WO2019003913A1 - Photosensitive resin composition, resin film, and electronic device - Google Patents

Abstract

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

Description

Photosensitive resin composition, resin film and electronic device

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

Heretofore, in the field of photosensitive resin compositions, various techniques have been developed for the purpose of obtaining photosensitive resin compositions which can form a cured film which is not brittle even when cured at low temperature and is rich in heat resistance. ing. An example of this type of technology is the technology described in Patent Document 1.
According to Patent Document 1, it is described that a film obtained by applying a resin composition containing a compound having a phenolic hydroxyl group to a polyamide having a specific structure and curing at a temperature of 200 ° C. or less exhibits high elongation at break. It is done.

JP 2007-213032 A

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

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

According to the invention, an alkali soluble resin,
A photosensitizer,
A solvent, and
The photosensitive resin composition is provided, wherein the solvent comprises a urea compound or an amide compound having a non-cyclic structure.

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

Moreover, according to the present invention, an electronic device provided with the above-mentioned resin film is provided.

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

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

It is a sectional view showing an example of the electronic device concerning this embodiment.

Hereinafter, the present embodiment will be described using drawings as appropriate. In all the drawings, the same components are denoted by the same reference numerals and the description thereof will be omitted.

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

In recent years, with the miniaturization of electronic devices, metal members such as Al pads and copper circuits of electronic devices tend to be smaller. Here, when the metal member is small, the adhesion between the cured film of the photosensitive resin composition formed on the metal member and the metal member is low, and the cured film is peeled off. In the case where the cured film is peeled off, there is a problem that a leak current or the like is generated from the portion where the peeling occurs, and the electrical reliability of the electronic device is lowered.

The present inventors examined the raw material component of the photosensitive resin composition which can improve the adhesiveness of the cured film of the photosensitive resin composition after post-baking, and metals, such as Al pad and a copper circuit. As a result, it was found that adhesion can be improved by containing a urea compound or an amide compound having a non-cyclic structure as a solvent of the photosensitive resin composition.
Although the detailed mechanism which can improve adhesiveness is not certain, it is guessed as follows. As a mechanism for improving the adhesion, first, a lone electron pair included in the urea compound and the amide compound having a non-cyclic structure and a metal atom such as Al or Cu form a strong coordination bond. Conceivable. Thereby, it is considered that the components of the varnish of the photosensitive resin composition before drying are pulled by the coordination bond formed by the solvent and strongly coupled to the metal such as Al and Cu. Thereafter, the photosensitive resin composition is prebaked, exposed and developed to produce a resin film patterned in a desired shape, and then the resin film is cured by post-baking to produce a cured film. It is speculated that the molecular coordination of the component other than the solvent of the photosensitive resin composition can be frozen while the component other than the solvent of the photosensitive resin composition and the coordination in which the metal atom is strongly coupled. Therefore, it is considered that the adhesion between the post-baked cured film and a metal such as Al or Cu can be improved.
In addition, it is assumed that the mechanism which forms the strong coordination bond mentioned above differs between a urea compound and the amide compound of a non-cyclic structure. First, as a premise, in the conventional photosensitive resin composition, an amide compound having a cyclic structure such as N-methylpyrrolidone (NMP) has been used as a solvent. The urea compound has two or more nitrogen atoms having lone electron pairs in the molecular structure due to the urea bond. As a result, it is assumed that coordination bonds become stronger in proportion to the number of lone electron pairs. Therefore, when a urea compound is used, it is considered that a stronger coordination bond can be formed as compared with a compound used as a solvent of a conventional photosensitive resin composition. In addition, it is assumed that the amide compound having a non-cyclic structure is more likely to form a coordinate bond than the amide compound having a cyclic structure used in the conventional photosensitive resin composition. This is considered to be due to the fact that the amide compound having a non-cyclic structure is less restricted in molecular motion and has a higher degree of freedom in deformation of the molecular structure, as compared with the amide compound having a cyclic structure. Therefore, when an amide compound having an acyclic structure is used, it is considered that a stronger coordination bond can be formed as compared with a compound used as a solvent of a conventional photosensitive resin composition.
From the above, it is assumed that the photosensitive resin composition according to the present embodiment can improve the adhesion between the post-baked cured film and a metal such as Al or Cu by containing a specific compound as a solvent.

