This allows the aromatic rings of the polyamide resin to be densely arranged. Therefore, the molecule structure can be frozen and the adhesion can be improved by the coordination in which the molecule of 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, 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 An alkynyl group such as an ethynyl group; an alkylidene group such as a methylidene group and an ethylidene group; an aryl group such as a tolyl group, a xylyl group, a phenyl group, a naphthyl group and an anthracenyl group; an aralkyl group such as a benzyl group and a phenethyl group; an adamantyl group; Cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cyclooctyl group; Group, and the like 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 and 4,4′-methylenebis (2-amino-3). , 6 dimethylphenol), 4,4′-methylenebis (2-aminophenol), 1,1-bis (3-amino4-hydroxyphenyl) ethane, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, etc. Is mentioned. By using these diamine monomers, the aromatic rings of the polyamide resin can be closely arranged. Therefore, the molecule structure can be frozen and the adhesion can be improved by the coordination in which the molecule of the alkali-soluble resin and the metal molecule are more strongly bound. As the diamine monomer, one kind or a combination of two or more kinds among the above specific examples can be used.
The structural formulas of these diamine monomers are shown below.

(Dicarboxylic acid monomer)
The dicarboxylic acid monomer used for the polymerization is not limited, and for example, it is preferable to use a dicarboxylic acid monomer containing an aromatic ring in the structure.
As the dicarboxylic acid monomer containing an aromatic ring, it is preferable to use, for example, one represented by the following general formula (DC1). By producing a polyamide resin using such a dicarboxylic acid monomer as a raw material, the conformation of the polyamide resin can be controlled and the dispersibility in a mixed solvent can be improved. The improved dispersibility makes it easier to control the values of θ _max −θ _min and θ _ave to desired values.

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

In addition, for example, when the dicarboxylic acid monomer represented by the following general formula (DC1) is used, the polyamide resin typically includes a structural unit represented by the following general formula (PA3). In the general formula (PA3), the definitions of R ¹¹ and R ¹² to 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 hydrogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, chlorine atom, fluorine atom and bromine atom. A group formed by one or more atoms.
R ¹¹ is a divalent group. Here, the divalent group means valence. That is, it shows that R ¹¹ has two bonds to bond with 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, preferably a group having 1 to 10 carbon atoms, The group having a number of 1 or more and 5 or less is more preferable, and the group having a carbon number of 1 or more and 3 or less 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. As the linear alkylene group, specifically, 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, 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 An alkylmethylene group such as CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2- ; -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 Groups 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.
As the halogen-substituted alkylene group and the halogen-substituted arylene group, specifically, those in which the hydrogen atom in the above-mentioned alkylene group and arylene group is substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom are used. You can Among these, it is preferable to use one in which a hydrogen atom is replaced by a fluorine atom.

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

R ^{12 to} R ¹⁹ in formulas (DC1) and (PA3) are each independently hydrogen or an organic group having 1 to 30 carbon atoms, such as hydrogen or an organic group having 1 to 10 carbon atoms. It is preferable that hydrogen or an organic group having 1 to 5 carbon atoms is more preferable, hydrogen or an organic group having 1 to 3 carbon atoms is further preferable, and hydrogen is further preferable.

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, 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 An alkynyl group such as an ethynyl group; an alkylidene group such as a methylidene group and an ethylidene group; an aryl group such as a tolyl group, a xylyl group, a phenyl group, a naphthyl group and an anthracenyl group; an aralkyl group such as a benzyl group and a phenethyl group; an adamantyl group; Cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cyclooctyl group; Lil group, and alkaryl groups, such as xylyl group.

As the dicarboxylic acid monomer, specifically, diphenyl ether 4,4'-dicarboxylic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid or the like can be used. As the dicarboxylic acid monomer, it is preferable to use diphenyl ether 4,4'-dicarboxylic acid or isophthalic acid among the above specific examples, and more preferable to use diphenyl ether 4,4'-dicarboxylic acid. The aromatic rings of the polyamide resin can be closely arranged. Therefore, the molecule structure of the alkali-soluble resin and the metal molecule are more strongly bound to each other, so that the molecular structure can be frozen and the adhesion can be improved.

Incidentally, it is preferable to modify the amino group present at the terminal of the polyamide resin at the same time as or after the polymerization step (S1). The modification can be performed, for example, by reacting a diamine monomer or a polyamide resin with a specific acid anhydride or a specific monocarboxylic acid. Therefore, the polyamide resin according to the present embodiment preferably has a terminal amino group modified with a specific acid anhydride or a specific monocarboxylic acid. The specific acid anhydride and the specific monocarboxylic acid have at least one functional group consisting of an alkenyl group, an alkynyl group, and a hydroxyl group. As the above-mentioned specific acid anhydride and specific monocarboxylic acid, for example, those containing a nitrogen atom are preferable. This can improve the adhesion between the photosensitive resin composition after post-baking and the metal.

Specific examples of the specific acid anhydride include maleic acid anhydride, citraconic acid anhydride, 2,3-dimethylmaleic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid anhydride, and exo-3. , 6-Epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride Compounds, het acid anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride and the like. As the specific acid anhydride, one or a combination of two or more of the above specific examples can be used.

When the amino group existing at the end of the polyamide resin is modified with a ring-shaped specific acid anhydride, the ring-shaped specific acid anhydride is opened. Here, after modifying the polyamide resin, a ring-shaped structural unit derived from a specific acid anhydride may be closed to form an imide ring. Examples of the method for ring closure include heat treatment and the like.
Specific examples of the above-mentioned monocarboxylic acid include 5-norbornene-2-carboxylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid and the like. As the specific monocarboxylic acid, one kind or a combination of two or more kinds out of the above specific examples can be used.

Further, the carboxyl group existing at the terminal of the polyamide resin may be modified at the same time as the polymerization step (S1) or after the polymerization step (S1). The modification can be performed, for example, by reacting a dicarboxylic acid monomer or a polyamide resin with a specific nitrogen atom-containing heteroaromatic compound. Therefore, it is preferable that the terminal carboxyl group of the polyamide resin according to this embodiment is modified with a specific nitrogen atom-containing heteroaromatic compound. The specific nitrogen atom-containing heteroaromatic compound means 1- (5-1H-triazoyl) methylamino group, 3- (1H-pyrazolyl) amino group, 4- (1H-pyrazoyl) amino group, 5- (1H-pyrazolyl) amino group, 1- (3-1H-pyrazolyl) methylamino group, 1- (4-1H-pyrazolyl) methylamino group, 1- (5-1H-pyrazolyl) methylamino group, (1H- One or more functional groups consisting of a tetrazol-5-yl) amino group, a 1- (1H-tetrazol-5-yl) methyl-amino group and a 3- (1H-tetrazol-5-yl) benz-amino group It has a group. This can increase the number of lone electron pairs in the photosensitive resin composition. Therefore, the adhesion between the photosensitive resin composition after pre-baking and post-baking and the 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))
After the polymerization step (S1), a low molecular weight component removing step (S2) is preferably performed to remove the low molecular weight component.
Specifically, 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 redissolved in an organic solvent such as water / isopropanol. As a result, the precipitate can be filtered off to obtain a polyamide resin from which the low molecular weight component has been removed.

