TW202024193A - Photosensitive resin composition for producing of permanent film, cured film, electronic device, method for producing cured film, and method for producing electronic device - 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 permanent film formation, cured film, electronic device, cured film manufacturing method, and electronic device manufacturing method

The present invention relates to a photosensitive resin composition for permanent film formation, a cured film, an electronic device, a method of manufacturing a cured film, and a method of manufacturing an electronic device

As a permanent film constituting an electronic device, a cured film obtained by exposing a photosensitive resin composition may be used. As a technique related to such a photosensitive resin composition, for example, the one described in Patent Document 1 can be cited. According to Patent Document 1, there is described a photosensitive resin composition having a polymer and a fluorine-based surfactant. The polymer contains: a structural unit having a residue in which an acid group is protected by an acid decomposable group; The constituent unit of a sexual group. Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2016-189006

[The problem to be solved by the invention]

With the miniaturization of electronic devices, the wiring and L/S (wiring width, wiring spacing) that constitute the electronic device can be further refined and densified. With this, the requirements for permanent films for electronic devices have become increasingly strict. As a characteristic required for permanent films, it is required to further improve the wettability with the metal constituting the fine wiring. In the conventional photosensitive resin composition, a fluorine-based surfactant is used as the surfactant, and therefore, from the viewpoint of environmental impact, the addition amount of the surfactant is limited. As a result, the requirement for further improvement of the wettability with metals cannot be met. Therefore, the present invention provides a technology related to a photosensitive resin composition for forming a permanent film with improved wettability with metals. [Technical means to solve the problem]

（式（1）中，X表示聚醚基、聚酯基或芳烷基，m、n分別表示1以上且100以下的整數。）According to the present invention, there is provided a photosensitive resin composition for permanent film formation, which contains an alkali-soluble resin (A), a photosensitizer (B), and a surfactant (C). The surfactant (C) includes the following formula: (1) Said organically modified dimethylsiloxane.

(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 or more and 100 or less.)

Moreover, according to the present invention, there is provided a cured film obtained by curing the above-mentioned photosensitive resin composition for forming a permanent film.

Furthermore, according to the present invention, an electronic device containing the above-mentioned cured film is provided.

（上述式（1）中，X表示聚醚基、聚酯基或芳烷基，m、n分別表示1以上且100以下的整數。）In addition, according to the present invention, there is provided a method of manufacturing a cured film of a photosensitive resin composition for permanent film formation, the manufacturing method comprising: a coating film forming step, coating the photosensitive resin composition for permanent film formation to form a coating A film, the photosensitive resin composition for forming a permanent film contains an alkali-soluble resin (A), a photosensitizer (B), and a surfactant (C), and the surfactant (C) includes the one represented by the following formula (1) Organically modified dimethylsiloxane; the exposure step is to expose the formed coating film; the developing step is to develop the exposed coating film; and the heating step is to perform the remaining coating film after the development Heating hardens the coating film and forms a permanent film.

(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.)

Furthermore, according to the present invention, there is provided a method of manufacturing an electronic device including a method of manufacturing a cured film of the photosensitive resin composition for forming a permanent film in the step. [Effects of Invention]

According to the present invention, it is possible to provide a technology related to a photosensitive resin composition for forming a permanent film with improved wettability with metals.

Hereinafter, embodiments of the present invention will be described in detail. In addition, in this specification, the marks of "a to b" in the description of the numerical range, unless otherwise specified, indicate a or more and b or less.

（式（1）中，X表示聚醚基、聚酯基或芳烷基，m、n分別表示1以上且100以下的整數。） 依本實施形態的永久膜形成用感光性樹脂組成物，能夠提高與基板、尤其與金屬的潤濕性，進而能夠提高使用了永久膜形成用感光性樹脂組成物之膜的成膜性。作為能夠期待基於本實施形態的永久膜形成用感光性樹脂組成物之潤濕性的提高之金屬，可舉出Cu、Al。作為對金屬的潤濕性的指標，可舉出與金屬的接觸角。The photosensitive resin composition for permanent film formation of this embodiment contains an alkali-soluble resin (A), a photosensitizer (B), and a surfactant (C), and the surfactant (C) includes the one represented by the following formula (1) Organically modified dimethylsiloxane.

(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 or more and 100 or less.) According to the photosensitive resin composition for permanent film formation of this embodiment, The wettability with the substrate, especially with the metal can be improved, and the film forming properties of the film using the photosensitive resin composition for permanent film formation can be improved. Examples of metals that can be expected to improve the wettability of 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 metal, the contact angle with metal can be mentioned.

Hereinafter, each component contained in the photosensitive resin composition for permanent film formation of the present embodiment (hereinafter, the photosensitive resin composition for permanent film formation 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 the mechanical properties, optical properties and other physical properties required by the resin film. Specific examples of the alkali-soluble resin (A) include polyamide resin, polybenzoxazole resin, polyimide resin, phenol resin, hydroxystyrene resin, cyclic olefin resin, and the like. As alkali-soluble resin (A), 1 type or a combination of 2 or more types in the said specific example can be used. As the alkali-soluble resin (A), it is preferable to use a polyamide resin or a polybenzoxazole resin in the above-mentioned specific examples, and it is more preferable to use a polybenzoxazole resin. Thereby, the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition for permanent film formation can be improved. In addition, it is also from the viewpoint that the mechanical strength and other physical properties of the cured film (permanent film) composed of the photosensitive resin composition for permanent film formation can be improved, whereby the uniformity of the film thickness can be improved and the occurrence of damage can be suppressed. Better.

(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 the polyamide, and more preferably containing the following The structural unit represented by the formula (PA1). Thereby, the physical properties, such as the mechanical strength, of the resin film comprised by the photosensitive resin composition can be improved. Therefore, it is also preferable from the viewpoint that the uniformity of the film thickness can be improved and the occurrence of breakage can be suppressed. In addition, in this embodiment, the aromatic ring means a benzene ring; a condensed aromatic ring such as a naphthalene ring, an anthracene ring, and a pyrene ring; and a heteroaromatic ring such as a pyridine ring and 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 the precursor of the polybenzoxazole resin. The polyamide resin containing the structural unit represented by the above formula (PA1) can be prepared, for example, by performing a heat treatment at a temperature of 150°C or more and 380°C for 30 minutes or more and 50 hours or less for dehydration and ring closure. Into polybenzoxazole resin. Here, the structural unit of the above formula (PA1) becomes a structural unit represented by the following formula (PBO1) by dehydration and ring closure.

When the alkali-soluble resin (A) of this embodiment is a polyamide resin containing the structural unit represented by the above formula (PA1), for example, the photosensitive resin composition can be subjected to the above heat treatment to perform dehydration and ring closure , And made of polybenzoxazole resin. That is, the photosensitive resin composition subjected to the above-mentioned heat treatment contains a polybenzoxazole resin as the alkali-soluble resin (A). In addition, in the case where the alkali-soluble resin (A) is a polyamide resin containing the structural unit represented by the above formula (PA1), it can be dehydrated by performing the above heat treatment after the resin film and the electronic device described below are produced The ring is closed to produce polybenzoxazole resin. When a polybenzoxazole resin is prepared by dehydrating and ring-opening a polyamide resin, the mechanical properties and thermal properties can be improved. This is advantageous in terms of being able to suppress the deformation of the resin film.

(Polyamide resin, polyimide resin) In addition, as the polyamide resin, for example, those containing a structural unit represented by the following formula (PA2) can be used. The polyimide resin containing the structural unit represented by the following formula (PA2) is a precursor of the polyimide resin. The polyamide resin containing the structural unit represented by the following formula (PA2) can be dehydrated and ring closed by heat treatment at a temperature of 150°C or higher and 380°C or lower for 30 minutes or more and 50 hours or less, for example, Made into polyimide resin. Here, the structural unit of the following formula (PA2) becomes a structural unit represented by the following formula (PI1) by dehydration and ring closure. In the case where the alkali-soluble resin (A) of this embodiment is a polyamide resin containing a structural unit represented by the following formula (PA2), the photosensitive resin composition can be subjected to the above heat treatment to perform dehydration and ring closure. And made of polyimide resin. That is, the photosensitive resin composition that has been subjected to the above heat treatment contains a polyimide resin as the alkali-soluble resin (A). In addition, in the case where the alkali-soluble resin (A) is a polyamide resin containing a structural unit represented by the following formula (PA2), it can be carried out by performing the above-mentioned heat treatment after the resin film and electronic device described below are produced Dehydration and ring closure are made into polyimide resin.