In addition to the above-mentioned adhesion improvement between the post-baked cured film and metals such as Al and Cu, the urea compound is more effective for the human body than the solvent used in the conventional photosensitive resin composition. It is also convenient from the viewpoint of less adverse effects. The amide compound having a cyclic structure such as N-methylpyrrolidone which has been used in the prior art has various adverse effects such as impaired reproductive function by being taken into the human body, and the production process of the photosensitive resin composition is It was necessary to devise. However, since the urea compound has a slight adverse effect on the human body, it is advantageous in that the device of the production process is not necessary.
Examples of urea compounds that have less adverse effects on the human body include tetramethyl urea.

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

(Alkali-soluble resin)
The alkali-soluble resin is not limited, and can be selected according to physical properties such as mechanical properties and optical properties required for the resin film. Specific examples of the alkali-soluble resin include polyamide resin, polybenzoxazole resin, phenol resin, hydroxystyrene resin and the like. Among the above specific examples, it is preferable to use, for example, a polyamide resin or a polybenzoxazole resin as the alkali-soluble resin. Thereby, it is considered that a strong interaction such as a hydrogen bond can be formed between the amide bond of the polyamide resin and the urea compound or the amide compound having a non-cyclic structure. Therefore, when making a photosensitive resin composition into a cured film, it is thought that molecular structure can be frozen by coordination which alkali-soluble resin and a metal molecule couple | bonded more strongly. In addition, as alkali-soluble resin, 1 type (s) or 2 or more types can be included among the said specific examples.

<Polyamide resin, polybenzoxazole resin>
As the polyamide resin, for example, an aromatic polyamide containing an aromatic ring in a structural unit of polyamide is preferably used, and a resin containing a structural unit represented by the following formula (PA1) is more preferable. As a result, the molecular chains of the polyamide resin are hydrogen-bonded via the amide bond, and further, the aromatic ring portion is densely aligned, so that the alkali-soluble resin and metal molecules are more strongly coordinated. , Can freeze the molecular structure. This coordination is more suitable for improving adhesion when the solvent contains tetramethylurea as a urea compound. Accordingly, it is preferable from the viewpoint of improving adhesion that a polyamide resin is contained as the alkali-soluble resin and tetramethylurea is contained as the urea compound in the solvent.
In the present embodiment, the aromatic ring indicates a benzene ring; a fused aromatic ring such as a naphthalene ring, an anthracene ring, or a pyrene ring; a heteroaromatic ring such as a pyridine ring or a pyrrole ring. The polyamide resin of the present embodiment preferably contains a benzene ring as an aromatic ring from the viewpoint of forming the above-described dense structure.

The polyamide resin containing the structural unit represented by the said Formula (PA1) is a precursor of polybenzoxazole resin. The polyamide resin containing the structural unit represented by the above formula (PA1) undergoes, for example, dehydration ring closure by heat treatment under conditions of 150 ° C. to 380 ° C. for 30 minutes to 50 hours, 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.
In the case where the alkali-soluble resin according to the present embodiment is a polyamide resin including a structural unit represented by the above formula (PA1), for example, the photosensitive resin composition is subjected to the above heat treatment to perform dehydration ring closure, and a polybenzoxazole resin It may be That is, the photosensitive resin composition subjected to the heat treatment contains a polybenzoxazole resin which is an alkali-soluble resin.
In addition, when the alkali-soluble resin is a polyamide resin including a structural unit represented by the above formula (PA1), after the resin film described later and the electronic device are manufactured, the above heat treatment is performed to perform dehydration ring closure. It may be an oxazole resin. When it is set as polybenzoxazole resin by carrying out dehydration ring-opening of the polyamide resin, tensile elongation at break and glass transition temperature can be enlarged. This is convenient from the viewpoint of improving the strength and heat resistance of the resin film and the electronic device.