Regarding the polyamide resin, for example, it is preferable to prepare a photosensitive resin composition which is a varnish without going through the step of completely drying the solvent after the step of removing the low molecular weight component. This can prevent the dispersibility of the polyamide from decreasing due to the interaction between the molecules of the polyamide resin, which is derived from the amide bond. Therefore, the contact angles of various materials on the substrate of the panel level package can be kept uniform.

(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; phenols such as novolac-type phenol resins, resole-type phenol resins, and cresol novolac 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, and the like. In addition, as a phenol resin, 1 type (s) or 2 or more types can be included among the said specific examples.

The above-mentioned phenol compound used in the reaction product of the phenol compound and the aldehyde compound or the reaction product of the phenol compound and the dimethanol compound 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, 3,5-xylenol and other xylenols; o-ethylphenol, m-ethylphenol, p-ethylphenol and other ethylphenols; isopropylphenol, butylphenol, p-tert- Examples thereof include alkylphenols such as butylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, pyrogallol, and phloroglucinol; and biphenyl phenols such as 4,4′-biphenol. As the phenol compound, one or more of the above specific examples can be used.

The aldehyde compound used in 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 the aldehyde compound, one or more of the above specific examples can be used.

The dimethanol compound used in the reaction product of the phenol compound and the dimethanol compound described above is not limited.
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-naphthalenedimethanol and 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 , Etc., bis (alkoxymethyl) compounds, or 1,4-bis (chloromethyl) benzene, 1,3-bis (chloromethyl) Benzene, 1,4-bis (bromomethyl) benzene, 1,3-bis (bromomethyl) benzene, 4,4′-bis (chloromethyl) biphenyl, 3,4′-bis (chloromethyl) biphenyl, 3,3 ′ -Bis (halgenoalkyl) compounds such as bis (chloromethyl) biphenyl, 4,4'-bis (bromomethyl) biphenyl, 3,4'-bis (bromomethyl) biphenyl or 3,3'-bis (bromomethyl) biphenyl, Examples include biphenylaralkyl compounds such as 4,4′-bis (methoxymethyl) biphenyl and 4,4′-bis (methoxymethyl) biphenyl. As the dimethanol compound, one or more of the above specific examples can be used.

(Hydroxystyrene resin)
The hydroxystyrene resin is not limited, and specifically, a polymerization reaction product or copolymer obtained by polymerizing or copolymerizing one kind or two or more kinds selected from the group consisting of hydroxystyrene, hydroxystyrene derivative, styrene and styrene derivative. A polymerization reaction product can be used.
Specific examples of the hydroxystyrene derivative and the styrene derivative include those in which the hydrogen atom of the aromatic ring of hydroxystyrene or styrene is replaced with a monovalent organic group. Examples of the monovalent organic group 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; methylidene group, Examples thereof include an alkylidene group such as an ethylidene group; a cycloalkyl group such as a cyclopropyl group; a heterocyclic group such as an epoxy group and an 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 kind or two or more kinds selected from the group consisting of norbornene and norbornene derivatives is used. be able to.
Here, as the norbornene derivative, specifically, norbornadiene, bicyclo [2.2.1] -hept-2-ene (conventional name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl- 2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (1-Methyl-4-pentenyl) -2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, 5-norbornene- Examples thereof include methyl 2-carboxylate and 5-norbornene-2,3-dicarboxylic acid anhydride.

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, further preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more. As a result, the dispersibility of the alkali-soluble resin in the photosensitive resin composition can be improved and the contact angle for various materials can be set within a desired numerical range.
Further, 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, and 90 It is more preferably not more than 85 parts by mass, further preferably not more than 85 parts by mass.
In the present embodiment, the total solid content of the photosensitive resin composition refers to the total of the components contained in the photosensitive resin composition excluding the solvent.

(Photosensitizer)
As the photosensitizer, a photoacid generator that generates an acid by absorbing light energy can be used.
Specific examples of the photoacid generator include diazoquinone compounds; diaryl iodonium salts; 2-nitrobenzyl ester compounds; N-iminosulfonate compounds; imidosulfonate compounds; 2,6-bis (trichloromethyl) -1,3. 5-triazine compounds; dihydropyridine compounds and the like. Among these, it is preferable to use the 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. The photoacid generator may include one or more of the above specific examples.
When the photosensitive resin composition is a positive type, in addition to the above specific examples, a triarylsulfonium salt; an onium salt such as a sulfonium / borate salt may be used in combination with the above specific examples. This can further improve the sensitivity of the photosensitive resin composition.

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).
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 appearance of the photosensitive resin composition can be improved.

The lower limit of the content of the photosensitizer 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. It is more preferably 5 parts by mass or more. Thereby, the photosensitive resin composition can exhibit appropriate sensitivity.
Further, the upper limit of the content of the photosensitizer in the photosensitive resin composition is, for example, 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 preferable. This can prevent the photosensitive resin composition from being repelled by the material present on the surface of the substrate.

(solvent)
The photosensitive resin composition according to the present embodiment contains, as the solvent (C), a water-soluble solvent having a glycol ether structure (C-1) having a boiling point of 130 ° C. or higher.

Incidentally, the water-soluble solvent in the present invention means a solvent having a solubility of 10 g or more in 100 g of water at 20 ° C. The solubility of the solvent (C-1) in 100 g of water at 20 ° C. is 10 g or more, preferably 30 g or more, more preferably 50 g or more, and the higher the solubility, the more it is dissolved in water or the developer. Mixing is easy and preferred.

Further, the solvent (C-1) having a glycol ether structure has a boiling point of 130 ° C. or higher, more preferably 135 ° C. or higher, and particularly preferably 140 ° C. or higher. The solvent (C-1) having a glycol ether structure can have a boiling point of 200 ° C. or lower, and more preferably 190 ° C. or lower. This makes it possible to improve the wettability between the photosensitive resin composition and the material on the surface of various substrates, and to control the drying rate of the solvent, so that the substrate can be evenly spread and evenly spread. It is possible to form a resin film having various thicknesses and compositions.

Also, the solvent (C-1) having a glycol ether structure preferably has a surface energy of 30 mN / m. The surface tension of each solvent can be known from a solvent handbook (published by Kodansha Scientific Co., Ltd.), SDS of each solvent, and the like.