（式（PA2）中，R^B 及R^C 分別獨立地為碳數1以上且30以下的有機基團。）

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

式（PI1）中，R^B 及R^C 與上述式（PA2）相同。

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

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

(Manufacturing method of polyamide resin) The polyamide resin of this embodiment is polymerized in the following manner, for example. First, through the polymerization step (S1), the diamine monomer and the dicarboxylic acid monomer are polycondensed, thereby polymerizing the polyamide. Next, the low-molecular-weight component removal step (S2) removes the low-molecular-weight component to obtain a polyamide resin containing polyamide as a main component.

(Aggregation step (S1)) In the polymerization step (S1), the diamine monomer and the dicarboxylic acid monomer are polycondensed. The polycondensation method for polymerizing polyamide is not limited, and specific examples include melt polycondensation, acid chloride method, and direct polycondensation. In addition, a compound selected from the group consisting of tetracarboxylic dianhydride, trimellitic anhydride, dicarboxylic acid dichloride, or active ester dicarboxylic acid can be used instead of dicarboxylic acid Acid monomer. As a method of obtaining an active ester type dicarboxylic acid, specifically, the method of reacting dicarboxylic acid with 1-hydroxy-1,2,3-benzotriazole etc. can be mentioned.

Hereinafter, the diamine monomer and the dicarboxylic acid monomer used in the polymerization of the polyamide resin will be described. In addition, each of the diamine monomer and the dicarboxylic acid monomer may use only one type each, or two or more types of diamine monomers and/or two or more types of dicarboxylic acid monomers may be used.

(Diamine monomer) The diamine monomer used for polymerization is not limited. For example, a diamine monomer containing an aromatic ring in the structure is preferably used, and a diamine monomer containing a phenolic hydroxyl group in the structure is more preferably used. By using this type of diamine monomer as a raw material to produce a polyamide resin, the structure of the polyamide resin can be controlled, and the dispersibility when it is made into a composition can be further improved.

Here, as the diamine monomer containing a phenolic hydroxyl group in the structure, for example, one represented by the following formula (DA1) is preferred. By using this type of diamine monomer as a raw material to produce a polyamide resin, the structure of the polyamide resin can be controlled, and the molecular chains of the polyamide resin can be formed into a tighter structure. Therefore, it is considered that the coordination in which the molecules of the alkali-soluble resin (A) and the metal molecules are more firmly bonded can freeze the molecular structure and improve the adhesion to the substrate. In addition, 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 of this embodiment preferably contains, for example, a structural unit represented by the following formula (PA3).

式（DA1）中，R⁴ 為由選自由氫原子、碳原子、氧原子、氮原子、硫原子、磷原子、矽原子、氯原子、氟原子、溴原子組成之群中之1種或2種以上的原子形成之基團。R⁵ ～R¹⁰ 分別獨立地表示氫或碳數1以上且30以下的有機基團。

In the formula (DA1), R ⁴ is one or two 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 more than one atom. R ⁵ to R ¹⁰ each independently represent hydrogen or an organic group having 1 to 30 carbon atoms.

式（PA3）中，R⁴ 、R⁵ ～R¹⁰ 與上述式（DA1）相同。

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

R ^{4 in} formula (DA1) and formula (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 kinds of atoms. In addition, R ⁴ is a divalent group. Here, the divalent group represents the valence. That is, R ⁴ represents that there are two bonding bonds to other atoms.

When R ⁴ in formula (DA1) and formula (PA3) contains carbon atoms, R ^{4 is,} for example, a group having 1 or more and 30 or less carbon atoms, preferably a group having 1 or more and 10 or less carbon atoms, It is more preferably a group having 1 or more and 5 or less carbon atoms, and still more preferably a group having 1 or more and 3 or less carbon atoms.

When R ⁴ in formula (DA1) and formula (PA3) contains a carbon atom, as R ⁴ , specifically, alkylene, aryl, halogen-substituted alkylene, halogen-substituted arylene Base etc. As the alkylene group, for example, it may be a straight-chain alkylene group or a branched-chain alkylene group. As the linear alkylene group, specifically, methylene, ethylene, propylene, butylene, pentylene, hexylene, and heptylene ), octyl, nonyl, decyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc. Specific examples of the branched alkylene group include -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ )( CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) -, -C (CH ₂ CH ₃ ) ₂ -and other alkyl methylene groups; -CH (CH ₃ ) CH ₂ -, -CH (CH ₃ ) CH (CH ₃ ) -, -C (CH ₃ ) ₂ CH ₂ -, -CH (CH ₂ CH ₃ ) CH ₂ -, -C (CH ₂ CH ₃ ) ₂ -CH ₂ -etc. Alkylethylene and the like. As the aryl group, specifically, a phenyl group, a biphenylene group, a naphthyl group, an anthrylene group, and two or more aryl groups bonded to each other can be mentioned. As the halogen-substituted alkylene group and the halogen-substituted arylene group, specifically, those obtained by substituting a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom for the hydrogen atom in the above-mentioned alkylene group and the arylene group can be used. Among these, it is preferable to use one obtained by substituting fluorine atoms for hydrogen atoms.

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

R ⁵ to R ^{10 in} formula (DA1) and 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 is preferred. The group is more preferably hydrogen or an organic group having a carbon number of 1 or more and 5 or less, further preferably hydrogen or an organic group having a carbon number of 1 or more and 3 or less, and still more preferably hydrogen or a carbon number of 1 or more and 2 The following organic groups. Thereby, the aromatic rings of the polyamide resin can be closely aligned with each other. Therefore, the molecular structure of the alkali-soluble resin (A) can be frozen and the adhesion can be improved by the coordination that more firmly bonds the molecules of the alkali-soluble resin (A) and the metal molecules.

Specific examples of the organic groups having 1 or more and 30 carbon atoms of R ⁵ to R ¹⁰ in formula (DA1) and formula (PA3) include methyl, ethyl, n-propyl, isopropyl, Alkyl groups such as n-butyl, isobutyl, second butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.; allyl, pentenyl, Alkenyl groups such as vinyl; alkynyl groups such as ethynyl; alkylene groups such as methine and ethylene; aryl groups such as tolyl, xylyl, phenyl, naphthyl, anthracenyl, etc.; benzyl, phenethyl, etc. Aralkyl groups; cycloalkyl groups such as adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups; alkaryl groups such as tolyl and xylyl groups.

As the diamine monomer represented by the formula (DA1), specifically, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-methylenebis (2-Amino-3,6dimethylphenol), 4,4'-methylenebis(2-aminophenol), 1,1-bis(3-amino4-hydroxyphenyl)ethane , 3,3'-diamino-4,4'-dihydroxydiphenyl ether, etc. By using these diamine monomers, the aromatic rings of the polyamide resin can be closely aligned with each other. Therefore, the molecular structure of the alkali-soluble resin (A) can be frozen and the adhesion can be improved by the coordination that more firmly bonds the molecules of the alkali-soluble resin (A) and the metal molecules. In addition, as the diamine monomer, one type of the above-mentioned specific examples or a combination of two or more types can be used. The structural formulas of these diamine monomers are shown below.

(Dicarboxylic acid monomer) The dicarboxylic acid monomer used for polymerization is not limited. For example, a dicarboxylic acid monomer containing an aromatic ring in the structure is preferably used. As the dicarboxylic acid monomer containing an aromatic ring, for example, one represented by the following formula (DC1) is preferably used. By using this type of dicarboxylic acid monomer as a raw material to produce a polyamide resin, the structure of the polyamide resin can be controlled, and the dispersibility in a mixed solvent can be improved. In addition, by improving the dispersibility, it is possible to suppress the unevenness of the wettability to the metal material.

式（DC1）中，R¹¹ 為由選自由氫原子、碳原子、氧原子、氮原子、硫原子、磷原子、矽原子、氯原子、氟原子、溴原子組成之群中之1種或2種以上的原子形成之基團。R¹² ～R¹⁹ 分別獨立地表示氫或碳數1以上且30以下的有機基團。

In the formula (DC1), R ¹¹ is one or two 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 more than one atom. R ¹² to R ¹⁹ each independently represent hydrogen or an organic group having 1 to 30 carbon atoms.

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

R ^{11 in} formula (DC1) and formula (PA4) 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 kinds of atoms. In addition, R ¹¹ is a divalent group. Here, the divalent group represents the valence. That is, R ¹¹ represents that there are two bonding bonds to other atoms.

R in (DC1) and of formula (PA4) of the case containing ¹¹ carbon atoms, R ¹¹ or more carbon atoms, for example 1 to 30 the following groups, more preferably 1 to 10 carbon atoms the following groups, and more It is preferably a group having 1 or more and 5 or less carbon atoms, and more preferably a group having 1 or more and 3 or less carbon atoms.