<Method of producing polyamide resin>
The polyamide resin according to the present embodiment is, for example, polymerized as follows.
First, a polyamide is polymerized by polycondensing a diamine monomer and a dicarboxylic acid monomer in a polymerization step (S1). Next, the low molecular weight component is removed by the low molecular weight component removing step (S2) 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 polyamide is not limited, and specific examples thereof include melt polycondensation, acid chloride method, direct polycondensation and the like.
In place of the dicarboxylic acid monomer, a compound selected from the group consisting of tetracarboxylic acid dianhydride, trimellitic acid anhydride, dicarboxylic acid dichloride or activated ester type dicarboxylic acid may be used. As a method of obtaining active ester type dicarboxylic acid, specifically, a method of reacting 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. Each of the diamine monomer and the dicarboxylic acid monomer may be prepared singly or in combination of two or more.

<Diamine monomer>
The diamine monomer to be used for the polymerization is not limited. For example, it is preferable to use a diamine monomer containing an aromatic ring in the structure, and more preferable to use a diamine monomer containing a phenolic hydroxyl group in the structure. Here, as a diamine monomer containing a phenolic hydroxyl group in the structure, for example, a compound represented by the following general formula (DA1) is preferable. By producing a polyamide resin using such a diamine monomer as a raw material, the conformation of the polyamide resin can be controlled, and molecular chains of the polyamide resin can form a more dense structure. Therefore, the coordination in which the alkali-soluble resin and the metal molecule are more strongly bound can freeze the molecular structure and improve the adhesion.
In addition, for example, when using the diamine monomer represented by following General formula (DA1), a polyamide resin contains the structural unit represented by following General formula (PA2). That is, the polyamide resin according to the present embodiment preferably contains, for example, a structural unit represented by the following general formula (PA2).

(In the above general formula (DA1), R ⁴ 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, bromine atom 1 R ^{5 to} R ¹⁰ each independently represent hydrogen or an organic group having 1 to 30 carbon atoms.

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

R ⁴ in the general formulas (DA1) and (PA2) is selected from the group consisting of hydrogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, chlorine atom, fluorine atom and bromine atom A group formed by one or more atoms.
R ⁴ is a divalent group. Here, a bivalent group shows the thing of valence. That is, it indicates that there are two bonds where R ⁴ bonds to another atom.

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

Specifically, when R ⁴ in the general formulas (DA1) and (PA2) contains a carbon atom, an alkylene group, an arylene group, a halogen-substituted alkylene group, a halogen-substituted arylene group and the like can be mentioned as R ⁴ .
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 group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, nonylene group, decylene group, trimethylene group and tetramethylene group. And pentamethylene and hexamethylene groups. As the branched alkylene group, _{specifically, -C (CH 3) 2 -} , - CH (CH 3) -, - CH (CH 2 CH 3) -, - C (CH 3) (CH 2 Alkylmethylene groups such as CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2-, etc .; -CH (CH ₃ ) CH _2- , -CH ( _{CH 3) CH (CH 3)} -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH 3) 2 -CH 2 - alkyl, such as ethylene Groups and the like.
Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a group in which two or more arylene groups are bonded.
Specifically, as the halogen-substituted alkylene group and the halogen-substituted arylene group, those obtained by substituting the above-mentioned alkylene group and the hydrogen atom in the arylene group with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom are used. Can. Among these, one using a hydrogen atom substituted by a fluorine atom is preferable.

When R ⁴ in the general formulas (DA1) and (PA2) does not contain a carbon atom, specifically, a group consisting of an oxygen atom or a sulfur atom may, for example, be mentioned as R ⁴ .

R ^{5 to} R ¹⁰ in the general formulas (DA1) and (PA2) are each independently hydrogen or an organic group having 1 to 30 carbon atoms, for example, hydrogen or an organic group having 1 to 10 carbon atoms It is preferably hydrogen or an organic group having 1 to 5 carbon atoms, more preferably hydrogen or an organic group having 1 to 3 carbon atoms, and hydrogen or 1 to 2 carbon atoms. It is more preferable that it is an organic group of Thereby, the aromatic rings of the polyamide resin can be densely arranged. Therefore, the coordination in which the alkali-soluble resin and the metal molecule are more strongly bound can freeze the molecular structure and improve the adhesion.