The solvent (C-1) having a glycol ether structure means a solvent having a structure in which one or both of the hydroxyl groups of glycol are etherified. Specific examples of the solvent (C-1) include ethylene glycol monotert-butyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, propylene glycol monopropyl ether, propylene glycol tertiary. Butyl ether, propylene glycol monoethyl ether, tripropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol n-butyl ether, 3-butylene glycol-3-monomethyl ether, selected from the group consisting of these. At least one of It is preferred. Further, the solvent (C-1) preferably contains an alkylene glycol monoalkyl ether.
The solvent (C-1) more preferably contains propylene glycol monopropyl ether or ethylene glycol monobutyl ether, and particularly preferably contains propylene glycol monopropyl ether.

By using the solvent (C-1) in the above mode, the compatibility between the photosensitive resin composition and various materials existing on the surface of the substrate is improved, and the photosensitive resin composition is prevented from being greatly repelled. Since a coating film having a uniform thickness can be formed, and the volatilization of the solvent is appropriately controlled in the drying step after forming the coating film, it becomes possible to form a resin film with less unevenness in thickness.
Further, the solvent (C-1) is preferably represented by the following formula.

In the above formula (GE), R ¹ to R ⁴ each independently represent a hydrogen atom or an organic group. It is preferable that the solvent (C-1) has a structure containing a hydroxyl group at its one end since the water solubility thereof becomes high and mixing with the developing solution becomes easy.

The solvent (C) may include at least one type of solvent (C-1) and may include two or more types.

Further, the photosensitive resin composition according to the present embodiment may contain, as the solvent (C), a solvent that is water-soluble and has a boiling point of 130 ° C. or higher, other than the solvent having a glycol ether structure (C-1).
That is, the solvent (C) is a mixed solvent containing the solvent (C-1) and a solvent other than the solvent (C-1) (hereinafter, referred to as other solvent (C-2)). Good.
Examples of the other solvent (C-2) include urea compounds, amide compounds, ether solvents, acetate solvents, alcohol solvents, ketone solvents, lactone solvents, carbonate solvents, sulfone solvents, ester solvents. , Aromatic hydrocarbon solvents and the like. As the other solvent (C-2), one of the above specific examples may be used, or two or more may be used in combination.

Specific examples of the other solvent (C-2) are described below. 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, Examples thereof include O-ethyl-N, N′-diisopropylisourea and O-benzyl-N, N′-diisopropylisourea.
Specific examples of the amide compound include N-methylpyrrolidone (NMP), 3-methoxy-N, N-dimethylpropanamide, N, N-dimethylformamide, N, N-dimethylpropionamide, N, N-diethyl. Examples include acetamide, 3-butoxy-N, N-dimethylpropanamide, N, N-dibutylformamide and the like.
Specific examples of the ether solvent include propylene glycol monomethyl ether (PGME), ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, ethylene glycol diethyl ether, and diethylene glycol dibutyl ether.
Specific examples of the acetate solvent include propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate and the like.
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, 2-heptanone and the like.
Specific examples of the lactone solvent include γ-butyrolactone (GBL) and γ-valerolactone.
Specific examples of the carbonate-based solvent include ethylene carbonate and propylene carbonate.
Specific examples of the sulfone-based solvent include dimethyl sulfoxide (DMSO) and sulfolane.
Specific examples of the ester solvent include methyl pyruvate, ethyl pyruvate, and methyl-3-methoxypropionate.
Specific examples of the aromatic hydrocarbon solvent include mesitylene, toluene, xylene and the like.
Among the above, urea compounds, lactone solvents, ether solvents and acetate solvents are preferable.

As the other solvent (C-2), from the viewpoint of solubility in an alkali-soluble resin or the like, among the above, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone (GBL), At least one selected from tetramethylurea (TMU) and N-methylpyrrolidone (NMP) is preferably used in combination with the solvent (C-1), and selected from PGME, PGMEA, GBL, TMU and NMP. More preferably, at least one is used in combination with propylene glycol monopropyl ether and / or ethylene glycol monobutyl ether, and at least one selected from PGME, PGMEA, GBL, TMU and NMP is used. It is particularly preferable to use in combination with the glycol monopropyl ether.

From the viewpoint of suppressing the thickness unevenness when the coating film is dried, the solvent (C-1) is combined with another solvent (C-2) having a boiling point different from the boiling point of the solvent (C-1) by 20 degrees or more. You may try. Specifically, it is preferable to combine propylene glycol monopropyl ether and propylene glycol monopropyl ether with a solvent having a boiling point different by 20 ° C. or more. Among these, it is preferable to use one having a boiling point of the other solvent (C-2) higher than that of the solvent (C-1) by 20 ° C. or more, or 25 ° C. or more. By using the mixed solvent thus combined, it is possible to volatilize the solvent at an optimum rate, so that it is possible to form a resin film having less unevenness.
The difference between the boiling point of the solvent (C-1) and the boiling point of the other solvent (C-2) may be, for example, 100 degrees or less.

The lower limit of the content of the solvent (C-1) in the solvent (C) is, for example, preferably 1 part by mass or more, and preferably 3 parts by mass or more, when the solvent (C) is 100 parts by mass. It is more preferable that the amount is 5 parts by mass or more, further preferably 10 parts by mass or more. This makes it possible to improve the wettability between the photosensitive resin composition and the material on the surface of various substrates and to control the drying rate of the solvent, thereby forming a resin film having a uniform thickness. be able to.
The upper limit of the content of the solvent (C-1) in the solvent is, for example, 100 parts by mass or less, 80 parts by mass or less, 60 parts by mass or less, 40 parts by mass or less, when the solvent is 100 parts by mass. Can be
From the viewpoint of solubility in an alkali-soluble resin and the like, and from the viewpoint of volatilizing the solvent at an optimum rate, the solvent (C) contains the solvent (C-1) and contains one other solvent (C-2). Alternatively, it is preferable to include two or more kinds.

Among the above, the solvent (C) contains propylene glycol monopropyl ether as the solvent (C-1) and propylene glycol monomethyl ether (PGME) as the other solvent (C-2),
An embodiment containing propylene glycol monopropyl ether as the solvent (C-1) and propylene glycol monomethyl ether acetate (PGMEA) as the other solvent (C-2),
An embodiment containing propylene glycol monopropyl ether as the solvent (C-1) and γ-butyrolactone (GBL) as the other solvent (C-2),
An embodiment containing propylene glycol monopropyl ether as the solvent (C-1) and tetramethylurea (TMU) as the other solvent (C-2),
An embodiment containing propylene glycol monopropyl ether as the solvent (C-1) and N-methylpyrrolidone (NMP) as the other solvent (C-2),
A preferred embodiment includes propylene glycol monopropyl ether as the solvent (C-1) and γ-butyrolactone (GBL) and tetramethylurea (TMU) as the other solvent (C-2).
By using the solvent in the above combination, it is possible to obtain a photosensitive resin composition having excellent wettability of the photosensitive resin composition with respect to the resin material, uniform film-forming ability, and solubility of the alkali-soluble resin.

