WO2020054644A1 - Permanent film-forming photosensitive resin composition, cured film, electronic device, cured film production method, and electronic device manufacturing method - Google Patents

Abstract

The permanent film-forming photosensitive resin composition according to one aspect of the present invention contains an alkali-soluble resin (A), a photosensitizer (B), and a surfactant (C), wherein the surfactant (C) contains an organic modified dimethylsiloxane represented by formula (1) (in formula (1), X represents a polyether group, a polyester group, or an aralkyl group, and m and n each represent an integer of 1-100).

Description

Photosensitive resin composition for forming permanent film, cured film, electronic device, method for producing cured film, and method for producing electronic device

The present invention relates to a photosensitive resin composition for forming a permanent film, a cured film, an electronic device, a method for producing a cured film, and a method for producing an electronic device.

As a permanent film constituting an electronic device, a cured film obtained by exposing a photosensitive resin composition to light may be used. As a technique relating to such a photosensitive resin composition, for example, a technique described in Patent Document 1 can be mentioned.
According to Patent Document 1, a photosensitive resin having a polymer having a structural unit having a residue in which an acid group is protected by an acid-decomposable group and a structural unit having a crosslinkable group, and a fluorine-based surfactant A composition is described.

JP 2016-189006 A

With the miniaturization of electronic devices, further finer and higher density wiring and L / S (wiring width, wiring interval) constituting the electronic devices have been achieved. As a result, demands for permanent films used in electronic devices have become severe. As a property required for a permanent film, further improvement in wettability with a metal constituting fine wiring is required.
Since the conventional photosensitive resin composition uses a fluorine-based surfactant as a surfactant, the amount of the surfactant to be added is limited from the viewpoint of environmental load. As a result, it has not been possible to meet the demand for further increasing the wettability with metal.
Then, this invention provides the technique regarding the photosensitive resin composition for permanent film formation which improved the wettability with metal.

According to the present invention, an organic solvent containing an alkali-soluble resin (A), a photosensitive agent (B), and a surfactant (C), wherein the surfactant (C) is represented by the following formula (1): Provided is a photosensitive resin composition for forming a permanent film, comprising a modified dimethylsiloxane.

(In the formula (1), X represents a polyether group, a polyester group, or an aralkyl group, and m and n each represent an integer of 1 to 100.)

According to the present invention, there is also provided a cured film obtained by curing the above-described photosensitive resin composition for forming a permanent film.

According to the present invention, there is also provided an electronic device including the above-described cured film.

Further, according to the present invention, the composition includes an alkali-soluble resin (A), a photosensitive agent (B), and a surfactant (C), and the surfactant (C) is represented by the following formula (1). Forming a coating film by applying a photosensitive resin composition for forming a permanent film containing an organically modified dimethylsiloxane, forming an application film, exposing the formed coating film, and developing the exposed coating film. And a heating step of heating the coating film remaining after the development to cure the coating film and form a permanent film, and a method of manufacturing a cured film of the photosensitive resin composition for forming a permanent film. Provided.

(In the above formula (1), X represents a polyether group, a polyester group, or an aralkyl group, and m and n each represent an integer of 1 or more and 100 or less.)

According to the present invention, there is also provided a method of manufacturing an electronic device including, in a process, a method of manufacturing a cured film of the above-described photosensitive resin composition for forming a permanent film.

According to the present invention, it is possible to provide a technique relating to a photosensitive resin composition for forming a permanent film having improved wettability with a metal.

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

It is a figure showing an example of an electronic device containing the photosensitive resin composition for permanent film formation of this embodiment.

Hereinafter, embodiments of the present invention will be described in detail. In the present specification, the notation “a to b” in the description of the numerical range indicates that the number is a or more and b or less unless otherwise specified.

The photosensitive resin composition for forming a permanent film according to the present embodiment includes an alkali-soluble resin (A), a photosensitive agent (B), and a surfactant (C), wherein the surfactant (C) has the following formula: It contains the organically modified dimethylsiloxane represented by (1).

(In the formula (1), X represents a polyether group, a polyester group, or an aralkyl group, and m and n each represent an integer of 1 to 100.)
According to the photosensitive resin composition for forming a permanent film of the present embodiment, it is possible to enhance the wettability with a substrate, particularly a metal, and thereby enhance the film forming property of a film using the photosensitive resin composition for forming a permanent film. it can. Examples of metals that can be expected to improve wettability with the photosensitive resin composition for forming a permanent film according to the present embodiment include Cu and Al. As an index of the wettability to a metal, a contact angle to the metal is exemplified.

Hereinafter, each component contained in the photosensitive resin composition for forming a permanent film according to the present embodiment (hereinafter, the photosensitive resin composition for forming a permanent film may be referred to as a photosensitive resin composition) will be described.

(Alkali-soluble resin (A))
The alkali-soluble resin (A) can be selected according to physical properties such as mechanical properties and optical properties required for the resin film. Specific examples of the alkali-soluble resin (A) include a polyamide resin, a polybenzoxazole resin, a polyimide resin, a phenol resin, a hydroxystyrene resin, and a cyclic olefin resin. As the alkali-soluble resin (A), one or a combination of two or more of the above specific examples can be used. As the alkali-soluble resin (A), among the above specific examples, for example, a polyamide resin or a polybenzoxazole resin is preferably used, and more preferably a polybenzoxazole resin is used. Thereby, the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition for forming a permanent film can be improved. In addition, by improving the physical properties such as the mechanical strength of a cured film (permanent film) made of the photosensitive resin composition for forming a permanent film, the uniformity of the film thickness is improved, and it is also preferable from the viewpoint of preventing the occurrence of defects. .

(Polyamide resin, polybenzoxazole resin)
As the polyamide resin, for example, it is preferable to use an aromatic polyamide having an aromatic ring as a structural unit of the polyamide, and more preferably a polyamide resin containing a structural unit represented by the following formula (PA1). Thereby, the physical properties such as the mechanical strength of the resin film made of the photosensitive resin composition can be improved. Therefore, it is 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 refers to a benzene ring; a condensed aromatic ring such as a naphthalene ring, an anthracene ring or a pyrene ring; or a heteroaromatic ring such as a pyridine ring or a pyrrole ring. The polyamide resin of the present embodiment preferably contains a benzene ring as an aromatic ring from the viewpoint of mechanical strength and the like.