When R ¹¹ in formula (DC1) and formula (PA4) contains carbon atoms, as R ¹¹ , specifically, alkylene, aryl, halogen-substituted alkylene, halogen-substituted aryl Base etc. As the alkylene group, for example, it may be a straight-chain alkylene group or a branched-chain alkylene group. Specific examples of the linear alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and nonylylene. , Decylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc. Specific examples of the branched alkylene group include -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ )( CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) -, -C (CH ₂ CH ₃ ) ₂ -and other alkyl methylene groups; -CH (CH ₃ ) CH ₂ -, -CH (CH ₃ ) CH (CH ₃ ) -, -C (CH ₃ ) ₂ CH ₂ -, -CH (CH ₂ CH ₃ ) CH ₂ -, -C (CH ₂ CH ₃ ) ₂ -CH ₂ -etc. Alkylethylene and the like. As the arylene group, specifically, a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and two or more arylene groups bonded to each other can be mentioned. As the halogen-substituted alkylene group and the halogen-substituted arylene group, specifically, those obtained by substituting a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom for the hydrogen atom in the above-mentioned alkylene group and the arylene group can be used. Among these, it is preferable to use one obtained by substituting fluorine atoms for hydrogen atoms.

When R ¹¹ in the formula (DC1) and the formula (PA4) does not contain a carbon atom, as R ¹¹ , specifically, a group composed of an oxygen atom or a sulfur atom, and the like can be given.

R ¹² to R ^{19 in} formula (DC1) and formula (PA4) are each independently hydrogen or an organic group having 1 or more and 30 carbon atoms, for example, hydrogen or an organic group having 1 or more and 10 carbon atoms is preferable The group is more preferably hydrogen or an organic group having 1 to 5 carbon atoms, still more preferably hydrogen or an organic group having 1 to 3 carbon atoms, and still more preferably hydrogen.

Specific examples of the organic groups having 1 or more and 30 carbon atoms of R ¹² to R ¹⁹ in formula (DC1) and formula (PA4) include methyl, ethyl, n-propyl, isopropyl, Alkyl groups such as n-butyl, isobutyl, second butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.; allyl, pentenyl, Alkenyl groups such as vinyl; alkynyl groups such as ethynyl; alkylene groups such as methine and ethylene; aryl groups such as tolyl, xylyl, phenyl, naphthyl, anthracenyl, etc.; benzyl, phenethyl, etc. Aralkyl groups; cycloalkyl groups such as adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups; alkaryl groups such as tolyl and xylyl groups.

As the dicarboxylic acid monomer, specifically, diphenyl ether 4,4'-dicarboxylic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyl dicarboxylic acid, etc. can be used. As the dicarboxylic acid monomer, it is preferable to use diphenyl ether 4,4'-dicarboxylic acid or isophthalic acid in the above-mentioned specific examples, and it is more preferable to use diphenyl ether 4,4'-dicarboxylic acid. The aromatic rings of the polyamide resin can be closely aligned with each other. Therefore, the molecular structure of the alkali-soluble resin (A) can be frozen and the adhesion can be improved by the coordination that more firmly bonds the molecules of the alkali-soluble resin (A) and the metal molecules.

In addition, it is preferable to modify the amine group existing at the terminal of the polyamide resin simultaneously with the polymerization step (S1) or after the polymerization step (S1). Regarding modification, for example, it can be performed by reacting a specific acid anhydride or a specific monocarboxylic acid with a diamine monomer or a polyamide resin. Therefore, in the polyamide resin of this embodiment, it is preferable that the terminal amine group is modified by a specific acid anhydride or a specific monocarboxylic acid. In addition, the above-mentioned specific acid anhydride and the above-mentioned specific monocarboxylic acid refer to those having one or more functional groups selected from the group consisting of alkenyl groups, alkynyl groups, and hydroxyl groups. Moreover, as the above-mentioned specific acid anhydride and specific monocarboxylic acid, for example, those containing a nitrogen atom are preferable. This can improve the wettability of the photosensitive resin composition after post-bake with metals such as Cu and Al.

As the above-mentioned specific acid anhydride, specifically, maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, Outer-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, methyl-5-norbornene-2, 3-Dicarboxylic anhydride, itaconic anhydride, chlorendic anhydride, 4-ethynyl phthalic anhydride, 4-phenylethynyl phthalic anhydride, 4-hydroxyphthalic anhydride, etc. As a specific acid anhydride, 1 type or a combination of 2 or more types of the said specific examples can be used.

In addition, when the amine group existing at the terminal of the polyamide resin is modified by the ring-shaped specific acid anhydride, the ring-shaped specific acid anhydride undergoes ring opening. Here, after modifying the polyimide resin, the structural unit derived from the specific acid anhydride of the ring shape is closed to form an imide ring. As a method of closing the loop, for example, heat treatment or the like can be cited. In addition, specific examples of the above-mentioned specific monocarboxylic acid include 5-norbornene-2-carboxylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, and the like. As the above-mentioned specific monocarboxylic acid, 1 type or a combination of 2 or more types of the above-mentioned specific examples can be used.

In addition, at the same time as the polymerization step (S1) or after the polymerization step (S1), the carboxyl group existing at the terminal of the polyamide resin may be modified. The modification can be carried out, for example, by reacting a specific nitrogen-containing heteroaromatic compound with a dicarboxylic acid monomer or a polyamide resin. Therefore, the polyamide resin of the present embodiment is preferably formed by modifying the terminal carboxyl group with a specific nitrogen-containing heteroaromatic compound. In addition, the above-mentioned specific nitrogen-containing heteroaromatic compound means having a group selected from 1-(5-1H-triazolyl)methylamino, 3-(1H-pyrazolyl)amino, 4-(1H -Pyrazolyl)amino, 5-(1H-pyrazolyl)amino, 1-(3-1H-pyrazolyl)methylamino, 1-(4-1H-pyrazolyl)methylamine Group, 1-(5-1H-pyrazolyl)methylamino group, (1H-tetrazol-5-yl)amino group, 1-(1H-tetrazol-5-yl)methyl-amino group and 3 -(1H-tetrazol-5-yl) phenyl-amino group consisting of one or more functional groups. This can increase the number of lone electron pairs in the photosensitive resin composition. Therefore, it is possible to improve the wettability of the photosensitive resin composition and metals such as Cu and Al after pre-bake and post-bake. Specific examples of the above-mentioned specific nitrogen-containing heteroaromatic compound include 5-aminotetrazole and the like.

(Low molecular weight component removal step (S2)) It is preferable to perform a low molecular weight component removal step (S2) after the above-mentioned polymerization step (S1) to remove low molecular weight components. Specifically, after concentrating an organic layer containing a mixture of a low molecular weight component and a polyamide resin by filtration or the like, it is dissolved again in an organic solvent such as water/isopropanol. Thereby, the precipitate can be filtered out, and a polyamide resin from which low molecular weight components have been removed can be obtained.

In addition, regarding the polyamide resin, for example, it is preferable to prepare the photosensitive resin composition as a varnish without going through the step of completely volatilizing and drying the solvent after the step of removing the low molecular weight components. Thereby, by the interaction between the molecules of the polyamide resin derived from the amide bond, it is possible to suppress the decrease in the dispersibility of the polyamide resin. Therefore, the contact angle with the metal material used for the electronic device can be maintained uniformly.

(Phenol resin) Specific examples of the phenol resin include novolac type phenol resins such as phenol novolak resin, cresol novolak resin, bisphenol novolak resin, phenol-biphenol novolak resin; novolak type phenol resin, soluble Reaction products of phenolic compounds such as phenolic resins and cresol novolac resins and aldehyde compounds; reaction products of phenolic compounds such as phenol aralkyl resins and dimethanol compounds, etc. Moreover, as a phenol resin, 1 type or 2 or more types of the said specific example can be contained.

The phenol compound used as the reactant of the phenol compound and the aldehyde compound or the reactant of the phenol compound and the dimethanol compound is not limited. As the phenol compound, specifically, 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 ethyl Alkylphenols such as isopropylphenol, butylphenol and p-tert-butylphenol; polyphenols such as resorcinol, catechol, hydroquinone, gallic phenol and phloroglucinol ; 4,4'-biphenol and other biphenyl phenols. As the phenol compound, one or two or more of the above-mentioned specific examples can be used.

The aldehyde compound used as the reactant of the above-mentioned phenol compound and aldehyde compound is not limited as long as it is a compound having an aldehyde group. Specific examples of such aldehyde compounds include formaldehyde, polyoxymethylene, acetaldehyde, benzaldehyde, salicaldehyde, and the like. As the aldehyde compound, one or two or more of the above-mentioned specific examples can be used.