When a polybenzoxazole resin is used as the alkali-soluble resin, it should contain N-methylpyrrolidone (NMP) and / or γ-butyrolactone (GBL) and / or tetramethylurea (TMU) as another solvent (C-2). Is preferred. When a polybenzoxazole resin is used as the alkali-soluble resin, it is preferable to include propylene glycol monomethyl ether (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) as the other solvent (C-2).
When a cyclic olefin resin is used as the alkali-soluble resin, propylene glycol monopropyl ether and / or ethylene glycol monobutyl ether is used as the solvent (C-1) and no other solvent (C-2) is added, or the solvent ( It is preferable to use propylene glycol monopropyl ether as C-1) and propylene glycol monomethyl ether (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) as other solvent (C-2). It is particularly preferable to use propylene glycol monopropyl ether and / or ethylene glycol monobutyl ether as C-1) and not add another solvent (C-2).
With the above combination, a photosensitive resin composition having a uniform composition having excellent compatibility with a resin can be obtained, and a photosensitive resin composition capable of forming a uniform coating film can be obtained even on the components. .

The lower limit of the content of the solvent (C) in the photosensitive resin composition is, for example, preferably 50 parts by mass or more, and 60 parts by mass or more, when the photosensitive resin composition is 100 parts by mass. It is more preferable that the amount is 70 parts by mass or more. The upper limit of the content of the solvent (C) in the photosensitive resin composition is, for example, preferably 130 parts by mass or less and 110 parts by mass or less when the photosensitive resin composition is 100 parts by mass. Is more preferable. Thereby, the dispersibility in the photosensitive resin composition can be improved, the contact angle with respect to various materials can be set within a desired numerical range, and the viscosity suitable for forming a coating film can be obtained.

The photosensitive resin composition according to this embodiment may have a composition in which an amide compound having a cyclic structure such as N-methylpyrrolidone (NMP) is less than 1% by mass as a solvent. In addition, the photosensitive resin composition according to the present embodiment may be a composition that does not include an amide compound having a cyclic structure such as N-methylpyrrolidone (NMP) as a solvent. Conventionally used amide compounds having a cyclic structure such as N-methylpyrrolidone have various adverse effects such as impaired reproductive function when taken into the human body, and amide compounds having a cyclic structure such as N-methylpyrrolidone (NMP). The safety can be improved by making the composition not more than 1 mass% less than 1% by mass.

The photosensitive resin composition according to the present embodiment further contains additives such as an adhesion aid, a silane coupling agent, a thermal crosslinking agent, a surfactant, an antioxidant, a dissolution accelerator, a filler, and a sensitizer. You may.
The representative components will be described in detail below.

(Adhesion aid)
The photosensitive resin composition according to this embodiment may further include an adhesion aid. As the adhesion aid, specifically, a triazole compound or aminosilane can be used. This can further increase the number of lone electron pairs derived from the nitrogen atom. Therefore, the components other than the solvent of the photosensitive resin composition can be coordinated with the metal atoms, and the adhesion can be further improved. As the adhesion aid, one of a triazole compound and aminosilane may be used, or a triazole compound and aminosilane may be used in combination.
Specific examples of the triazole compound include 4-amino-1,2,4-triazole, 4H-1,2,4-triazol-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-triazol-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 Include 1,2,4-triazole, such as Le-1,2,4-triazole-3-carboxamide. As the triazole compound, one kind or a combination of two or more kinds out of the above specific examples can be used.
Specific examples of the aminosilane include condensates of cyclohexene-1,2-dicarboxylic acid anhydride and 3-aminopropyltriethoxysilane, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 3 -Aminopropyltriethoxysilane condensate, 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- (trimethoxysilyl) ) Propyl] ethylenediamine, N, N'-bis- (3-triethoxysilylpropyl) ethylenediamine, N, N'-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N'-bis [3- ( Methyldiethoxysilyl) propyl] ethylenediamine, N, N′-bis [3- (dimethylmethoxysilyl) propyl] ethylenediamine, N- [3- (methyldimethoxysilyl) propyl] -N ′-[3- (trimethoxysilyl) ) Propyl] ethylenediamine, N, N'-bis [3- (trimethoxysilyl) propyl] diaminopropane, N, N'-bis [3- (trimethoxysilyl) propyl] diaminohexane, N, N'-bis [ 3- (trimethoxysilyl) propyl] diethylenetriamine and the like. As the aminosilane, one or a combination of two or more of the above specific examples can be used.

The lower limit value of the content of the adhesion aid in the photosensitive resin composition is, for example, preferably 0.1 part by mass or more, and 1.0 part by mass or more with respect to 100 parts by mass of the alkali-soluble resin. It is more preferably 2.0 parts by mass or more, further preferably 3.0 parts by mass or more. Thereby, the triazole compound is preferably coordinated with the metal atom such as Al and Cu, and the adhesion can be further improved.
Further, the upper limit of the content of the adhesion aid in the photosensitive resin composition is, for example, preferably 10 parts by mass or less, and 7 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin. It is more preferable that the amount is 5 parts by mass or less. As a result, the adhesion aid can be suitably dispersed in the photosensitive resin composition, and the adhesion can be improved.

(Silane coupling agent)
The photosensitive resin composition according to this embodiment may further include a silane coupling agent. Examples of the silane coupling agent include those other than the aminosilane exemplified as the adhesion aid.
Specific examples of the silane coupling agent having a structure different from that of the above-mentioned silane compound include vinyl silane such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3 -Epoxysilanes such as glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; p-styryltrimethoxysilane Styrylsilane such as; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. Acrylic silane such as 3-acryloxypropyltrimethoxysilane; Isocyanurate silane; Alkylsilane; Ureidosilane such as 3-ureidopropyltrialkoxysilane; 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Mercaptosilanes; isocyanate silanes such as 3-isocyanatopropyltriethoxysilane; titanium compounds; aluminum chelates; aluminum / zirconium compounds. As the silane coupling agent, one kind or two or more kinds of the above specific examples can be blended.