ポ リ ア ミ ド A polyamide resin containing a structural unit represented by the above formula (PA1) is a precursor of a polybenzoxazole resin. The polyamide resin containing the structural unit represented by the above formula (PA1) is subjected to a heat treatment at a temperature of 150 ° C. or more and 380 ° C. or less for 30 minutes or more and 50 hours or less, thereby dehydrating and ring-closing the polyamide resin. 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 (A) according to the present embodiment is a polyamide resin containing a structural unit represented by the formula (PA1), for example, the photosensitive resin composition is subjected to the above-described heat treatment to be dehydrated and ring-closed to form a polystyrene. It may be a benzoxazole resin. That is, the heat-treated photosensitive resin composition contains a polybenzoxazole resin which is an alkali-soluble resin (A).
When the alkali-soluble resin (A) is a polyamide resin containing the structural unit represented by the formula (PA1), a resin film and an electronic device to be described later are manufactured, and the above heat treatment is performed to cause dehydration and ring closure. And a polybenzoxazole resin. When a polybenzoxazole resin is obtained by dehydrating and ring-opening a polyamide resin, mechanical properties and thermal properties can be improved. This is convenient from the viewpoint of suppressing deformation of the resin film.

(Polyamide resin, polyimide resin)
Further, as the polyamide resin, for example, a resin containing a structural unit represented by the following formula (PA2) may be used.
The polyamide resin containing a structural unit represented by the following formula (PA2) is a precursor of a polyimide resin. The polyamide resin containing the structural unit represented by the following formula (PA2) is subjected to a heat treatment at a temperature of 150 ° C. or more and 380 ° C. or less under a condition of 30 minutes or more and 50 hours or less, whereby the polyamide resin is dehydrated and closed, and the polyimide resin It can be. Here, the structural unit of the following formula (PA2) becomes a structural unit represented by the following formula (PI1) by dehydration ring closure.
When the alkali-soluble resin (A) according to this embodiment is a polyamide resin containing a structural unit represented by the following formula (PA2), the photosensitive resin composition is subjected to the above heat treatment to be dehydrated and closed to form a polyimide resin. Is also good. That is, the heat-treated photosensitive resin composition contains the polyimide resin which is the alkali-soluble resin (A).
When the alkali-soluble resin (A) is a polyamide resin containing a structural unit represented by the following formula (PA2), a resin film and an electronic device to be described later are produced, and then the above heat treatment is performed to cause dehydration and ring closure. And a polyimide resin.

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

Wherein (PI1), ^{R B} and ^{R C} are the same as those in the formula (PA2).

Specifically, R ^B and R ^C in the formulas (PA2) and (PI1) are preferably organic groups having an aromatic ring.
Specifically, as the organic group having an aromatic ring, those having a benzene ring, a naphthalene ring or an anthracene ring are preferable, and those having a benzene ring are more preferable. Thereby, the dispersibility of the alkali-soluble resin (A) can be improved, and the contact angle with the metal material can be set within a desired numerical range.

(Production method of polyamide resin)
The polyamide resin according to the present 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. Next, in a 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), the diamine monomer and the dicarboxylic acid monomer are polycondensed. The method of polycondensation for polymerizing the polyamide is not limited, and specific examples include melt polycondensation, an acid chloride method, and direct polycondensation.
Note that, instead of the dicarboxylic acid monomer, a compound selected from the group consisting of tetracarboxylic dianhydride, trimellitic anhydride, dicarboxylic dichloride or active ester dicarboxylic acid may be used. As a method for obtaining the active ester type dicarboxylic acid, specifically, a method of reacting a dicarboxylic acid with 1-hydroxy-1,2,3-benzotriazole or the like can be mentioned.

The diamine monomer and the dicarboxylic acid monomer used for the polymerization of the polyamide resin will be described below. The diamine monomer and the dicarboxylic acid monomer may each be used 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. 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 containing a phenolic hydroxyl group in the structure, for example, a compound represented by the following formula (DA1) is preferable. By producing a polyamide resin using such a diamine monomer as a raw material, the conformation of the polyamide resin is 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 (A) and the metal molecule are more strongly bound, and the adhesion to the substrate can be improved.
For example, when a diamine monomer represented by the following formula (DA1) is used, the polyamide resin contains a structural unit represented by the following formula (PA3). That is, the polyamide resin according to the present embodiment preferably contains, for example, a structural unit represented by the following formula (PA3).

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

In the formula (PA3), R ⁴ and R ⁵ to R ¹⁰ are the same as those in the above formula (DA1).

R ⁴ in the formula (DA1) and the formula (PA3) is selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. A group formed by one or more atoms.
Note that R ⁴ is a divalent group. Here, the divalent group indicates a valence. In other words, this indicates that R ⁴ has two bonds to be bonded to another atom.

When R ⁴ in the formula (DA1) and the formula (PA3) includes a carbon atom, R ⁴ is, for example, a group having 1 to 30 carbon atoms, preferably a group having 1 to 10 carbon atoms, It is more preferably a group having 1 to 5 carbon atoms, and further preferably a group having 1 to 3 carbon atoms.

When R ⁴ in Formula (DA1) and Formula (PA3) contains a carbon atom, specific examples of R ⁴ include an alkylene group, an arylene group, a halogen-substituted alkylene group, and a halogen-substituted arylene group.
The alkylene group may be, for example, a linear alkylene group or a branched alkylene group. Specific examples of the linear alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decanylene, trimethylene, and tetramethylene. , A pentamethylene group, a 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 Alkyl methylene groups such as CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) — and —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 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 a hydrogen atom in the above-described alkylene group or arylene group is substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom, respectively, are used. Can be. Among these, those using a hydrogen atom substituted by a fluorine atom are preferable.

When R ⁴ in the formula (DA1) and the formula (PA3) does not include a carbon atom, examples of R ⁴ include a group including an oxygen atom or a sulfur atom.

R ⁵ to R ¹⁰ in the formula (DA1) and the formula (PA3) are each independently hydrogen or an organic group having 1 to 30 carbon atoms, for example, hydrogen or an organic group having 1 to 10 carbon atoms. It is preferably hydrogen, or more preferably an organic group having 1 to 5 carbon atoms, more preferably hydrogen or an organic group having 1 to 3 carbon atoms, even more preferably hydrogen or an organic group having 1 to 2 carbon atoms. More preferably, it is an organic group. Thereby, the aromatic rings of the polyamide resin can be densely arranged. Therefore, the molecular structure can be frozen by coordination in which the molecule of the alkali-soluble resin (A) and the metal molecule are more strongly linked, and the adhesion can be improved.

Specific examples of the organic group having 1 to 30 carbon atoms of R ⁵ to R ¹⁰ in the formulas (DA1) 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; Cycloalkyl groups such as cyclopentyl, cyclohexyl and cyclooctyl; Group, and alkaryl groups, such as xylyl group.