The dimethanol compound used as the reactant of the above-mentioned phenol compound and dimethanol compound is not limited. As the dimethanol compound, specifically, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4'-biphenyldimethanol, 3,4'-biphenyldimethanol, Dimethanol compounds such as 3,3'-biphenyldimethanol, 2,6-naphthalene dimethanol, 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, 2,6-naphthalene dicarboxylate and other 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(chloromethyl)biphenyl, 4,4'-bis(bromomethyl)biphenyl, 3,4'-bis(bromomethyl)biphenyl Bis(haloalkyl) compounds such as benzene or 3,3'-bis(bromomethyl)biphenyl, 4,4'-bis(methoxymethyl)biphenyl, 4,4'-bis(methoxymethyl) Base) Biphenyl aralkyl compounds such as biphenyl. As the dimethanol compound, one or two or more of the above-mentioned specific examples can be used.

(Hydroxystyrene resin) The hydroxystyrene resin is not limited. Specifically, one or two or more selected from the group consisting of hydroxystyrene, hydroxystyrene derivatives, styrene and styrene derivatives can be polymerized or copolymerized. And the resulting polymerization reactant or copolymerization reactant. In addition, specific examples of hydroxystyrene derivatives and styrene derivatives include those obtained by substituting a monovalent organic group for hydrogen atoms included in the aromatic ring of hydroxystyrene and styrene. Examples of monovalent organic groups that replace hydrogen atoms include alkyl groups such as methyl, ethyl, and n-propyl; alkenyl groups such as allyl and vinyl; alkynyl groups such as ethynyl; methine, Alkylene such as ethylene; cycloalkyl such as cyclopropyl; heterocyclic group such as epoxy oxetanyl, etc.

(Cyclic olefin resin) The above-mentioned cyclic olefin resin is not limited, and specifically, a polymerization reaction product obtained by polymerizing or copolymerizing one or more selected from the group consisting of norbornene and norbornene derivatives can be used Or copolymerization reactant. Here, as the norbornene derivatives, 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-nor Camphene, 5-allyl-2-norcamvene, 5-(2-propenyl)-2-norcamvene, 5-(1-methyl-4-pentenyl)-2-norcamvene , 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenylethyl-2-norcamphene, 2-ethynyl-5-norbornene, 5-nor Camphene-2-carboxylic acid methyl ester, 5-norbornene-2,3-dicarboxylic acid anhydride, etc.

For example, when the total solid content of the photosensitive resin composition is 100 parts by mass, the lower limit of the content of the alkali-soluble resin (A) in the photosensitive resin composition is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, particularly preferably 70 parts by mass or more. With this, 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. Also, for example, when the total solid content of the photosensitive resin composition is 100 parts by mass, the upper limit of the content of the alkali-soluble resin (A) in the photosensitive resin composition is preferably 95 parts by mass or less, and more It is preferably 90 parts by mass or less, and more preferably 85 parts by mass or less. In addition, in this embodiment, the total solid content of the photosensitive resin composition means the total of the components contained in the photosensitive resin composition excluding the solvent.

化合物；二氫吡啶化合物等。該等中，較佳為使用感光性重氮醌化合物。藉此，能夠提高感光性樹脂組成物的感度。因此，能夠提高圖案的精度，並能夠提高外觀。另外，作為光酸產生劑，能夠含有上述具體例中的1種或2種以上。 又，在感光性樹脂組成物為正型之情形下，作為光敏劑（B），除了上述具體例以外，還可以同時使用三芳基鋶鹽；鋶•硼酸鹽等鎓鹽等。藉此，能夠進一步提高感光性樹脂組成物的感度。(Photosensitizer (B)) As the photosensitizer (B), a photoacid generator that generates 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; Acid ester compound; 2,6-bis(trichloromethyl)-1,3,5-tri

Compounds; dihydropyridine compounds, etc. Among these, it is preferable to use a photosensitive quinone diazide compound. Thereby, the sensitivity of the photosensitive resin composition can be improved. Therefore, the accuracy of the pattern can be improved, and the appearance can be improved. In addition, as the photoacid generator, one or two or more of the above-mentioned specific examples can be contained. In addition, when the photosensitive resin composition is a positive type, as the photosensitizer (B), in addition to the specific examples described above, onium salts such as triarylsulfonate; sulfonium borate, etc. may be used together. This can further improve the sensitivity of the photosensitive resin composition.

Hereinafter, the chemical formula is used to illustrate the quinone diazide compound.

In each of the above-mentioned quinone diazide 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 in each diazoquinone compound is a structure represented by the following formula (a), the following formula (b), and the following formula (c). Q as a quinone diazide compound preferably contains 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.

When the alkali-soluble resin (A) is 100 parts by mass, the lower limit of the content of the photosensitizer (B) in the photosensitive resin composition is preferably, for example, 1 part by mass or more, more preferably 3 parts by mass or more. More preferably, it is 5 parts by mass or more. Thereby, the photosensitive resin composition can exhibit appropriate sensitivity. In addition, when the alkali-soluble resin (A) is set to 100 parts by mass, for example, the upper limit of the content of the photosensitizer (B) in the photosensitive resin composition is preferably 30 parts by mass or less, more preferably 20 parts by mass The following. This can prevent the photosensitive resin composition from being repelled by the metal material present on the surface of the substrate of the semiconductor device.

（上述式（1）中，X表示聚醚（聚氧化烯）基、聚酯基或芳烷基，m、n分別表示1以上且100以下的整數。）(Surfactant (C)) As the surfactant (C), an organically modified dimethylsiloxane represented by the following formula (1) can be used. Preferred physical properties of the surfactant (C) include high polarity and low surface tension reduction ability. By using a highly polar surfactant (C), the compatibility of the alkali-soluble resin (A) with other components containing the solvent described later can be improved, and the formation of a coating film using the photosensitive resin composition for permanent film formation can be improved. Film performance at the time. In addition, by reducing the surface tension reduction ability, the wettability with the metal material can be improved, and the coating film performance when forming a coating film using the photosensitive resin composition for permanent film formation 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.)

（上述式（2-1）中，R²⁰ 表示碳數1以上且6以下的烷基，R²¹ 表示氫原子、碳數1以上且6以下的烷基、碳數1以上且6以下的烷基醚基或碳數1以上且6以下的不飽和烷基醚基，EO表示環氧乙烷基，PO表示環氧丙烷基。o表示1以上的整數，p表示0以上的整數。關於EO和PO的順序，可以隨機。）In the case where X in the above formula (1) is a polyether group, as X, a polyether group represented by the following formula (2-1) can be preferably used.

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

In the case where 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% Above, it is more preferably 10% or more, and still more preferably 20% or more. 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 still more preferably 80% or less. By setting the molar ratio of the propylene oxide group within the above range, the wettability with metals can be improved.

（上述式（2-2）中，R²² 、R²³ 、R²⁴ 及R²⁵ 分別獨立地表示碳數1以上且20以下的烷基，r表示1以上的整數。）In the case where X in the above formula (1) is a polyester group, as X, a polyester group represented by the following formula (2-2) can be preferably used.

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

（上述式（2-3）中，R²⁶ 表示碳數1以上且30以下的烷基。）In the case where X in the above formula (1) is an aralkyl group, as X, an aralkyl group represented by the following formula (2-3) can be preferably used.

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

The lower limit of the ratio of m to the total of m and n shown in 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. On the other hand, the upper limit of the ratio of m is preferably 60% or less, more preferably 50% or less, still more preferably 40% or less, particularly preferably 30% or less. By setting the ratio of m within the above range, the wettability with metal can be improved.

The content of the surfactant (C) in the photosensitive resin composition is not particularly limited, but from the viewpoint of fully obtaining the effect of the surfactant, the photosensitive resin composition is The lower limit of the content of the surfactant (C) in the resin composition is preferably 0.001 mass% (10 ppm) or more, more preferably 0.01 mass% (100 ppm) or more. In addition, the upper limit of the content of the surfactant (C) in the photosensitive resin composition is preferably 1% by mass (10000 ppm) or less, and more preferably 0.5, relative to the entire photosensitive resin composition (including the solvent). 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, the effect of the surfactant as a surfactant for increasing the compatibility of the alkali-soluble resin (A) with other components containing the solvent described later can be further improved.