Specific examples of the organic group having 1 to 30 carbon atoms of R ⁵ -R ¹⁰ in the general formulas (DA1) and (PA2) include methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group Alkyl groups such as isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl; alkenyls such as allyl, pentenyl and vinyl Groups: Alkynyl groups such as ethynyl groups; Alkylidene groups such as methylidene groups, ethylidene groups; Aryl groups such as tolyl groups, xylyl groups, phenyl groups, naphthyl groups, anthracenyl groups; Aralkyl groups such as benzyl groups or phenethyl groups; And cycloalkyl groups such as cyclopentyl, cyclohexyl and cyclooctyl Tolyl group, and alkaryl groups, such as xylyl group.

Specific examples of the diamine monomer represented by the above general formula (DA1) include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4′-methylenebis (2-amino- 3,6 dimethylphenol), 4,4'-methylenebis (2-aminophenol), 1,1-bis (3-amino 4-hydroxyphenyl) ethane, 3,3'-diamino-4,4'-dihydroxydiphenyl ether Etc. By using these diamine monomers, the aromatic rings of the polyamide resin can be arranged densely. Therefore, the coordination in which the alkali-soluble resin and the metal molecule are more strongly bound can freeze the molecular structure and improve the adhesion. In addition, as a diamine monomer, it can use combining 1 type, or 2 or more types among the said specific examples.
The structural formulas of these diamine monomers are shown below.

<Dicarboxylic acid monomer>
It is not limited as a dicarboxylic acid monomer used for superposition | polymerization, For example, it is preferable to use the dicarboxylic acid monomer which contains an aromatic ring in a structure.
As a dicarboxylic acid monomer containing an aromatic ring, for example, it is preferable to use one represented by the following general formula (DC1).
In addition, for example, when using the dicarboxylic acid monomer represented by following General formula (DC1), a polyamide resin contains the structural unit represented by following General formula (PA3). That is, it is preferable that the polyamide resin which concerns on this embodiment contains the structural unit represented, for example by the following general formula (DC1). Thereby, the aromatic rings of the polyamide resin can be densely arranged. Therefore, the coordination in which the alkali-soluble resin and the metal molecule are more strongly bound can freeze the molecular structure and improve the adhesion.

(In the above general formula (DC1), R ¹¹ 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, bromine atom 1 R ^{12 to} R ¹⁹ each independently represent hydrogen or an organic group having 1 to 30 carbon atoms.

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

R ¹¹ in the general formulas (DC1) and (PA3) is selected from the group consisting of hydrogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, chlorine atom, fluorine atom, bromine atom A group formed by one or more atoms.
R ¹¹ is a divalent group. Here, a bivalent group shows the thing of valence. That is, it indicates that there are two bonds which R ¹¹ bonds to other atoms.

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

When R ¹¹ in the above general formulas (DC1) and (PA3) contains a carbon atom, specifically, an alkylene group, an arylene group, a halogen-substituted alkylene group, a halogen-substituted arylene group and the like can be mentioned as R ¹¹ .
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 group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, nonylene group, decylene group, trimethylene group and tetramethylene group. And pentamethylene and hexamethylene groups. As the branched alkylene group, _{specifically, -C (CH 3) 2 -} , - CH (CH 3) -, - CH (CH 2 CH 3) -, - C (CH 3) (CH 2 Alkylmethylene groups such as CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2-, etc .; -CH (CH ₃ ) CH _2- , -CH ( _{CH 3) CH (CH 3)} -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH 3) 2 -CH 2 - alkyl, such as ethylene Groups and the like.
Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a group in which two or more arylene groups are bonded.
Specifically, as the halogen-substituted alkylene group and the halogen-substituted arylene group, those obtained by substituting the above-mentioned alkylene group and the hydrogen atom in the arylene group with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom are used. Can. Among these, one using a hydrogen atom substituted by a fluorine atom is preferable.

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

R ¹² -R ¹⁹ in the general formulas (DC1) and (PA3) are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and for example, hydrogen or an organic group having 1 to 10 carbon atoms It is preferably hydrogen or an organic group having 1 to 5 carbon atoms, more preferably hydrogen or an organic group having 1 to 3 carbon atoms, and still more preferably hydrogen.