Specific examples of the diamine monomer represented by the 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. No. By using these diamine monomers, the aromatic rings of the polyamide resin can be densely arranged. Therefore, the molecular structure can be frozen by coordination in which the molecule of the alkali-soluble resin (A) and the metal molecule are more strongly linked, and the adhesion can be improved. In addition, as the diamine monomer, one or more of the above specific examples can be used in combination.
The structural formulas of these diamine monomers are shown below.

(Dicarboxylic acid monomer)
The dicarboxylic acid monomer used for the polymerization is not limited. For example, it is preferable to use a dicarboxylic acid monomer containing an aromatic ring in the structure.
As the dicarboxylic acid monomer containing an aromatic ring, for example, a monomer represented by the following formula (DC1) is preferably used. 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. And the dispersion of the wettability with respect to a metal material can be suppressed by improving dispersibility.

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

For example, when a dicarboxylic acid monomer represented by the following formula (DC1) is used, the polyamide resin typically includes a structural unit represented by the following formula (PA4). Note that in the formula (PA4), the definitions of R ¹¹ and R ¹² to R ¹⁹ are the same as those in the above formula (DC1).

R ¹¹ in the formulas (DC1) and (PA4) is selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. A group formed by one or more atoms.
Note that R ¹¹ is a divalent group. Here, the divalent group indicates a valence. That is, it shows that R ¹¹ has two bonds to be bonded to another atom.

When R ¹¹ in the formula (DC1) and the formula (PA4) 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, It is more preferably a group having 1 to 5 carbon atoms, and further preferably a group having 1 to 3 carbon atoms.

When R ¹¹ in the formulas (DC1) and (PA4) includes a carbon atom, examples of R ¹¹ include an alkylene group, an arylene group, a halogen-substituted alkylene group, and a halogen-substituted arylene group.
The alkylene group may be, for example, a linear alkylene group or a branched alkylene group. Specific examples of the linear alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decanylene, trimethylene, and tetramethylene. , A pentamethylene group, a 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 Alkyl methylene groups such as CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) — and —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 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 a hydrogen atom in the above-described alkylene group or arylene group is substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom, respectively, are used. Can be. Among these, those using a hydrogen atom substituted by a fluorine atom are preferable.

When R ¹¹ in the formulas (DC1) and (PA4) does not include a carbon atom, specific examples of R ¹¹ include a group including an oxygen atom or a sulfur atom.

R ¹² to R ¹⁹ in the formula (DC1) and the formula (PA4) are each independently hydrogen or an organic group having 1 to 30 carbon atoms, for example, hydrogen or an organic group having 1 to 10 carbon atoms. Preferably, it is hydrogen or an organic group having 1 to 5 carbon atoms, more preferably hydrogen or an organic group having 1 to 3 carbon atoms, and even more preferably hydrogen.

Specific examples of the organic group having 1 to 30 carbon atoms of R ¹² to R ¹⁹ in the formulas (DC1) and (PA4) 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; Cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl; Group, and the like alkaryl groups such as xylyl group.

Specific examples of the dicarboxylic acid monomer include diphenyl ether 4,4'-dicarboxylic acid, isophthalic acid, terephthalic acid, and 4,4'-biphenyldicarboxylic acid. As the dicarboxylic acid monomer, among the above specific examples, it is preferable to use diphenyl ether 4,4′-dicarboxylic acid or isophthalic acid, and it is more preferable to use diphenyl ether 4,4′-dicarboxylic acid. The aromatic rings of the polyamide resin can be densely arranged. Therefore, the molecular structure can be frozen by coordination in which the molecule of the alkali-soluble resin (A) and the metal molecule are more strongly linked, and the adhesion can be improved.

It is preferable to modify the amino group present at the terminal of the polyamide resin at the same time as the polymerization step (S1) or after the polymerization step (S1). The modification can be performed, for example, by reacting a diamine monomer or a polyamide resin with a specific acid anhydride or a specific monocarboxylic acid. Therefore, it is preferable that the terminal amino group of the polyamide resin according to the present embodiment is 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 selected from the group consisting of an alkenyl group, an alkynyl group, and a hydroxyl group. The specific acid anhydride and the specific monocarboxylic acid preferably include, for example, a nitrogen atom. Thereby, the wettability between the post-baked photosensitive resin composition and a metal such as Cu and Al can be improved.

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

In addition, when the amino group present at the terminal of the polyamide resin is modified with a specific acid anhydride having a ring shape, the specific acid anhydride having a ring shape 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. As a method of ring closure, for example, heat treatment and the like can be mentioned.
Specific examples of the specific monocarboxylic acid include 5-norbornene-2-carboxylic acid, 4-hydroxybenzoic acid, and 3-hydroxybenzoic acid. As the specific monocarboxylic acid, one or a combination of two or more of the above specific examples can be used.

Further, the carboxyl group present at the terminal of the polyamide resin may be modified simultaneously with the polymerization step (S1) or after the polymerization step (S1). The modification can be performed, for example, by reacting a specific nitrogen atom-containing heteroaromatic compound with a dicarboxylic acid monomer or a polyamide resin. Therefore, it is preferable that the terminal carboxyl group of the polyamide resin according to the present embodiment is modified with a specific nitrogen-containing heteroaromatic compound. The specific nitrogen-containing heteroaromatic compound includes a 1- (5-1H-triazoyl) methylamino group, a 3- (1H-pyrazolyl) amino group, a 4- (1H-pyrazolyl) amino group, and a 5- (1H-pyrazolyl) amino group. (1H-pyrazolyl) amino group, 1- (3-1H-pyrazolyl) methylamino group, 1- (4-1H-pyrazolyl) methylamino group, 1- (5-1H-pyrazolyl) methylamino group, (1H- At least one functional group 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. Thereby, the number of lone electron pairs in the photosensitive resin composition can be increased. Therefore, the wettability between the photosensitive resin composition after prebaking and postbaking and a metal such as Cu and Al can be improved.
Specific examples of the specific nitrogen-containing heteroaromatic compound include 5-aminotetrazole.

(Low molecular weight component removal step (S2))
Subsequent to the polymerization step (S1), a low molecular weight component removing step (S2) is preferably performed to remove the low molecular weight component.
Specifically, the organic layer containing the mixture of the low molecular weight component and the polyamide resin is concentrated by filtration or the like, and then dissolved again in an organic solvent such as water / isopropanol. Thereby, a precipitate can be filtered out to obtain a polyamide resin from which low molecular weight components have been removed.

Regarding the polyamide resin, for example, it is preferable to prepare a photosensitive resin composition that is a varnish without passing through a step of completely evaporating and drying the solvent after the low molecular weight component removing step. Thereby, it can suppress that the dispersibility of a polyamide falls by the interaction derived from the amide bond between the molecules of the polyamide resin. Therefore, the contact angle with respect to the metal material used in the electronic device can be kept uniform.