(Solvent) The photosensitive resin composition for permanent film formation of this embodiment may contain a solvent. As the solvent, organic solvents are typically used. Specific examples of the solvent include N-methyl-2-pyrrolidone (NMP), 3-methoxy-N,N-dimethylpropanamide, and N,N-dimethylformamide. Amine, N,N-dimethylpropanamide, N,N-diethylacetamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dibutylmethanamide, etc. Amide solvents; N,N-dimethylacetamide, tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone, tetrabutylurea, N,N'-dimethyl Allyl urea, 1,3-dimethoxy-1,3-dimethylurea, N,N'-diisopropyl-O-methylisourea, O,N,N'-triisopropyl Isourea, O-tert-butyl-N,N'-diisopropylisourea, O-ethyl-N,N'-diisopropylisourea, O-benzyl-N,N'-di Urea-based solvents such as isopropyl isourea; propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, ethylene two Alcohol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, 1,3-butanediol-3-monomethyl ether and other ether solvents; propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butanediol acetate and other acetate solvents; tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol, Alcohol solvents such as butanediol and isopropanol; ketone solvents such as cyclopentanone, cyclohexanone, diacetone alcohol and 2-heptanone; lactones such as γ-butyrolactone (GBL) and γ-valerolactone Solvents; carbonate-based solvents such as ethylene carbonate and propylene carbonate; dimethyl sulfide (DMSO), cyclobutane and other sulfite-based solvents; methyl pyruvate, ethyl pyruvate, methyl-3-methoxy Ester solvents such as methyl propionate; aromatic hydrocarbon solvents such as symmetric trimethylbenzene, toluene and xylene. As a solvent, 1 type or a combination of 2 or more types of the above-mentioned specific examples can be used. Among these, the lactone-based solvent is preferred from the viewpoint of coating properties and drip prevention.

The solvent is preferably one or more selected from the group consisting of amide-based solvents and urea-based solvents and selected from the group consisting of acetate-based solvents and lactone-based solvents in the above-mentioned specific examples. More than one kind. Thereby, the dispersibility of alkali-soluble resin (A) can be improved.

When the solvent is 100 parts by mass, the total content of the amide-based solvent and the urea-based solvent in the solvent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 25 parts by mass or more. This can increase the polarity in the mixed solvent. Therefore, the dispersibility of alkali-soluble resin (A), such as polyamide resin, polybenzoxazole resin, and polyimide resin, can be improved.

When the photosensitive resin composition for permanent film formation of this embodiment contains a solvent, the addition amount of a solvent can be adjusted suitably according to the characteristics, such as viscosity, required for the photosensitive resin composition for permanent film formation. When the photosensitive resin composition for forming a permanent film is coated by the slit coating method, for example, the content of the solvent in the photosensitive resin composition relative to the whole photosensitive resin composition (including the solvent) is 0.0001% by mass (1ppm) or more and 1% by mass (10000ppm) or less.

The photosensitive resin composition for permanent film formation of this embodiment may further contain additives such as an adhesion assistant, a thermal crosslinking agent, a silane coupling agent, an antioxidant, a dissolution accelerator, a filler, and a sensitizer.

(Adhesive bonding agent) The photosensitive resin composition for permanent film formation of this embodiment may contain an adhesion auxiliary agent. As the adhesion assistant, specifically, a triazole compound, an aminosilane, or an imine compound can be used. Thereby, the affinity of the photosensitive resin composition for permanent film formation and metal members, such as Cu and Al, can be improved.

As the triazole compound, specifically, 4-amino-1,2,4-triazole, 4H-1,2,4-triazole-3-amine, 4-amino-3,5- Di-2-pyridyl-4H-1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-methyl-4H-1,2, 4-triazole-3-amine, 3,4-diamino-4H-1,2,4-triazole, 3,5-diamino-4H-1,2,4-triazole, 1,2 ,4-Triazole-3,4,5-triamine, 3-pyridyl-4H-1,2,4-triazole, 4H-1,2,4-triazole-3-methanamide (4H- 1,2,4-triazole-3-carboxamide), 3,5-diamino-4-methyl-1,2,4-triazole, 3-pyridyl-4-methyl-1,2,4 -Triazole, 4-methyl-1,2,4-triazole-3-carboxamide and other 1,2,4-triazoles. As the triazole compound, one of the above-mentioned specific examples can be used or two or more of them can be used in combination.

Specific examples of aminosilanes include the condensation product of cyclohexene-1,2-dicarboxylic anhydride and 3-aminopropyltriethoxysilane, 3,3',4,4'-diphenyl Condensate of ketone tetracarboxylic dianhydride and 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-( Aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) 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) Group) propyl] ethylenediamine, N,N'-bis[3-(trimethoxysilyl)propyl]diaminopropane, N,N'-bis[3-(trimethoxysilyl)propane Base] diaminohexane, N,N'-bis[3-(trimethoxysilyl)propyl]diethylenetriamine, etc. As the aminosilane, one type or a combination of two or more types of the above-mentioned specific examples can be used.

As the imine compound, the compounds exemplified below can be mentioned. These can be used 1 type or in combination of 2 or more types.

For example, with respect to 100 parts by mass of the alkali-soluble resin (A), the lower limit of the content of the adhesion assistant in the photosensitive resin composition for permanent film formation is preferably 0.1 part by mass or more, more preferably 1.0 part by mass or more, and more It is preferably 2.0 parts by mass or more, and more preferably 3.0 parts by mass or more.

Also, for example, the upper limit of the content of the adhesion assistant in the photosensitive resin composition for permanent film formation is preferably 10 parts by mass or less, and more preferably 7 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A). More preferably, it is 5 parts by mass or less. When the content of the adhesion assistant is within the above numerical range, the adhesion assistant can be appropriately dispersed in the photosensitive resin composition for permanent film formation, and the adhesion of the photosensitive resin composition for permanent film formation to the adherend can be improved. Tight relay. This is preferable in terms of being able to prevent foreign matter from being mixed between the resin film and the adherend of the resin film.

(Silane coupling agent) The photosensitive resin composition for permanent film formation of this embodiment may contain a silane coupling agent. Examples of the silane coupling agent include those other than the aminosilane exemplified as the adhesion aid. As the silane coupling agent, specifically, vinyl silanes such as vinyl trimethoxy silane and vinyl triethoxy silane; 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxy propyl methyl dimethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3- Silicone oxide such as glycidoxypropyl triethoxysilane; Styryl silane such as p-styryltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and other methyl groups Acrylic silane; 3-acryloxypropyltrimethoxysilane and other acrylic silanes; triisocyanate silane; alkyl silane; 3-ureidopropyl trialkoxysilane and other ureido silanes; 3-mercaptopropane Mercapto silanes such as methyl dimethoxysilane and 3-mercaptopropyl trimethoxy silane; isocyanate silanes such as 3-isocyanate propyl triethoxy silane; titanium compounds; aluminum chelate compounds; aluminum/zirconium series Compound etc. As the silane coupling agent, one or two or more of the above-mentioned specific examples can be blended.

化合物、二羥甲基伸乙基脲等羥甲基脲化合物；二氰基苯胺、二氰基苯酚、氰基苯碸酸等氰化合物；1,4-伸苯基二異氰酸酯、3,3'-二甲基二苯甲烷-4,4'-二異氰酸酯等異氰酸酯化合物；乙二醇二環氧丙基醚、雙酚A二環氧丙基醚、異三聚氰酸三環氧丙酯、雙酚A型環氧樹脂、雙酚F型環氧樹脂、萘系環氧樹脂、聯苯型環氧樹脂、苯酚酚醛清漆樹脂型環氧樹脂等含環氧基之化合物；N,N'-1,3-伸苯基二順丁烯二醯亞胺、N,N'-亞甲基二順丁烯二醯亞胺等順丁烯二醯亞胺化合物等。作為熱交聯劑，能夠使用上述具體例中的1種或組合2種以上來使用。(Thermal crosslinking agent) The photosensitive resin composition for permanent film formation of this embodiment may contain a thermal crosslinking agent that can react with the alkali-soluble resin (A) by heat. Thereby, regarding the cured product obtained by post-baking the photosensitive resin composition for forming a permanent film, mechanical properties such as tensile elongation at break can be improved. Moreover, it is also advantageous from the viewpoint that the sensitivity of the resin film formed from the photosensitive resin composition for permanent film formation can be improved. As the thermal crosslinking agent, specifically, 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol (p-xylylene alcohol), 1,3,5-benzene Trimethanol, 4,4-biphenyldimethanol, 2,6-pyridine dimethanol, 2,6-bis(hydroxymethyl)-p-cresol, 4,4'-methylenebis(2,6-di Alkoxymethyl phenol) and other hydroxymethyl compounds; phenols such as phloroglucide; 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 Benzene, methyl 2,6-naphthalenedicarboxylate, 4,4'-methylenebis(2,6-dimethoxymethylphenol) and other compounds with alkoxymethyl groups; with hexamethylol Melamine, hexabutanol and melamine are represented by methylol melamine compounds; alkoxy melamine compounds such as hexamethoxy melamine; alkoxy methyl acetylene urea compounds such as tetramethoxymethyl acetylene carbamide; methylol benzoguanidine

Compounds, methylol urea compounds such as dimethylolethylene urea; cyano compounds such as dicyanoaniline, dicyanophenol, cyanobenzene acid; 1,4-phenylene diisocyanate, 3,3'-Dimethyldiphenylmethane-4,4'-diisocyanate and other isocyanate compounds; ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, triglycidyl isocyanurate, Epoxy-containing compounds such as bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, phenol novolak resin epoxy resin, etc.; N,N'- Maleic imide compounds such as 1,3-phenylene dimaleimide and N,N'-methylene dimaleimide, etc. As a thermal crosslinking agent, 1 type or a combination of 2 or more types of the above-mentioned specific examples can be used.