(Thermal crosslinking agent)
The photosensitive resin composition according to the present embodiment may include a thermal crosslinking agent capable of reacting with an alkali-soluble resin by heat. This makes it possible to improve mechanical properties such as tensile elongation at break of a cured product obtained by post-baking the photosensitive resin composition. It is also convenient from the viewpoint of improving the sensitivity of the resin film formed of 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) Compounds having: phenols such as phlorogluside; 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 , A compound having an alkoxymethyl group such as 4,4′-methylenebis (2,6-dimethoxymethylphenol); a methylolmelamine compound represented by hexamethylolmelamine, hexabutanolmelamine and the like; an alkoxymelamine compound such as hexamethoxymelamine; Alkoxymethylglycoluril compounds such as tetramethoxymethylglycoluril; methylolurea compounds such as methylolbenzoguanamine compounds and dimethylolethyleneurea; cyano compounds such as dicyanoaniline, dicyanophenol, cyanophenylsulfonic acid; 1,4-phenylene diisocyanate , 3,3′-Dimethyldiphenylmethane-4,4′-diisocyanate and other isocyanate compounds; ethylene glycol diglycidyl ether, bi 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 novolac resin type epoxy resin; N, N ′ Examples thereof include maleimide compounds such as -1,3-phenylene dimaleimide and N, N'-methylenedimaleimide. As the thermal cross-linking agent, one kind or a combination of two or more kinds among 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, relative to 100 parts by mass of the alkali-soluble resin. , 12 parts by mass or less, more preferably 10 parts by mass or less. Thereby, even if the thermal cross-linking agent has a solvating functional group such as a phenolic hydroxyl group, it is possible to suppress deterioration in chemical resistance after post-baking.
The lower limit of the content of the thermal crosslinking agent in the photosensitive resin composition is, for example, 0.1 part by mass or more, and preferably 1 part by mass or more, based on 100 parts by mass of the alkali-soluble resin. It is more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, 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 lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other polyoxyethylene alkyl ethers; polyoxyethylene octyl phenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as nonyl phenyl 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.), MegaFac F171, MegaFac F172, MegaFac F173, MegaFac F177, MegaFac F444, MegaFac F 70, MegaFac F471, MegaFac F475, MegaFac F482, MegaFac 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 Company Fluorine-based surfactants commercially available under the names such as; organosiloxane copolymer KP341 (produced by Shin-Etsu Chemical Co., Ltd.); (meth) acrylic acid-based copolymer Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
As the surfactant, a silicone-based surfactant (for example, polyether-modified dimethylsiloxane) can also be preferably used. Specific examples of the silicone-based surfactant include SH series, SD series and ST series manufactured by Toray Dow Corning, BYK series manufactured by Big Chemie Japan, KP series manufactured by Shin-Etsu Chemical Co., Ltd., and deformed by NOF CORPORATION ( The registered trademark) series, TSF series of Toshiba Silicone Co., Ltd., and the like can be mentioned.
Among these, it is preferable to use a fluorosurfactant having a perfluoroalkyl group. Examples of the fluorosurfactant having a perfluoroalkyl group include Megafac F171, Megafac F173, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, and Megafac among the above specific examples. One or more selected from F477 (manufactured by DIC), Surflon S-381, Surflon S-383, Surflon S-393 (manufactured by AGC Seimi Chemical Co.), Novec FC4430 and Novec FC4432 (manufactured by 3M Japan). Is preferably used.

(Antioxidant)
The photosensitive resin composition according to this embodiment may further include 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 the 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] and 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-t-butylphenol), bis [3,3-bis (4-hydroxy-3-) -Butylphenyl) butyric acid] glycol ester, 4,4'-butylidene bis (6-t-butyl-m-cresol), 2,2'-ethylidene bis (4,6-di-t-butylphenol), 2, 2'-ethylidene bis (4-s-butyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, bis [2-t- Butyl-4-methyl-6- (2-hydroxy-3-t-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-t-butyl-4-hydroxy-5-methylphenyl) propionate], Triethylene glycol bis [β- (3-t- Butyl-4-hydroxy-5-methylphenyl) propionate], 1,1′-bis (4-hydroxyphenyl) cyclohexane, 2,2′-methylene (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (6- (1-methylcyclohexyl) -4-methyl Phenol), 4,4′-butylidene bis (3-methyl-6-t-butylphenol), 3,9-bis (2- (3-t-butyl-4-hydroxy-5-methylphenylpropionyloxy) 1,1 -Dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-bis (3,4) 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 thereof include styrenated phenol and 2,4-bis ((octylthio) methyl) -5-methylphenol.
Examples of phosphorus antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenylphosphite), and tetrakis (2 , 4-Di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis- (2,6 -Dicumylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, tris (mixed mono and di-nonylphenylphosphite), bis (2,2 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methoxycalcium Examples thereof include bonylethyl-phenyl) pentaerythritol diphosphite and bis (2,6-di-t-butyl-4-octadecyloxycarbonylethylphenyl) pentaerythritol diphosphite.
As the thioether type antioxidant, dilauryl-3,3'-thiodipropionate, bis (2-methyl-4- (3-n-dodecyl) thiopropionyloxy) -5-t-butylphenyl) sulfide , Distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis (3-lauryl) thiopropionate and the like.

(Filler)
The photosensitive resin composition according to this embodiment may further contain a filler. As the filler, an appropriate filler can be selected depending on the 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 fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, silica such as finely divided silica; alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, silicon carbide. , Metal compounds such as aluminum hydroxide, magnesium hydroxide, and titanium white; talc; clay; mica; glass fiber and the like. As the inorganic filler, one kind or a combination of two or more kinds among the above specific examples can be used.
Specific examples of the organic filler include organosilicone powder and polyethylene powder. As the organic filler, one kind or a combination of two or more kinds out of the above specific examples can be used.

(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 as a varnish can be obtained.
In the photosensitive resin composition, the solid content concentration of the entire photosensitive resin composition can be, for example, 10 to 30% by mass.

(Photosensitive resin composition)
The photosensitive resin composition according to the present embodiment, for example, a varnish of the photosensitive resin composition is applied to a substrate having a relatively large area including a semiconductor element or the like, and then prebaked to dry the resin. It is used by forming a film, then exposing and developing to pattern the resin film into a desired shape, and then post-baking the resin film to cure it to form a cured film.
In the case of producing the above-mentioned permanent film, the prebaking condition may be, for example, a heat treatment at a temperature of 90 ° C. or higher and 130 ° C. or lower for 30 seconds or longer and 1 hour or shorter. In addition, as the post-baking condition, for example, heat treatment at a temperature of 150 ° C. or higher and 350 ° C. or lower for 30 minutes or longer and 10 hours or shorter can be performed.

The viscosity of the photosensitive resin composition according to this embodiment can be appropriately set according to the desired thickness of the resin film. The viscosity of the photosensitive resin composition can be adjusted by adding a solvent. During the adjustment, it is preferable to keep the content of the solvent (C-1) in the solvent (C) constant.
The upper limit of the viscosity of the photosensitive resin composition according to the exemplary embodiment may be, for example, 5000 mPa · s or less, 1800 mPa · s or less, or 1500 mPa · s or less. Further, the lower limit of the viscosity of the photosensitive resin composition according to the present embodiment may be, for example, 1 mPa · s or more, or 10 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, for example, with an E-type viscometer at a temperature of 25 ° C. and 300 seconds after the start of rotation.

The flash point of the photosensitive resin composition according to the present embodiment is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and particularly preferably 60 ° C. or higher. Here, the flash point refers to the flash point obtained by the tag closing method based on JIS K 2265-1. By setting the flash point to be equal to or higher than the above lower limit, it is possible to maintain handling safety in manufacturing during transportation.