(Phenolic resin)
Specific examples of the phenol resin include novolak phenol resins such as phenol novolak resin, cresol novolak resin, bisphenol novolak resin, and phenol-biphenyl novolak resin; 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; The phenol resin may include one or more of the above specific examples.

The phenol compound used for the reaction product of the phenol compound and the aldehyde compound or the reaction product of the phenol compound and the dimethanol compound 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, Xylenols such as 2,6-xylenol, 3,4-xylenol, 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol; isopropylphenol, butylphenol, p-tert- Alkylphenols such as butylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, pyrogallol, and phloroglucinol; and biphenyl-based 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 for the reaction product of the phenol compound and the aldehyde compound described above is not limited as long as it has an aldehyde group.
Specific examples of such an aldehyde compound include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and salicylaldehyde. As the aldehyde compound, one or more of the above specific examples can be used.

The dimethanol compound used for 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, Dimethanol compounds such as 3'-biphenyldimethanol, 2,6-naphthalenedimethanol, 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., 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; Biphenyl aralkyl compounds such as 4,4'-bis (methoxymethyl) biphenyl and 4,4'-bis (methoxymethyl) biphenyl are exemplified. 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, is a polymerization reaction product or copolymer obtained by polymerizing or copolymerizing one or more selected from the group consisting of hydroxystyrene, hydroxystyrene derivatives, styrene and styrene derivatives. A polymerization reactant can be used.
Specific examples of the hydroxystyrene derivative and the styrene derivative include those in which a hydrogen atom of an aromatic ring of hydroxystyrene or styrene is substituted with a monovalent organic group. Examples of the monovalent organic group that substitutes for a hydrogen atom include an alkyl group such as a methyl group, an ethyl group, and an n-propyl group; an alkenyl group such as an allyl group and a vinyl group; an alkynyl group such as an ethynyl group; An alkylidene group such as an ethylidene group; a cycloalkyl group such as a cyclopropyl group; a heterocyclic group such as an epoxy group oxetanyl group.

(Cyclic olefin resin)
The cyclic olefin-based resin is not limited, and specifically, a polymerization reaction product or a copolymerization reaction product obtained by polymerizing or copolymerizing one or more selected from the group consisting of norbornene and norbornene derivatives is used. be able to.
Here, as the norbornene derivative, specifically, norbornadiene, bicyclo [2.2.1] -hept-2-ene (common 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 anhydride.

The lower limit of the content of the alkali-soluble resin (A) in the photosensitive resin composition is, for example, preferably 30 parts by mass or more when the total solid content of the photosensitive resin composition is 100 parts by mass, It is more preferably at least 40 parts by mass, further preferably at least 50 parts by mass, further preferably at least 60 parts by mass, particularly preferably at least 70 parts by mass. Thereby, the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition can be improved, and the contact angle with the metal material can be set within a desired numerical range.
The upper limit of the content of the alkali-soluble resin (A) in the photosensitive resin composition may be, for example, 95 parts by mass or less when the total solid content of the photosensitive resin composition is 100 parts by mass. Preferably, it is 90 parts by mass or less, more preferably 85 parts by mass or less.
In addition, in this embodiment, the total solid content of the photosensitive resin composition indicates the total of the components contained in the photosensitive resin composition excluding the solvent.

(Photosensitizer (B))
As the photosensitive agent (B), a photoacid generator that generates an acid by absorbing light energy can be used.
Specific examples of the photoacid generator include diazoquinone compounds; diaryliodonium salts; 2-nitrobenzyl ester compounds; N-iminosulfonate compounds; imidosulfonate compounds; 2,6-bis (trichloromethyl) -1,3,3 5-triazine compounds; dihydropyridine compounds and the like. Among these, it is preferable to use a photosensitive diazoquinone compound. Thereby, the sensitivity of the photosensitive resin composition can be improved. Therefore, the precision 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 of a positive type, as the photosensitive agent (B), in addition to the above specific examples, an onium salt such as a triarylsulfonium salt; a sulfonium / borate salt may be used. Good. Thereby, the sensitivity of the photosensitive resin composition can be further improved.

Hereinafter, diazoquinone compounds will be exemplified using chemical formulas.

In each of the above diazoquinone compounds, Q is a structure represented by the following formula (a), the following formula (b) or 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).
It is preferable that Q of the diazoquinone compound 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 photosensitive agent (B) 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 (A) is 100 parts by mass. Is more preferable, and the content 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 photosensitive agent (B) in the photosensitive resin composition is preferably, for example, 30 parts by mass or less when the alkali-soluble resin (A) is 100 parts by mass, and 20 parts by mass. Parts or less is more preferable. This can prevent the photosensitive resin composition and the metal material present on the substrate surface of the semiconductor device from being repelled.

(Surfactant (C))
As the surfactant (C), an organically modified dimethylsiloxane represented by the following formula (1) is used. Desirable physical properties of the surfactant (C) include high polarity and low surface tension lowering ability. By using the surfactant (C) having a high polarity, the compatibility between the alkali-soluble resin (A) and other components including a solvent described below is increased, and by using the photosensitive resin composition for forming a permanent film. The coating film performance when forming a coating film can be improved. In addition, by lowering the surface tension lowering ability, the wettability to a metal material can be increased, and the coating film performance when a coating film is formed using the photosensitive resin composition for forming a permanent film can be improved.

(In the above formula (1), X represents a polyether (polyoxyalkylene) group, a polyester group or an aralkyl group, and m and n each represent an integer of 1 or more and 100 or less.)

When X in the above formula (1) is a polyether group, X is preferably a polyether group represented by the following formula (2-1).

(In the above formula (2-1), R ²⁰ represents an alkyl group having 1 to 6 carbon atoms, and R ²¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Represents an ether group or an unsaturated alkyl ether group having 1 to 6 carbon atoms, EO represents an ethylene oxide group, PO represents a propylene oxide group, o represents an integer of 1 or more, and p represents an integer of 0 or more. The order of EO and PO may be random.)

When X in the above formula (1) contains a propylene oxide group, the lower limit of the molar ratio of the propylene oxide group to the total molar amount of the ethylene oxide group and the propylene oxide group is preferably 1% or more, more preferably 10% or more. , 20% or more is more preferable. On the other hand, the upper limit of the molar ratio of the propylene oxide group is preferably 99% or less, more preferably 90% or less, and further preferably 80% or less. By adjusting the molar ratio of the propylene oxide group to the above range, the wettability with the metal can be improved.

When X in the above formula (1) is a polyester group, a polyester group represented by the following formula (2-2) is preferably used as X.