The lower limit of the content of the thermal crosslinking agent in the photosensitive resin composition for permanent film formation relative to 100 parts by mass of the alkali-soluble resin (A) is, for example, preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and more It is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and particularly preferably 8 parts by mass or more.

In addition, the upper limit of the content of the thermal crosslinking agent in the photosensitive resin composition for permanent film formation relative to 100 parts by mass of the alkali-soluble resin (A) is, for example, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, It is more preferably 12 parts by mass or less, and still more preferably 10 parts by mass or less. Thereby, even in the case where the thermal crosslinking agent has a solvated functional group such as a phenolic hydroxyl group, it is possible to suppress a decrease in chemical resistance after post-baking.

(Antioxidants) The photosensitive resin composition for permanent film formation of this embodiment may contain antioxidant. As the antioxidant, one or more selected from phenol-based antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants can be used. The antioxidant can suppress oxidation of the resin film formed from the photosensitive resin composition for permanent film formation.

、2,2'-亞甲基雙（4-甲基-6-第三丁基-6-丁基苯酚）、2,2'-亞甲基雙（4-乙基-6-第三丁基苯酚）、雙〔3,3-雙（4-羥基-3-第三丁基苯基）丁酸〕二醇酯、4,4'-亞丁基雙（6-第三丁基-間甲酚）、2,2'-亞乙基雙（4,6-二-第三丁基苯酚）、2,2'-亞乙基雙（4-第二丁基-6-第三丁基苯酚）、1,1,3-三（2-甲基-4-羥基-5-第三丁基苯基）丁烷、雙〔2-第三丁基-4-甲基-6-（2-羥基-3-第三丁基-5-甲基苄基）苯基〕對苯二甲酸酯、1,3,5-三（2,6-二甲基-3-羥基-4-第三丁基苄基）異氰脲酸酯、1,3,5-三（3,5-二-第三丁基-4-羥基苄基）-2,4,6-三甲基苯、1,3,5-三〔（3,5-二-第三丁基-4-羥基苯基）丙醯氧基乙基〕異氰脲酸酯、四〔亞甲基-3-（3,5-二-第三丁基-4-羥基苯基）丙酸酯〕甲烷、2-第三丁基-4-甲基-6-（2-丙烯醯氧基-3-第三丁基-5-甲基苄基）苯酚、3,9-雙（1,1-二甲基-2-羥乙基）-2,4-8,10-四氧雜螺[5,5]十一烷-雙〔β-（3-第三丁基-4-羥基-5-甲基苯基）丙酸酯〕、三乙二醇雙〔β-（3-第三丁基-4-羥基-5-甲基苯基）丙酸酯〕、1,1'-雙（4-羥基苯基）環己烷、2,2'-亞甲基雙（4-甲基-6-第三丁基苯酚）、2,2'-亞甲基雙（4-乙基-6-第三丁基苯酚）、2,2'-亞甲基雙（6-（1-甲基環己基）-4-甲基苯酚）、4,4'-亞丁基雙（3-甲基-6-第三丁基苯酚）、3,9-雙（2-（3-第三丁基-4-羥基-5-甲基苯基丙醯氧基）1,1-二甲基乙基）-2,4,8,10-四氧雜螺（5,5）十一烷、4,4'-硫代雙（3-甲基-6-第三丁基苯酚）、4,4'-雙（3,5-二-第三丁基-4-羥基苄基）硫醚、4,4'-硫代雙（6-第三丁基-2-甲基苯酚）、2,5-二-第三丁基氫醌、2,5-二-第三戊基氫醌、2-第三丁基-6-（3-第三丁基-2-羥基-5-甲基苄基）-4-甲基苯基丙烯酸酯、2,4-二甲基-6-（1-甲基環己基、苯乙烯化苯酚、2,4-雙（（辛硫基）甲基）-5-甲基苯酚等。Examples of phenolic antioxidants include neopentylerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[ 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}2,4,8,10-tetraoxaspiro[ 5,5] Undecane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis[3-( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl -4-hydroxybenzyl)benzene, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-diphenyl -4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl) -4-hydroxybenzyl) phosphate, thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis(6 -Tertiary butyl-m-cresol), 2-octylthio-4,6-bis(3,5-di-tertiary butyl-4-hydroxyphenoxy)-symmetric three

, 2,2'-methylene bis(4-methyl-6-tertiary butyl-6-butylphenol), 2,2'-methylene bis(4-ethyl-6-tertiary butyl) Phenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylene bis(6-tert-butyl-m-methyl Phenol), 2,2'-ethylenebis(4,6-di-tertiary butylphenol), 2,2'-ethylenebis(4-secondbutyl-6-tertiary butylphenol) ), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2- Hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-third Butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1, 3,5-Tris[(3,5-Di-tert-butyl-4-hydroxyphenyl)propionoxyethyl]isocyanurate, tetrakis[methylene-3-(3,5- Di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6-(2-propenyloxy-3-tert-butyl-5- Methylbenzyl)phenol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4-8,10-tetraoxaspiro[5,5]undecane-bis [Β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methyl Phenyl)propionate], 1,1'-bis(4-hydroxyphenyl)cyclohexane, 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-ethyl-6-tertiary butylphenol), 2,2'-methylenebis(6-(1-methylcyclohexyl)-4-methylphenol ), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 3,9-bis(2-(3-tert-butyl-4-hydroxy-5-methylbenzene) Propyl propionyloxy) 1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, 4,4'-thiobis(3-methyl 6-tert-butylphenol), 4,4'-bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-thiobis(6-th Tributyl-2-methylphenol), 2,5-di-tertiary butyl hydroquinone, 2,5-di-tertiary pentyl hydroquinone, 2-tertiary butyl-6-(3-th Tributyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-dimethyl-6-(1-methylcyclohexyl, styrenated phenol, 2, 4-bis((octylthio)methyl)-5-methylphenol, etc.

Examples of phosphorus-based antioxidants include bis(2,6-di-tert-butyl-4-methylphenyl) neopentaerythritol diphosphite, tris(2,4-di-tert-butyl Phenyl phosphite), tetrakis (2,4-di-tertiary butyl-5-methylphenyl)-4,4'-biphenylene diphosphite, 3,5-di-tertiary Butyl-4-hydroxybenzyl phosphate-diethyl ester, bis-(2,6-diisopropylphenyl) neopentylerythritol diphosphite, 2,2-methylene bis(4,6 -Di-tertiary butyl phenyl) octyl phosphite, tris (mixed mono and di-nonyl phenyl phosphite), bis (2,4-di-tertiary butyl phenyl) neopentyl tetrakis Alcohol diphosphite, bis(2,6-di-tert-butyl-4-methoxycarbonylethyl-phenyl) neopentylerythritol diphosphite, bis(2,6-di-third Butyl-4-octadecyloxycarbonyl ethyl phenyl) neopentyl erythritol diphosphite, etc.

Examples of thioether antioxidants include dilauryl-3,3'-thiodipropionate, bis(2-methyl-4-(3-n-dodecyl)thiopropionyloxy )-5-tert-butylphenyl) sulfide, distearyl-3,3'-thiodipropionate, neopentylerythritol-tetrakis(3-lauryl)thiopropionate, etc.

(filler) The photosensitive resin composition for permanent film formation of this embodiment may contain a filler. As the filler, an appropriate filler can be selected based on the mechanical properties and thermal properties required for the resin film formed from the photosensitive resin composition for permanent film formation.