The surface energy of the photosensitive resin composition according to this embodiment is preferably 21.0 mN / m or less. Here, the surface energy can be obtained, for example, by evaluating the contact angle with respect to sputtered Cu and a bare silicon wafer. Specifically, at a temperature of 25 ° C., the contact angle 10 seconds after the deposition of 2 ml of the viscosity-adjusted varnish of the photosensitive resin composition on each substrate can be evaluated by the droplet method. it can. For the measurement, for example, a contact angle meter (DROPMASTER-501 manufactured by Kyowa Interface Science Co., Ltd.) can be used. The lower limit of the surface energy is not particularly limited, but can be set to 15 mN / m, for example.

(Use)
The cured film obtained by curing the photosensitive resin composition of the present embodiment is used for the purpose of using a permanent film, for example, it can be used for buffer coating and can be used for various electronic devices.
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 formed by drying or curing the photosensitive resin composition.

The permanent film is, for example, a cured film obtained by applying a photosensitive resin composition, then performing pre-baking, exposure and development, patterning into a desired shape, and curing by post-baking. Composed. The permanent film can be used as a protective film for electronic devices, an interlayer film, a dam material, and the like.

<Method of manufacturing electronic device>
The manufacturing method of the electronic device of the present invention is
A step of providing an electronic component on one surface of the substrate,
On one surface of the substrate,
Alkali-soluble resin (A),
A coating film forming step of forming a coating film by applying a photosensitive resin composition containing a photosensitive material (B) and a solvent (C);
An exposure step of exposing the formed coating film,
A developing step of developing the exposed coating film, and a heating step of heating the coating film remaining after the development to cure the coating film to form a permanent film,
The solvent (C) includes a solvent (C-1) having a glycol ether structure, which is water-soluble and has a boiling point of 130 ° C. or higher.

In the manufacturing method according to this embodiment, the substrate is not particularly limited, and examples thereof include a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, and a GaN wafer. In the step of providing the electronic component on one surface of the substrate, the electronic component such as the semiconductor element or the display element can be provided by a known method.

In the present embodiment, a photosensitive resin composition containing an alkali-soluble resin (A), a photosensitive material (B), and a solvent (C) is applied onto a substrate to form a coating film. Further, the solvent (C) includes a solvent (C-1) having a glycol ether structure, which is water-soluble and has a boiling point of 130 ° C. or higher. The photosensitive resin composition according to this embodiment is as described above. The coating film can be formed by spin coating, spray coating, dipping, printing, roll coating, an inkjet method or the like, and for example, slit coating is preferable. Thereby, a uniform resin film can be formed in a wide area.

The thickness of the permanent film is not particularly limited, but is, for example, about 2 to 30 μm, preferably about 5 to 20 μm.
After coating the photosensitive resin composition, it is preferable to perform a method of removing the solvent, and various methods can be applied to remove the solvent (for example, heating). When forming a coating film having a relatively large area, it is preferable to apply vacuum drying. That is, it is preferable to dry the panel coated with the photosensitive resin composition under a reduced pressure environment (for example, under an environment of 30 Pa or less). Note that drying under reduced pressure also has an advantage of reducing microbubbles that may occur during coating.

When prebaking is performed, the conditions are, for example, 70 to 160 ° C. and 5 seconds to 30 minutes.
For exposure, electromagnetic waves of various wavelengths, particle beams, etc. can be used. For example, ultraviolet rays such as g-rays and i-rays, visible rays, lasers, X-rays, electron rays and the like are used. Ultraviolet rays such as g rays or i rays are preferable. The exposure amount is appropriately set according to the sensitivity of the photosensitive adhesive composition and the like, but is, for example, about 30 to 3000 mJ / cm ² . The exposure is usually performed by using an appropriate mask pattern.
Various developers can be applied for the development. For example, alkali metal carbonates, alkali metal hydroxides, alkali developers such as tetramethylammonium hydroxide, dimethylformamide, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, acetic acid. Examples include organic developers such as butyl. Among these, an alkali developing solution is preferable, and an aqueous solution of tetramethylammonium hydroxide is particularly preferable. Examples of the method for supplying the developing solution include spraying, paddle, dipping and the like. The spray method is preferable in terms of processing a large-area panel.
The post-baking condition (curing condition) is not particularly limited, but is, for example, 80 to 300 ° C. and 30 to 300 minutes.

A panel level package will be described as one of electronic devices including a resin film obtained by curing the photosensitive resin composition of the present embodiment.
Panel-level packages have various structures such as cores, chips, prepregs (reinforced plastic materials obtained by uniformly impregnating a fibrous reinforcing material such as glass cloth or carbon fiber with a thermosetting resin such as epoxy). It is sealed or fixed with a sheet-shaped sealing material to form a panel. Further, in the panel level package, metals such as Cu and Al are usually used as wirings (these metals are usually incorporated in the panel level package by a plating method or a sputtering method), and a passivation film such as silicon nitride is also used. May be included. Further, in one aspect, the panel-level package has a resin film formed by curing the photosensitive resin composition (for example, a resin film formed by curing the photosensitive resin composition of the present embodiment) on the surface. .

That is, on the surface of the panel level package, a prepreg, Cu foil for forming a conductor circuit pattern, Cu / Al (wiring, pad, etc.) formed by sputtering, a cured product of a photosensitive resin composition, and silicon nitride passivation. The film, the Si chip, and the cured product of the encapsulant can be exposed.
As described above, the photosensitive resin composition of the present embodiment can form a uniform film in various panel level packages as described above by including the solvent (C-1).

The shape and size of the panel level package is, for example, a substantially rectangular shape with a length of 300 to 800 mm and a width of 300 to 800 mm. In the industry, for example, 470 mm × 370 mm, 610 mm × 457 mm (24 inches × 18 inches), and panel level packages have been proposed. By collectively manufacturing such a large-area package, it is possible to reduce the cost of manufacturing the electronic device.