(In the formula (2-2), R ²² , R ²³ , R ^24, and R ²⁵ each independently represent an alkyl group having 1 to 20 carbon atoms, and r represents an integer of 1 or more.)

When X in the above formula (1) is an aralkyl group, X is preferably an aralkyl group represented by the following formula (2-3).

(In the above formula (2-3), R ²⁶ represents an alkyl group having 1 to 30 carbon atoms.)

The lower limit of the ratio of m to the sum of m and n represented by the above formula (1) is preferably 0.5% or more, more preferably 1% or more, still more preferably 5% or more, and particularly preferably 10% or more. preferable. On the other hand, the upper limit of the ratio of m is preferably 60% or less, more preferably 50% or less, further preferably 40% or less, and particularly preferably 30% or less. By setting the ratio of m in the above range, the wettability with metal can be improved.

Although the content of the surfactant (C) in the photosensitive resin composition is not particularly limited, the lower limit of the content of the surfactant (C) in the photosensitive resin composition is sufficient for the effect of the surfactant. In light of the above, the content is preferably 0.001% by mass (10 ppm) or more, more preferably 0.01% by mass (100 ppm) or more, based on the entire photosensitive resin composition (including the solvent). Further, the upper limit of the content of the surfactant (C) in the photosensitive resin composition is preferably 1% by mass (10000 ppm) or less based on the entire photosensitive resin composition (including the solvent). , 0.5 mass% (5000 ppm) or less, more preferably 0.1 mass% (1000 ppm) or less. By setting the content of the surfactant (C) within the above range, it is possible to further enhance the effect of the surfactant, that is, to enhance the compatibility between the alkali-soluble resin (A) and other components including a solvent described below. it can.

(solvent)
The photosensitive resin composition for forming a permanent film according to the present embodiment may include a solvent. As the solvent, an organic solvent is typically used.
Specific examples of the solvent include N-methyl-2-pyrrolidone (NMP), 3-methoxy-N, N-dimethylpropanamide, N, N-dimethylformamide, N, N-dimethylpropionamide, N, N- Amide solvents such as diethylacetamide, 3-butoxy-N, N-dimethylpropanamide, N, N-dibutylformamide; N, N-dimethylacetamide, tetramethylurea (TMU), 1,3-dimethyl-2-imidazo Lydinone, tetrabutylurea, N, N'-dimethylpropyleneurea, 1,3-dimethoxy-1,3-dimethylurea, N, N'-diisopropyl-O-methylisourea, O, N, N'-triisopropyliso Urea, O-tert-butyl-N, N'-diisopropylisourea, O-ethyl-N, N'-diisopropylisourea Urea solvents such as propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, ethylene Ether solvents such as glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, 1,3-butylene glycol-3-monomethyl ether; propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate; Butyl lactate, methyl-1,3-butylene glycol acetate Acetate solvents such as tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol, butanediol, and isopropyl alcohol; ketone solvents such as cyclopentanone, cyclohexanone, diacetone alcohol, and 2-heptanone; γ Lactone solvents such as butyrolactone (GBL) and γ-valerolactone; carbonate solvents such as ethylene carbonate and propylene carbonate; sulfonic solvents such as dimethyl sulfoxide (DMSO) and sulfolane; methyl pyruvate, ethyl pyruvate and methyl Ester solvents such as -3-methoxypropionate; and aromatic hydrocarbon solvents such as mesitylene, toluene and xylene. As the solvent, one or more of the above specific examples can be used in combination. Among these, a lactone-based solvent is preferable from the viewpoints of coatability and sag prevention.

As the solvent, for example, one or more selected from the group consisting of amide-based solvents and urea-based solvents and one or more selected from the group consisting of acetate-based solvents and lactone-based solvents are used in combination with the above specific examples. Is preferred. Thereby, the dispersibility of the alkali-soluble resin (A) can be improved.

The total content of the amide solvent and the urea solvent in the solvent, when the solvent is 100 parts by mass, is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and more preferably 25 parts by mass or more. Is more preferable. Thereby, the polarity in the mixed solvent can be improved. Therefore, the dispersibility of the alkali-soluble resin (A) such as a polyamide resin, a polybenzoxazole resin, and a polyimide resin can be improved.

場合 When the photosensitive resin composition for forming a permanent film according to the present embodiment contains a solvent, the amount of the solvent to be added is appropriately adjusted according to characteristics such as viscosity required of the photosensitive resin composition for forming a permanent film. When the photosensitive resin composition for forming a permanent film is applied by slit coating, the content of the solvent in the photosensitive resin composition is, for example, 0.0001 with respect to the entire photosensitive resin composition (including the solvent). It is at least 1 mass% (1 ppm) and at most 1 mass% (10000 ppm).

The photosensitive resin composition for forming a permanent film according to the present embodiment further includes additives such as an adhesion aid, a thermal crosslinking agent, a silane coupling agent, an antioxidant, a dissolution promoter, a filler, and a sensitizer. May be.

(Adhesion aid)
The photosensitive resin composition for forming a permanent film according to the present embodiment may further include an adhesion aid. Specifically, a triazole compound, an aminosilane or an imide compound can be used as the adhesion aid. Thereby, the affinity between the photosensitive resin composition for forming a permanent film and a metal member such as Cu and Al can be improved.

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- Include 1,2,4-triazole, such as chill-1,2,4-triazole-3-carboxamide. As the triazole compound, one or a combination of two or more of the above specific examples can be used.

Examples of the aminosilane include condensates of cyclohexene-1,2-dicarboxylic 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- (trimethoxysilane) L) propyl] ethylenediamine, N, N'-bis- (3-triethoxysilylpropyl) ethylenediamine, N, N'-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N'-bis [3- (Methyldiethoxysilyl) propyl] ethylenediamine, N, N'-bis [3- (dimethylmethoxysilyl) propyl] ethylenediamine, N- [3- (methyldimethoxysilyl) propyl] -N '-[3- (trimethoxy (Silyl) propyl] ethylenediamine, N, N'-bis [3- (trimethoxysilyl) propyl] diaminopropane, N, N'-bis [3- (trimethoxysilyl) propyl] diaminohexane, N, N'-bis [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.

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

The lower limit of the content of the adhesion aid in the photosensitive resin composition for forming a permanent film is, for example, preferably 0.1 part by mass or more based on 100 parts by mass of the alkali-soluble resin (A). It is more preferably 0 parts by mass or more, further preferably 2.0 parts by mass or more, and still more preferably 3.0 parts by mass or more.