As a filler, an inorganic filler, an organic filler, etc. are mentioned specifically,. As the above-mentioned inorganic fillers, specifically, fused crushed silica, molten spherical silica, crystalline silica, secondary agglomerated silica, finely powdered silica and other silica; alumina, Silicon nitride, aluminum nitride, boron nitride, titanium oxide, silicon carbide, aluminum hydroxide, magnesium hydroxide, titanium dioxide and other metal compounds; talc; clay; mica; glass fiber, etc. As the inorganic filler, one type or a combination of two or more types of the above-mentioned specific examples can be used.

Specific examples of the above-mentioned organic filler include organopolysiloxane powder, polyethylene powder, and the like. As an organic filler, 1 type or a combination of 2 or more types in the said specific example can be used.

(Preparation of photosensitive resin composition for permanent film formation) The method for preparing the photosensitive resin composition for permanent film formation in this embodiment is not limited, and a known method can be used depending on the components contained in the photosensitive resin composition. For example, it can be prepared by mixing and dissolving the above-mentioned components in a solvent. Thereby, the photosensitive resin composition for permanent film formation as a varnish can be obtained.

In addition, in this embodiment, from the viewpoint of setting the contact angle with the metal material present on the substrate of the electronic device within a desired value, it is preferable to adjust the total amount of the photosensitive resin composition for permanent film formation. The steps are all carried out in a nitrogen environment. Thereby, it is possible to suppress the deterioration of the components in the photosensitive resin composition for forming a permanent film, which is reactive with air-containing components such as oxygen. Therefore, the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition can be improved.

(use) The photosensitive resin composition of this embodiment can be used to form a permanent film of a semiconductor device such as a panel-level package.

The above-mentioned permanent film is obtained by, for example, coating a photosensitive resin composition, followed by pre-baking, exposure, and development, and patterning in a desired shape, and then curing by post-baking. The hardened film composition. Permanent film can be used for buffer coating (protective film), interlayer film, dam material, etc. of electronic devices. Among them, the above-mentioned permanent film can be preferably used as a buffer coating film.

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

The thickness of the permanent film is not particularly limited, and is, for example, about 2 to 30 μm, preferably about 5 to 20 μm. Regarding the method of removing the solvent after coating the photosensitive resin composition, various methods (for example, heating, etc.) can be applied, but in the case of use in a panel-level package, in view of the relatively large area, it is preferably applied Dry under reduced pressure. 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). In addition, if drying under reduced pressure, it also has the advantage of reducing microbubbles that may be generated during coating.

In the case of pre-baking, the conditions are, for example, 70 to 160°C and about 5 seconds to 30 minutes. Regarding 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, electron beams, etc. can be used. It is preferably ultraviolet rays such as g-rays or i-rays. The exposure amount can be appropriately set according to the sensitivity of the photosensitive adhesive composition and the like, and as an example, it is about 30 to 3000 mJ/cm ² . Regarding exposure, usually, it is performed using an appropriate mask pattern or the like. Regarding development, various developers can be applied. Examples include alkali metal carbonates, alkali metal hydroxides, alkali developers such as tetramethylammonium hydroxide, dimethylformamide, N-methyl-2-pyrrolidone, and propylene glycol. Organic developers such as monomethyl ether acetate, propylene glycol monomethyl ether, and butyl acetate. Among them, an alkali developer is preferred, and an aqueous solution of tetramethylammonium hydroxide is particularly preferred. Examples of methods for supplying the developer include spraying, coating, dipping, and the like. From the viewpoint of processing large-area panels, spraying is preferred. The conditions (hardening conditions) of the post-baking are not particularly limited, and are, for example, 80 to 300°C for 30 to 300 minutes.

Next, an example of the electronic device 100 containing the photosensitive resin composition for forming a permanent film of this embodiment will be described. The electronic device 100 shown in FIG. 1 is, for example, a semiconductor chip. In this case, for example, the semiconductor package can be obtained by mounting the electronic device 100 on the wiring substrate via the bump 52. The electronic device 100 includes a semiconductor substrate provided with semiconductor elements such as a transistor, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. An interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided in the uppermost layer of the multilayer wiring layer. The uppermost layer wiring 34 is made of, for example, Al. In addition, a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34. An opening exposing the uppermost layer wiring 34 is provided in a part of the passivation film 32.

A rewiring layer 40 is provided on the passivation film 32. The rewiring layer 40 has an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and the rewiring 46. An opening for exposing the uppermost layer wiring 34 is formed in the insulating layer 42. The rewiring 46 is formed on the insulating layer 42 and in the opening provided on the insulating layer 42 and is electrically connected to the uppermost layer wiring 34. The insulating layer 44 is provided with an opening exposing a specific area of the redistribution 46. In the opening provided on the insulating layer 44, a bump 52 is formed, for example, through a UBM (Under Bump Metallurgy) layer 50. The electronic device 100 is connected to a wiring board or the like via bumps 52, for example.

In this embodiment, for example, one or more of the insulating layer 42 and the insulating layer 44 can be constituted by a cured film (permanent film) formed by curing the photosensitive resin composition for forming a permanent film. In this case, for example, by exposing a coating film formed of a photosensitive resin composition for forming a permanent film to ultraviolet rays and developing it to pattern it, it is heated and hardened to form the insulating layer 42 or Insulation layer 44. In other words, the cured film of the photosensitive resin composition for permanent film formation is formed by the following steps, and the cured film can be used as the insulating layer 42 or the insulating layer 44 constituting the electronic device 100. The above steps are: the coating film forming step, The photosensitive resin composition for forming a permanent film is coated to form a coating film; the exposure step is to expose the formed coating film; the development step is to develop the exposed coating film; and the heating step, after the development The remaining coating film is heated to harden the coating film and form a permanent film.

The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can be used. [Example]

Hereinafter, the present invention will be described based on Examples and Comparative Examples, but the present invention is not limited to these.

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

＜Alkali-soluble resin＞ According to the following procedure, alkali-soluble resin 1 which is a polyamide resin was prepared. Put 206.58g of diphenyl ether-4,4'-dicarboxylic acid represented by the following formula (DC2) into a four-neck glass separable flask equipped with a thermometer, a stirrer, a raw material input port, and a dry nitrogen introduction tube ( 0.800mol) and 1-hydroxy-1,2,3-benzotriazole•monohydrate 216.19g (1.600mol) to obtain a mixture of dicarboxylic acid derivatives 170.20g (0.346mol), 5-amine Tetrazole 4.01g (0.047mol), 4,4'-methylenebis(2-aminophenol) represented by the following formula (DA2) 45.22g (0.196mol) and represented by the following formula (DA3) Of 4,4'-methylenebis(2-amino-3,6-dimethylphenol) 56.24g (0.196mol). Then, 578.3 g of N-methyl-2-pyrrolidone was added to the separable flask, and each raw material component was dissolved. Next, an oil bath was used to react at 90°C for 5 hours. Next, 24.34g (0.141mol) of 4-ethynyl phthalic anhydride and 121.7g of N-methyl-2-pyrrolidone were added to the separable flask, and the reaction was carried out while stirring at 90°C for 2 hours After that, it was cooled to 23°C and the reaction was terminated.

The filtrate obtained by filtering the reaction mixture in the separable flask is poured into a solution of water/isopropanol = 7/4 (volume ratio). After that, the precipitate was filtered out and sufficiently washed with water, and thereafter, it was dispersed in NMP (N-methylpyrrolidone) without drying, thereby obtaining a solution of the target alkali-soluble resin 1. The weight average molecular weight Mw of the obtained alkali-soluble resin 1 was 18081.

＜Photosensitizer＞ The photosensitizer 1 was synthesized as a quinone diazide compound by the following procedure. Put 11.04g (0.026mol) of the compound represented by the following formula (P-1), 1,2-naphthoquinone-2 in a four-neck separable flask equipped with a thermometer, a mixer, a raw material input port, and a dry nitrogen inlet pipe -Diazide-5-sulfonyl chloride 18.81 g (0.070 mol) and 170 g of acetone were stirred and dissolved.