It should be noted that the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the scope of achieving the object of the present invention are included in the present invention.
Hereinafter, an example of the reference mode will be additionally described.
1. Alkali-soluble resin (A),
Including a photosensitizer (B) and a solvent (C),
A photosensitive resin composition for forming a permanent film, wherein the solvent (C) contains a solvent (C-1) having a glycol ether structure, which is water-soluble and has a boiling point of 130 ° C. or higher.
2. The solvent (C-1) is ethylene glycol mono-tert-butyl ether, ethylene glycol mono-butyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, propylene glycol monopropyl ether, propylene glycol tertiary butyl ether, propylene glycol mono-ether. 1 or more containing at least one selected from the group consisting of ethyl ether, tripropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol n-butyl ether, 3-butylene glycol-3-monomethyl ether, 1 ． The photosensitive resin composition according to item 1.
3. The solvent (C-1) contains an alkylene glycol monoalkyl ether. Or 2. The photosensitive resin composition according to item 1.
4. 1. The alkali-soluble resin (A) contains at least one selected from the group consisting of polyamide resin, polybenzoxazole resin, polyimide resin, phenol resin, hydroxystyrene resin, and cyclic olefin resin. ~ 3. The photosensitive resin composition according to any one of 1.
5. The flash point of the photosensitive resin composition is 40 ° C. or higher; ~ 4. The photosensitive resin composition according to any one of 1.
6. The viscosity of the photosensitive resin composition measured at 25 ° C. using an E-type viscometer is 0.1 mPa · S or more and 5000 mPa · S or less. ~ 5. The photosensitive resin composition according to any one of 1.
7. Used for wafer level package or panel level package ~ 6. The photosensitive resin composition according to any one of 1.
8. 1. The photosensitizer (B) is a photo-acid generator. ~ 7. The photosensitive resin composition according to any one of 1.
9. In the photosensitive resin composition, the solid content concentration of the entire photosensitive resin composition is 10 to 30% by mass. ~ 8. The photosensitive resin composition according to any one of 1.
10. In the photosensitive resin composition, the solvent (C-1) is contained in an amount of 1% by mass or more and 100% by mass or less with respect to the entire solvent (C). ~ 9. The photosensitive resin composition according to any one of 1.
11. In the photosensitive resin composition, N-methyl-2-pyrrolidone is less than 1% by mass with respect to the entire photosensitive resin composition. ~ 10. The photosensitive resin composition according to any one of 1.
12. The solvent (C) is at least selected from propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone (GBL), tetramethylurea (TMU) and N-methylpyrrolidone (NMP). Including one more type, 1. ~ 11. The photosensitive resin composition according to any one of 1.
13. 1. ~ 12. A cured film obtained by curing the photosensitive resin composition according to any one of 1.
14. 13. An electronic device comprising the cured film according to claim 1.
15. A step of providing an electronic component on one surface of the substrate,
On one surface of the substrate,
Alkali-soluble resin (A),
A coating film forming step of coating a photosensitive resin composition containing a photosensitive material (B) and a solvent (C) to form a coating film;
An exposure step of exposing the formed coating film,
A cured film of the photosensitive resin composition is included, which includes a developing step of developing the exposed coating film, and a heating step of heating the coating film remaining after the development to cure the coating film to form a permanent film. A method of manufacturing an electronic device, comprising:
The method for producing an electronic device, wherein the solvent (C) includes a solvent (C-1) having a glycol ether structure, which is water-soluble and has a boiling point of 130 ° C. or higher.

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

(Preparation of Photosensitive Resin Compositions of Examples and Comparative Examples)
The photosensitive resin compositions of Examples and Comparative Examples were prepared as follows.

<Alkali-soluble resin>
The alkali-soluble resin 1 which is a polyamide resin was prepared by the following procedure.
In a 4-neck 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 1-hydroxy-1,2,3-benzotriazole monohydrate 216.19 g (1.600 mol) were reacted to obtain 170.20 g (0) of a mixture of dicarboxylic acid derivatives. .346 mol), 4.01 g (0.047 mol) of 5-aminotetrazole, and 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-3,6dimethylphenol) represented by the following formula (DA3), It was. Then, 578.3 g of N-methyl-2-pyrrolidone was added to the separable flask to dissolve each raw material component. Next, using an oil bath, reaction was carried out at 90 ° C. for 5 hours. Then, 24.34 g (0.141 mol) of 4-ethynylphthalic anhydride and 121.7 g of N-methyl-2-pyrrolidone were added to the separable flask and reacted at 90 ° C. for 2 hours with stirring. After that, 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). Then, the precipitate was filtered off, washed thoroughly with water, and dried under vacuum to obtain the desired alkali-soluble resin 1. The weight average molecular weight Mw of the obtained alkali-soluble resin 1 was 18081.

<Photosensitizer>
As the photosensitizer 1, a compound represented by the following formula was used.
Photosensitizer 1, which is a diazoquinone compound, was synthesized by the following procedure.
In a four-neck 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) and 1, 18.81 g (0.070 mol) of 2-naphthoquinone-2-diazide-5-sulfonyl chloride and 170 g of acetone were put and stirred to be dissolved.
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 as it is at room temperature for 3 hours, 1.05 g (0.017 mol) of acetic acid was added and further reacted for 30 minutes. Then, after filtering the reaction mixture, the filtrate was poured into a mixed solution of water / acetic acid (990 mL / 10 mL). Then, the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum. Thus, a photosensitizer 1 represented by the structure of formula (Q-1) below was obtained.

<Solvent>
The compounds listed in Table 1 were used as the solvent.

The following surfactant 1 was used as the surfactant.
-Surfactant 1: Fluorine-based surfactant (FC4430 manufactured by 3M Japan)

<Adhesion aid>
The following coupling agent was used as an adhesion aid.
(Coupling agent 1)
As the coupling agent 1, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine (X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula (S1) was prepared.

(Coupling agent 2)
As the coupling agent 2, a coupling agent 2, which is a condensate of cyclohexene-1,2-dicarboxylic acid anhydride represented by the following formula (S1) and 3-aminopropyltriethoxysilane, was synthesized by the following method. Details of the synthesis method will be described.
Cyclohexene-1,2-dicarboxylic acid anhydride (45.6 g, 300 mmol) was dissolved in N-methyl-2-pyrrolidone (970 g) in a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube, and a thermostat The temperature was adjusted to 30 ° C. Next, 3-aminopropyltriethoxysilane (62 g, 280 mmol) was placed in a dropping funnel and added dropwise to the solution over 60 minutes. After completion of dropping, the mixture was stirred under conditions of 30 ° C. and 18 hours to obtain a coupling agent 2 represented by the following formula (S2).

<Preparation of photosensitive resin composition>
The photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 6 were prepared as follows.
First, the solvent was mixed according to the blending ratio shown in Table 2 or Table 3 below to prepare a mixed solvent.
Then, to the mixed solvent, each raw material component other than the solvent was added, stirred, and filtered with a PTFE membrane filter having a pore size of 0.2 μm to obtain a varnish of the photosensitive resin composition of each Example and each Comparative Example. Got
The amount of the surfactant added is the concentration (ppm) of the photosensitive resin composition containing the mixed solvent in the whole varnish.
Further, the tag closed flash point of the photosensitive resin composition of Example 1 based on JIS K 2265-1 was 60.4 ° C.

(Contact angle / surface energy)
With respect to the photosensitive resin compositions of Examples and Comparative Examples, the contact angle with respect to a substrate having sputtered Cu as a surface layer, a substrate having sputtered Al as a surface layer, and a bare silicon wafer was measured.