Further, the upper limit of the content of the adhesion auxiliary agent in the photosensitive resin composition for forming a permanent film is, for example, preferably 10 parts by mass or less, and more preferably 7 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). Parts by weight or less, more preferably 5 parts by weight or less.
When the content of the adhesion aid is within the above numerical range, the adhesion aid is suitably dispersed in the photosensitive resin composition for forming a permanent film, and the adherend of the photosensitive resin composition for forming a permanent film is used. Can be improved. This is preferable from the viewpoint that foreign substances can be prevented from being mixed between the resin film and the adherend of the resin film.

(Silane coupling agent)
The photosensitive resin composition for forming a permanent film 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 include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, Epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; 3-methacryloxy Methacrylsilanes such as propylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and 3-methacryloxypropyltriethoxysilane; 3-acryloxypro Acrylic silanes such as tritrimethoxysilane; isocyanurate silanes; alkyl silanes; ureido silanes such as 3-ureidopropyl trialkoxysilane; mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; 3-isocyanate Isocyanate silanes such as propyltriethoxysilane; titanium compounds; aluminum chelates; and aluminum / zirconium compounds. As the silane coupling agent, one or more of the above specific examples can be blended.

(Thermal crosslinking agent)
The photosensitive resin composition for forming a permanent film according to the present embodiment may include a thermal crosslinking agent capable of reacting with the alkali-soluble resin (A) 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 for forming a permanent film. It is also advantageous from the viewpoint of improving the sensitivity of the resin film formed by the photosensitive resin composition for forming a permanent film.
Specific examples of the thermal crosslinking agent include 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol (para-xylene glycol), 1,3,5-benzenetrimethanol, Methylol groups such as 4,4-biphenyldimethanol, 2,6-pyridinedimethanol, 2,6-bis (hydroxymethyl) -p-cresol, and 4,4′-methylenebis (2,6-dialkoxymethylphenol) A phenol 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 Compounds having an alkoxymethyl group such as 4,4'-methylenebis (2,6-dimethoxymethylphenol); methylolmelamine compounds represented by hexamethylolmelamine, hexabutanolmelamine and the like; alkoxymelamine compounds such as hexamethoxymelamine; Alkoxymethyl glycoluril compounds such as tetramethoxymethylglycoluril; methylolurea compounds such as methylolbenzoguanamine compounds and dimethylolethyleneurea; cyano compounds such as dicyanoaniline, dicyanophenol, cyanophenylsulfonic acid; and 1,4-phenylene diisocyanate Compounds such as 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; ethylene glycol diglycidyl ether; Epoxy group-containing compounds such as phenol A diglycidyl ether, triglycidyl isocyanurate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenol novolak resin type epoxy resin; N, N ' Maleimide compounds such as -1,3-phenylenedimaleimide and N, N'-methylenedimaleimide are exemplified. As the thermal crosslinking agent, one or more of the above specific examples can be used in combination.

The lower limit of the content of the thermal crosslinking agent in the photosensitive resin composition for forming a permanent film is, for example, preferably 0.1 part by mass or more, and more preferably 1 part by mass with respect to 100 parts by mass of the alkali-soluble resin (A). It is more preferably at least 3 parts by mass, still more preferably at least 5 parts by mass, even more preferably at least 8 parts by mass.

Further, the upper limit of the content of the thermal crosslinking agent in the photosensitive resin composition for forming a permanent film is, for example, preferably 20 parts by mass or less, and more preferably 15 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). Parts by weight or less, more preferably 12 parts by weight or less, even more preferably 10 parts by weight or less. Thereby, even when the thermal cross-linking agent has a solvating functional group such as a phenolic hydroxyl group, a decrease in chemical resistance after post-baking can be suppressed.

(Antioxidant)
The photosensitive resin composition for forming a permanent film according to the present embodiment may further include an antioxidant. As the antioxidant, at least one selected from phenolic antioxidants, phosphorus antioxidants and thioether antioxidants can be used. The antioxidant can suppress oxidation of the resin film formed by the photosensitive resin composition for forming a permanent film.

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-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert-butyl-4-methylphenol, 2,6-di t-butyl-4-ethylphenol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-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′-butylidenebis (6-t-butyl-m-cresol), 2,2′-ethylidenebis (4,6-di-t-butylphenol), 2, 2'-ethylidenebis (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], triethyleneglycolbis [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'-butylidenebis (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 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-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2,4-dimethyl-6- (1-methylcyclohexyl), Styrenated phenol, 2,4-bis ((octylthio) methyl) -5-methylphenol, and the like.

Examples of the phosphorus-based antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenylphosphite), 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) octyl phosphite, tris (mixed mono and di-nonylphenyl phosphite), bis (2 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methoxyca) Rubynylethyl-phenyl) pentaerythritol diphosphite; bis (2,6-di-t-butyl-4-octadecyloxycarbonylethylphenyl) pentaerythritol diphosphite;

Examples of the thioether-based antioxidant include 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 for forming a permanent film according to the present embodiment may further include a filler. As the filler, an appropriate filler can be selected according to the mechanical and thermal properties required for the resin film formed by the photosensitive resin composition for forming a permanent film.

Specific examples of the filler include an inorganic filler and an organic filler.
Specific examples of the inorganic filler include silica such as fused silica, fused spherical silica, crystalline silica, secondary aggregated silica, and finely divided silica; alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, and silicon carbide. , Aluminum hydroxide, magnesium hydroxide, metal compounds such as titanium white; talc; clay; mica; As the inorganic filler, one or more of the above specific examples can be used in combination.

Specific examples of the organic filler include organosilicone powder and polyethylene powder. As the organic filler, one or a combination of two or more of the above specific examples can be used.

(Preparation of photosensitive resin composition for permanent film formation)
The method for preparing the photosensitive resin composition for forming a permanent film in the present embodiment is not limited, and a known method can be used according to 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. This makes it possible to obtain a photosensitive resin composition for forming a permanent film as a varnish.

In the present embodiment, the steps of adjusting the photosensitive resin composition for forming a permanent film are all performed under a nitrogen atmosphere from the viewpoint of setting the contact angle with respect to a metal material existing on the substrate of the electronic device to a desired value. It is preferred to do so. As a result, deterioration of components in the photosensitive resin composition for forming a permanent film, which is reactive with components contained in air such as oxygen, can be suppressed. Therefore, the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition can be improved.

(Application)
The photosensitive resin composition of the present embodiment is used for forming a permanent film of a semiconductor device such as a panel level package.

The permanent film is, for example, a cured film obtained by coating a photosensitive resin composition, then performing pre-baking, exposure and development, patterning into a desired shape, and curing by post-baking. Be composed. The permanent film can be used as a buffer coat film (protective film) of an electronic device, an interlayer film, a dam material, and the like. Above all, the above-mentioned permanent film can be suitably used as a buffer coat film.