Next, while cooling the flask with a water bath to prevent the temperature of the reaction solution from becoming 35° C. or higher, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise. After reacting for 3 hours at room temperature in this state, 1.05 g (0.017 mol) of acetic acid was added, and the reaction was continued for 30 minutes. Next, after filtering the reaction mixture, the filtrate was poured into a mixed solution of water/acetic acid (990 mL/10 mL). Next, the precipitate was collected by filtration and washed sufficiently with water, and then dried under vacuum. Thereby, a photosensitizer 1 represented by the structure of the following formula (Q-1) was obtained

<Adhesion Aid> •Adhesion Aid 1: Silane coupling agent represented by the following formula (3)

In addition, the adhesion assistant 1 is obtained by synthesizing in the following manner. In a reaction vessel of appropriate size equipped with a stirrer and a cooling tube, dissolve cyclohexene-1,2-dicarboxylic anhydride (45.6g, 300mmol) in N-methyl-2-pyrrolidone (970g), and Use a constant temperature bath to adjust to 30°C. Next, 3-aminopropyltriethoxysilane (62 g, 280 mmol) was put into the dropping funnel, and it was added dropwise to the dissolving liquid over 60 minutes. After the dropping was completed, stirring was performed under the conditions of 30°C for 18 hours to obtain the silane coupling agent represented by the above formula (3). • Adhesion aid 2: Shin-Etsu Chemica. Co., Ltd., X12-5263-HP

＜Thermal crosslinking agent＞ • Thermal crosslinking agent 1: p-xylyl alcohol (manufactured by IHARANIKKEI CHEMICAL INDUSTRY CO., LTD., PXG)

＜Surface active agent＞ • Surfactant 1: Polyether modified polydimethylsiloxane (liquid polysiloxane compound with polyether group, manufactured by BYK Japan K.K., BYK-333) • Surfactant 2: Polyether modified polydimethylsiloxane (manufactured by BYK Japan K.K., BYK-349) • Surfactant 3: Polyester modified polydimethylsiloxane (manufactured by BYK Japan K.K., BYK-313) • Surfactant 4: Aralkyl modified polydimethylsiloxane (manufactured by BYK Japan K.K., BYK-323) • Surfactant 5: Fluorine-based surfactant (manufactured by 3M Japan Limited, FC4430)

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

(Preparation of photosensitive resin composition) The photosensitive resin compositions of Examples 1 to 12, Comparative Example 1 and Comparative Example 2 were prepared in the following manner. To the solvent shown in Table 1, each raw material component other than the solvent was added and stirred, and then filtered with a PTFE membrane filter with a pore size of 0.2 μm, thereby obtaining each example and each comparative example The varnish of the photosensitive resin composition. The amount of the solvent is adjusted so that the solid content concentration in each composition is 10-40% by mass and the viscosity is about 50-2000 mPa•s. In addition, the process of preparing the varnish of the photosensitive resin composition of each Example and each comparative example was performed in a nitrogen atmosphere.

(Contact angle) About the photosensitive resin composition for permanent film formation of each Example and a comparative example, the contact angle with a sputtered copper substrate was measured.

In addition, as the sputtered copper substrate, one produced by the following procedure was used. (1) A titanium substrate was prepared. (2) A copper thin film with a thickness of 0.3 μm was formed on the above-mentioned substrate by sputtering.

As the specific order of contact angle measurement, first, for the composition of each example and comparative example, a mixed solvent containing tetramethylurea (TMU) and gamma-butyrolactone (GBL) (mixing ratio 3:7) The viscosity was adjusted so that after rotating for 300 seconds at a rotation frequency of 100 rpm and a temperature of 25°C, the viscosity measured with the E-type viscometer became 50 mPa•s. Next, 2 μl of the varnish of the above-mentioned photosensitive resin composition for permanent film formation with viscosity adjustment was dropped on each substrate at a temperature of 25° C., and the contact angle after 10 seconds was evaluated by the drop method. In addition, the measurement was performed using a contact angle meter (manufactured by Kyowa Interface Science, Inc, DROPMASTER-501). In this way, the contact angle (θ _Cu ) with the sputtered copper substrate was evaluated. The evaluation results are shown in Table 1 below. In addition, the unit is "°". The ratio (%) of the contact angle θ _Cu of each Example and Comparative Example 2 to the contact angle θ _Cu of Comparative Example 1 was calculated and described in Table 1. [Table 1] product name Comparative example 1 Comparative example 2 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Composition Alkali-soluble resin Alkali-soluble resin 1 - [Mass parts] 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Photosensitizer Photosensitizer 1 - 12 12 12 12 12 12 12 12 12 12 12 12 12 12 Surfactant Surfactant 1 (polyether modified polydimethylsiloxane) BYK-333 [ppm] - - 500 5000 20000 - - - - - - - - - Surfactant 2 (polyether modified polydimethylsiloxane) BYK-349 - - - - - 500 5000 20000 - - - - - - Surfactant 3 (polyester modified polydimethylsiloxane) BYK-313 - - - - - - - - 500 5000 20000 - - - Surfactant 4 (aralkyl modified polydimethylsiloxane) BYK-323 - - - - - - - - - - - 500 5000 20000 Surfactant 5 (Fluorine-based surfactant) FC-4430 50 - - - - - - - - - - - - - Adhesive agent Adhesive agent 1 - [Mass parts] 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Adhesion aid 2 X12-5263-HP 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Thermal crosslinking agent Thermal crosslinking agent 1 PXG 8 8 8 8 8 8 8 8 8 8 8 8 8 8 Solvent Solvent 1 - 158 158 158 158 158 158 158 158 158 158 158 158 158 158 Solvent 2 - 368 368 368 368 368 368 368 368 368 368 368 368 368 368 Evaluation Contact angle θ _Cu [°] 59.6 65.1 50 44.2 40.9 56 48.3 42.2 50.5 31.1 30.1 57 48.2 42.9 Ratio of θ _Cu relative to Comparative Example 1 [%] 100 109 84 74 69 94 81 71 85 52 51 96 81 72

As shown in Table 1, it was confirmed that in the photosensitive resin composition for permanent film formation of Examples 1 to 12, the contact angle with the sputtered copper substrate was lower than that of Comparative Example 1. Therefore, it can be said that the photosensitive resin composition for permanent film formation of Examples 1 to 12 has improved wettability to metals compared with Comparative Example 1.

This application claims priority based on Japanese application Japanese Patent Application No. 2018-170030 filed on September 11, 2018, and uses all the contents disclosed here.

30: Interlayer insulating film 32: Passivation film 34: The uppermost wiring 40: Redistribution layer 42: Insulation layer 44: insulating layer 46: rewiring 50: UBM layer 52: bump 100: electronic device

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

FIG. 1 is a diagram showing an example of an electronic device containing the photosensitive resin composition for forming a permanent film of the present embodiment.

30: Interlayer insulating film

32: Passivation film

34: The uppermost wiring

40: Redistribution layer

42: Insulation layer

44: insulating layer

46: rewiring

50: UBM layer

52: bump

100: electronic device

Claims (11)

A photosensitive resin composition for permanent film formation, comprising: an alkali-soluble resin (A); a photosensitizer (B); and a surfactant (C), the surfactant (C) comprising the following formula (1) Said organically modified dimethylsiloxane,

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 or more and 100 or less. For example, the photosensitive resin composition for permanent film formation in the first item of the patent application, wherein X in the above 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, 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. Group or unsaturated alkyl ether group with carbon number 1 or more and 6 or less, EO represents ethylene oxide group, PO represents propylene oxide group, o represents an integer greater than 1 and p represents an integer greater than 0. Regarding EO and PO The order can be random. For example, the photosensitive resin composition for permanent film formation of the second item of the scope of patent application, 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 % Above and below 99%. The photosensitive resin composition for permanent film formation according to the first item of the scope of patent application, wherein the ratio of m in the above formula (1) to the total of m and n is 0.5% or more and 60% or less. For example, the photosensitive resin composition for permanent film formation in the first item of the patent application, wherein the alkali-soluble resin (A) is selected from polyamide resin, polybenzoxazole resin, polyimide resin, and phenol resin One or more of the group consisting of hydroxystyrene resin and cyclic olefin resin. For example, the photosensitive resin composition for permanent film formation of the first item of the patent application, wherein the photosensitizer (B) contains a photoacid generator. For example, the photosensitive resin composition for permanent film formation in the first item of the scope of patent application is used for buffer coating. A cured film formed by curing the photosensitive resin composition for permanent film formation in any one of the first to seventh patent applications. An electronic device containing the cured film of item 8 in the scope of patent application. A method of manufacturing a cured film of a photosensitive resin composition for permanent film formation, the manufacturing method comprising: a coating film forming step, coating the photosensitive resin composition for permanent film formation to form a coating film, the permanent film formation The photosensitive resin composition contains an alkali-soluble resin (A), a photosensitizer (B), and a surfactant (C). The surfactant (C) contains an organic modified dimethyl silicon represented by the following formula (1) Oxyane; Exposure step to expose the formed coating film; Development step to develop the exposed coating film; and Heating step to heat the remaining coating film after development to harden the coating film , And form a permanent film,

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. A method of manufacturing an electronic device, which includes the method of manufacturing a cured film of a photosensitive resin composition for permanent film formation of the tenth item in the scope of patent application.

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