The sputtered Cu was purchased from Kyodo International Co., Ltd.
The bare silicon wafer used was purchased from Advantech Co., Ltd.

As a specific procedure for measuring the contact angle, first, with respect to the compositions of Examples and Comparative Examples, the viscosity measured after rotating for 300 seconds at a rotation frequency of 100 rpm and a temperature of 25 ° C. by an E-type viscometer is 50 mPa · s. Thus, the viscosity was adjusted with the solvent used in each of the examples and comparative examples. When adjusting the viscosity, the solvent was added so that the compounding ratio of each solvent contained in each resin composition was constant.
Next, at a temperature of 25 ° C., 2 ml of the varnish of the photosensitive resin composition having the viscosity adjusted above was dropped on each substrate, and the contact angle 10 seconds after the drop was evaluated by a droplet method. The measurement was performed using a contact angle meter (DROPMASTER-501 manufactured by Kyowa Interface Science Co., Ltd.).
This evaluated the contact angle with respect to sputtered Cu and a bare silicon wafer. For the evaluation, the measurement was repeated 10 times, the average value thereof was calculated, and this was taken as the contact angle θ (°). Moreover, the surface energy (mN / m) of the photosensitive resin composition was evaluated by this.

<Evaluation of coating properties>
The applicability of the photosensitive resin compositions of Examples and Comparative Examples was evaluated. The details will be described below.

(Method for preparing evaluation sample)
First, a copper clad laminated substrate in which a copper foil was attached to the substrate was prepared. The substrate had a rectangular shape of 200 mm × 300 mm.
For the compositions of Examples and Comparative Examples, use the E-type viscometer so that the viscosity measured after rotating for 300 seconds at a rotation frequency of 100 rpm and a temperature of 25 ° C. is 50 mPa · s. The viscosity was adjusted with the solvent used. When adjusting the viscosity, the solvent was added so that the compounding ratio of each solvent contained in each resin composition was constant.
A coating film was formed on the surface of the substrate by using a film applicator with a film thickness adjusting function of 300 mm (manufactured by All Good Co., Ltd.) using the photosensitive resin compositions of Examples and Comparative Examples. Further, the coating film was prebaked under the conditions shown in Table 2 or Table 3, and the coating film after the prebaking treatment was subjected to appearance observation. The film thickness of the coating film was adjusted so that the film thickness after prebaking was 10 μm.

The state of the photosensitive resin film on the substrate was observed and evaluated according to the following criteria.
(Sink)
○ No dents were found on the coating film. × Some dents occurred on the coating film (repelling).
○ There was no exposed part of the base × Part of the base was exposed

The photosensitive resin compositions of Examples 1 and 2 were more resistant to dents and underlayer exposure in the coating film as compared with Comparative Examples 2 to 4, and were more dried than those of Comparative Example 1 under reduced pressure. The result showed that sink marks (dents) were suppressed.
In addition, the photosensitive resin compositions of Examples 3 and 4 were more resistant to dents and exposure of the undercoat in the coating film as compared with Comparative Example 6, and compared with Comparative Example 5 in the coating film dried under reduced pressure. The result showed that sink marks (dents) were suppressed.
Therefore, the photosensitive resin compositions of Examples 1 to 4 were excellent in wettability with respect to the substrate containing the inorganic material, and the dents and the underlayer exposure in the coating film were suppressed, and a stable and uniform coating film was obtained. It turned out that it can be formed. Further, the photosensitive resin compositions of these examples can be suitably used for wafer level packages and panel level packages.

This application claims priority based on Japanese Patent Application No. 2018-196414 filed on October 18, 2018, and incorporates all of the disclosure thereof.

Claims (16)

1. Alkali-soluble resin (A),
   Including a photosensitizer (B) and a solvent (C),
   A photosensitive resin composition for forming a permanent film, wherein the solvent (C) contains a solvent (C-1) having a glycol ether structure, which is water-soluble and has a boiling point of 130 ° C. or higher.
2. The solvent (C-1) is ethylene glycol mono-tert-butyl ether, ethylene glycol mono-butyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, propylene glycol monopropyl ether, propylene glycol tertiary butyl ether, propylene glycol mono-ether. Claims containing at least one selected from the group consisting of ethyl ether, tripropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol n-butyl ether and 3-butylene glycol-3-monomethyl ether. Item 1. The photosensitive resin composition according to item 1. .
3. The photosensitive resin composition according to claim 1 or 2, wherein the solvent (C-1) contains an alkylene glycol monoalkyl ether.
4. The alkali-soluble resin (A) contains 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. 3. The photosensitive resin composition according to any one of 3 above.
5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the photosensitive resin composition has a flash point of 40 ° C or higher.
6. 6. The photosensitivity according to claim 1, wherein the photosensitive resin composition has a viscosity of 0.1 mPa · S or more and 5000 mPa · S or less measured at 25 ° C. using an E-type viscometer. Resin composition.
7. The photosensitive resin composition according to any one of claims 1 to 6, which is used for a wafer level package or a panel level package.
8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the photosensitizer (B) is a photoacid generator.
9. The photosensitive resin composition according to any one of claims 1 to 8, wherein in the photosensitive resin composition, the solid content concentration of the entire photosensitive resin composition is 10 to 30% by mass.
10. 10. The photosensitive material according to claim 1, wherein the solvent (C-1) is contained in the photosensitive resin composition in an amount of 1% by mass or more and 100% by mass or less based on the whole solvent (C). Resin composition.
11. The photosensitive resin composition according to any one of claims 1 to 10, wherein N-methyl-2-pyrrolidone in the photosensitive resin composition is less than 1% by mass based on the entire photosensitive resin composition. .
12. The solvent (C) is at least selected from propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone (GBL), tetramethylurea (TMU) and N-methylpyrrolidone (NMP). The photosensitive resin composition according to any one of claims 1 to 11, further comprising one kind.
13. The solvent (C) is a mixed solvent containing the solvent (C-1) and another solvent (C-2) having a boiling point higher by 20 ° C. or more than the boiling point of the solvent (C-1). The photosensitive resin composition according to any one of claims 1 to 12.
14. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 13.
15. An electronic device comprising the cured film according to claim 14.
16. A step of providing an electronic component on one surface of the substrate,
    A coating film forming step of coating a photosensitive resin composition containing an alkali-soluble resin (A), a photosensitive material (B), and a solvent (C) on one surface of the substrate to form a coating film;
    An exposure step of exposing the formed coating film,
    A developing step of developing the exposed coating film, and a heating step of heating the coating film remaining after the development to cure the coating film to form a permanent film,
    A method of manufacturing an electronic device including a cured film of the photosensitive resin composition, comprising:
    The method for producing an electronic device, wherein the solvent (C) includes a solvent (C-1) having a glycol ether structure, which is water-soluble and has a boiling point of 130 ° C. or higher.