In the above-described process of manufacturing the permanent film, the step of applying the photosensitive resin composition is preferably performed, for example, by slit coating. Thereby, a more uniform resin film can be formed on the substrate.

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 the photosensitive resin composition is applied, various methods can be applied for removing the solvent (for example, heating), but when used for a panel level package, a relatively large area is required. In view of this, 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, an environment of 30 Pa or less). In addition, there is also a merit that microbubbles that can be generated during coating can be reduced by performing drying under reduced pressure.

When prebaking is performed, the conditions are, for example, 70 to 160 ° C. for about 5 seconds to 30 minutes.
For exposure, electromagnetic waves of various wavelengths, particle beams, and the like can be used. For example, ultraviolet rays such as g-rays and i-rays, visible rays, lasers, X-rays, and electron beams are used. It is preferably ultraviolet light such as g-line or i-line. The exposure amount is appropriately set according to the sensitivity of the photosensitive adhesive composition and the like, and is, for example, about 30 to 3000 mJ / cm ² . The exposure is usually performed by using an appropriate mask pattern or the like.
For development, various developing solutions can be applied. 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 Organic developers such as butyl and the like can be mentioned. Among these, an alkali developer is preferable, and an aqueous solution of tetramethylammonium hydroxide is particularly preferable. Examples of the method of supplying the developer include a method such as spraying, paddle, and immersion. The spray method is preferable in terms of processing a large-area panel.
The post-baking conditions (curing conditions) are not particularly limited, but are, for example, 80 to 300 ° C. for 30 to 300 minutes.

Next, an example of the electronic device 100 including the photosensitive resin composition for forming a permanent film according to the present embodiment will be described.
The electronic device 100 shown in FIG. 1 is, for example, a semiconductor chip. In this case, for example, a semiconductor package is obtained by mounting electronic device 100 on a wiring board via bumps 52. The electronic device 100 includes a semiconductor substrate provided with a semiconductor element such as a transistor, and a multilayer wiring layer provided on the semiconductor substrate (not shown). In the uppermost layer of the multilayer wiring layers, an interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided. The uppermost layer wiring 34 is made of, for example, Al. Further, a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34. An opening through which the uppermost layer wiring 34 is exposed is provided in a part of the passivation film 32.

(4) The redistribution layer 40 is provided on the passivation film 32. The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, an insulating layer 44 provided on the insulating layer 42 and the rewiring 46, Having. An opening through which the uppermost layer wiring 34 is exposed is formed in the insulating layer 42. The rewiring 46 is formed on the insulating layer 42 and in an opening provided in the insulating layer 42, and is electrically connected to the uppermost wiring 34. The insulating layer 44 has an opening through which a predetermined region of the rewiring 46 is exposed. In an opening provided in the insulating layer 44, a bump 52 is formed via an UBM (Under \ Bump \ Metallurgy) layer 50, for example. The electronic device 100 is connected to a wiring board or the like via the bump 52, for example.

In the present embodiment, at least one of the insulating layer 42 and the insulating layer 44 is formed of, for example, a cured film (permanent film) formed by curing the above-described photosensitive resin composition for forming a permanent film. be able to. In this case, for example, the coating film formed of the photosensitive resin composition for forming a permanent film is exposed to ultraviolet rays, developed, patterned, and then cured by heating to form the insulating layer 42 or the insulating layer 44. Is formed.
In other words, a coating film forming step of applying the photosensitive resin composition for forming a permanent film to form a coating film, an exposure step of exposing the formed coating film, and a developing step of developing the exposed coating film A heating step of heating the coating film remaining after the development to cure the coating film and form a permanent film, thereby forming a cured film of the photosensitive resin composition for permanent film formation. It is used as the insulating layer 42 or the insulating layer 44 of the device 100.

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than the above can be adopted.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

First, the raw materials used in the examples and comparative examples will be described in detail.

<Alkali-soluble resin>
According to the following procedure, an alkali-soluble resin 1 as a polyamide resin was prepared.
206.58 g of diphenyl ether-4,4′-dicarboxylic acid represented by the following formula (DC2) was placed in a four-neck glass separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. (0.800 mol) and 170.20 g of a mixture of dicarboxylic acid derivatives obtained by reacting 216.19 g (1.600 mol) of 1-hydroxy-1,2,3-benzotriazole monohydrate. .346 mol), 4.01 g (0.047 mol) of 5-aminotetrazole, 45.22 g (0.196 mol) of 4,4′-methylenebis (2-aminophenol) represented by the following formula (DA2): 56.24 g (0.196 mol) of 4,4′-methylenebis (2-amino-3,6 dimethylphenol) represented by the following formula (DA3) It was. Thereafter, 578.3 g of N-methyl-2-pyrrolidone was added to the separable flask to dissolve each raw material component. Next, the reaction was performed at 90 ° C. for 5 hours using an oil bath. Next, 24.34 g (0.141 mol) of 4-ethynylphthalic anhydride and 121.7 g of N-methyl-2-pyrrolidone were added to the separable flask, and the mixture was reacted at 90 ° C. with stirring for 2 hours. After that, the reaction was terminated by cooling to 23 ° C.

(4) The filtrate obtained by filtering the reaction mixture in the separable flask was put into a solution of water / isopropanol = 7/4 (volume ratio). Thereafter, the precipitate was separated by filtration, sufficiently washed with water, and then dispersed in NMP (N-methylpyrrolidone) without drying to obtain a solution of the desired alkali-soluble resin 1. The weight average molecular weight Mw of the obtained alkali-soluble resin 1 was 18081.

<Photosensitizer>
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 a compound represented by the following formula (P-1) was added. 18.81 g (0.070 mol) of 2-naphthoquinone-2-diazido-5-sulfonyl chloride and 170 g of acetone were put therein, stirred and 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 reach 35 ° C. or higher. After allowing the reaction to proceed at room temperature for 3 hours, 1.05 g (0.017 mol) of acetic acid was added, followed by a further reaction 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). Next, the precipitate was collected by filtration, washed sufficiently with water, and dried under vacuum. Thus, Photosensitive Agent 1 represented by the following formula (Q-1) was obtained.

<Adhesion aid>
-Adhesion aid 1: a silane coupling agent represented by the following formula (3)

In addition, the adhesion aid 1 was synthesized as follows.
In a suitably sized reaction vessel equipped with a stirrer and a condenser, cyclohexene-1,2-dicarboxylic anhydride (45.6 g, 300 mmol) is dissolved in N-methyl-2-pyrrolidone (970 g), To 30 ° C. Next, 3-aminopropyltriethoxysilane (62 g, 280 mmol) was charged into the dropping funnel and dropped into the solution over 60 minutes. After completion of the dropwise addition, the mixture was stirred at 30 ° C. for 18 hours to obtain a silane coupling agent represented by the above formula (3).
・ Adhesion aid 2: X12-5263-HP manufactured by Shin-Etsu Chemical Co., Ltd.

<Thermal crosslinking agent>
-Thermal crosslinking agent 1: para-xylene glycol (PXG, manufactured by Ihara Nikkei Chemical Industry Co., Ltd.)

<Surfactant>
-Surfactant 1: polyether-modified polydimethylsiloxane (liquid silicone compound having a polyether group, BYK-333, manufactured by BYK Japan KK)
-Surfactant 2: polyether-modified polydimethylsiloxane (BYK-349, manufactured by BYK Japan KK)
-Surfactant 3: Polyester-modified polydimethylsiloxane (BYK-313, manufactured by BYK Japan KK)
-Surfactant 4: aralkyl-modified polydimethylsiloxane (BYK-323, manufactured by BYK Japan KK)
-Surfactant 5: fluorinated surfactant (FC4430, manufactured by 3M Japan Co., Ltd.)

<Solvent>
・ Solvent 1: Tetramethylurea (TMU)
-Solvent 2: γ-butyrolactone (GBL)

(Preparation of photosensitive resin composition)
The photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 and 2 were prepared as follows.
By adding each raw material component to the solvent shown in Table 1 other than the solvent, stirring, and filtering with a PTFE membrane filter having a pore size of 0.2 μm, the photosensitive resin composition of each Example and each Comparative Example was obtained. Varnish was obtained. The amount of the solvent was adjusted so that each composition had a solid concentration of 10 to 40% by mass and a viscosity of about 50 to 2000 mPa · s. Further, the step of producing a varnish of the photosensitive resin composition of each of the examples and comparative examples was performed under a nitrogen atmosphere.

(Contact angle)
With respect to the photosensitive resin compositions for forming a permanent film of each of Examples and Comparative Examples, contact angles with respect to a sputtered copper substrate were measured.

In addition, what was produced by the following procedures was used as a sputtered copper substrate.
(1) A substrate made of titanium was prepared.
(2) A copper thin film having a thickness of 0.3 μm was formed on the substrate by sputtering.

As a specific procedure of the contact angle measurement, first, for the compositions of the respective examples and comparative examples, the viscosity measured by the E-type viscometer after rotating at a rotation frequency of 100 rpm, a temperature of 25 ° C. and 300 seconds becomes 50 mPa · s. As described above, the viscosity was adjusted with a mixed solvent containing tetramethylurea (TMU) and γ-butyrolactone (GBL) (mixing ratio 3: 7).
Next, a contact angle 10 seconds after the varnish of 2 μl of the varnish of the photosensitive resin composition for forming a permanent film whose viscosity was adjusted as described above was dropped on each substrate at a temperature of 25 ° C., was evaluated by a droplet method. . The measurement was performed using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DROPMASTER-501).
Thereby, the contact angle (θ _Cu ) with respect to the sputtered copper substrate was evaluated. The evaluation results are shown in Table 1 below. The unit is “°”. The ratio (%) of the contact angle θ _Cu of each of Examples and Comparative Example 2 to the contact angle θ _Cu of Comparative Example 1 was calculated, and is shown in Table 1.

As shown in Table 1, it was confirmed that the photosensitive resin compositions for forming a permanent film of Examples 1 to 12 had lower contact angles with the sputtered copper substrate than Comparative Example 1. Therefore, it can be said that the photosensitive resin compositions for forming a permanent film of Examples 1 to 12 have improved wettability to metal as compared with Comparative Example 1.

This application claims priority based on Japanese Patent Application No. 2018-170030 filed on Sep. 11, 2018, the disclosure of which is incorporated herein in its entirety.

Claims (11)

1. An alkali-soluble resin (A),
   A photosensitive agent (B),
   A surfactant (C);
   Including
   A photosensitive resin composition for forming a permanent film, wherein the surfactant (C) contains an organically modified dimethylsiloxane represented by the following formula (1).
   

   

   (In the formula (1), X represents a polyether group, a polyester group, or an aralkyl group, and m and n each represent an integer of 1 to 100.)
2. 2. The photosensitive resin composition for forming a permanent film according to claim 1, wherein X in the formula (1) is represented by the following formula (2-1).
   

   

   (In the formula (2-1), R ²⁰ represents an alkyl group having 1 to 6 carbon atoms, and R ²¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkyl ether having 1 to 6 carbon atoms. A group or an unsaturated alkyl ether group having 1 to 6 carbon atoms, EO represents an ethylene oxide group, PO represents a propylene oxide group, o represents an integer of 1 or more, and p represents an integer of 0 or more. The order of EO and PO may be random.)
3. The photosensitive resin composition for forming a permanent film according to claim 2, wherein the molar ratio of the propylene oxide group to the total molar amount of the ethylene oxide group and the propylene oxide group is 1% or more and 99% or less.
4. The photosensitive resin for forming a permanent film according to any one of claims 1 to 3, wherein a ratio of m to a total of m and n represented by the formula (1) is 0.5% or more and 60% or less. Composition.
5. The alkali-soluble resin (A) is at least one selected from the group consisting of a polyamide resin, a polybenzoxazole resin, a polyimide resin, a phenol resin, a hydroxystyrene resin, and a cyclic olefin resin. The photosensitive resin composition for forming a permanent film according to claim 1.
6. The photosensitive resin composition for forming a permanent film according to any one of claims 1 to 5, wherein the photosensitive agent (B) contains a photoacid generator.
7. The photosensitive resin composition for forming a permanent film according to any one of claims 1 to 6, which is used for a buffer coat film.
8. A cured film obtained by curing the photosensitive resin composition for forming a permanent film according to any one of claims 1 to 7.
9. An electronic device comprising the cured film according to claim 8.
10. A permanent resin containing an alkali-soluble resin (A), a photosensitive agent (B), and a surfactant (C), wherein the surfactant (C) contains an organically modified dimethylsiloxane represented by the following formula (1): A coating film forming step of forming a coating film by applying a photosensitive resin composition for film formation,
    An exposure step of exposing the formed coating film,
    A developing step of developing the exposed coating film;
    A heating step of heating the coating film remaining after development to cure the coating film and form a permanent film,
    A method for producing a cured film of a photosensitive resin composition for forming a permanent film, comprising:
    

    

    (In the above formula (1), X represents a polyether group, a polyester group or an aralkyl group, and m and n each represent an integer of 1 or more and 100 or less.)
11. A method for manufacturing an electronic device, comprising a method for manufacturing a cured film of the photosensitive resin composition for forming a permanent film according to claim 10 in the process.

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