Specific examples of the organic group having 1 to 30 carbon atoms of R ¹² -R ¹⁹ in the general formulas (DC1) and (PA3) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group Alkyl groups such as isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl; alkenyls such as allyl, pentenyl and vinyl Groups: Alkynyl groups such as ethynyl groups; Alkylidene groups such as methylidene groups, ethylidene groups; Aryl groups such as tolyl groups, xylyl groups, phenyl groups, naphthyl groups, anthracenyl groups; Aralkyl groups such as benzyl groups and phenethyl groups; Adamantyl groups And cycloalkyl such as cyclopentyl, cyclohexyl and cyclooctyl Tolyl group, and alkaryl groups, such as xylyl group.

As the dicarboxylic acid monomer, specifically, diphenylether 4,4'-dicarboxylic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid and the like can be used. Among the above-mentioned specific examples, it is preferable to use diphenyl ether 4,4'-dicarboxylic acid or isophthalic acid as the dicarboxylic acid monomer, 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 coordination in which the alkali-soluble resin and the metal molecule are more strongly bound can freeze the molecular structure and improve the adhesion.

In addition, it is preferable to modify the amino group present at the end of the polyamide resin simultaneously with the polymerization step (S1) or after the polymerization step (S1). The modification can be carried out, for example, by reacting a specific acid anhydride or a specific monocarboxylic acid with a diamine monomer or a polyamide resin. Therefore, in the polyamide resin according to the present embodiment, the terminal amino group is preferably modified with a specific acid anhydride or a specific monocarboxylic acid. In addition, the said specific acid anhydride and the said specific monocarboxylic acid have one or more types of functional groups which consist of a group which consists of an alkenyl group, an alkynyl group, and a hydroxyl group. Moreover, as said specific acid anhydride and a specific monocarboxylic acid, what contains a nitrogen atom, for example is preferable. Thereby, the adhesiveness of the photosensitive resin composition after post-baking and metals, such as Al and Cu, can be improved.
Specific examples of the above-mentioned 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 , Hetic anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride and the like. As a specific acid anhydride, it can be used combining 1 type, or 2 or more types among the said specific examples.
When the amino group present at the end of the polyamide resin is modified with a specific acid anhydride of ring shape, the specific acid anhydride of ring shape is ring-opened. Here, after modifying the polyamide resin, an imide ring may be formed by ring closure of a structural unit derived from a specific acid anhydride of ring shape. Examples of the method for ring closure include heat treatment.
Further, specific examples of the above-mentioned specific monocarboxylic acids include 5-norbornene-2-carboxylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid and the like. As said specific monocarboxylic acid, it can be used combining 1 type, or 2 or more types among the said specific examples.

In addition, the carboxyl group present at the end of the polyamide resin may be modified simultaneously with the polymerization step (S1) or after the polymerization step (S1). The modification can be carried out, for example, by reacting a specific nitrogen atom-containing heteroaromatic compound with a dicarboxylic acid monomer or a polyamide resin. Therefore, in the polyamide resin according to the present embodiment, the terminal carboxyl group is preferably modified by a specific nitrogen atom-containing heteroaromatic compound. The above-mentioned specific nitrogen atom-containing heteroaromatic compounds are 1- (5-1H-triazolyl) methylamino group, 3- (1H-pyrazolyl) amino group, 4- (1H-pyrazolyl) amino group, 5- (1H-pyrazolyl) amino group, 1- (3-1H-pyrazolyl) methylamino group, 1- (4-1H-pyrazolyl) methylamino group, 1- (5-1H-pyrazolyl) methylamino group, (1H- One or more functional groups consisting of tetrazol-5-yl) amino group, 1- (1H-tetrazol-5-yl) methyl-amino group and 3- (1H-tetrazol-5-yl) benz-amino group Having a group. Thereby, the number of lone electron pairs in the photosensitive resin composition can be increased. Therefore, after prebaking, the adhesiveness of the photosensitive resin composition after postbaking and metals, such as Al, can be improved.
Specific examples of the above-mentioned specific nitrogen atom-containing heteroaromatic compound include 5-aminotetrazole and the like.

(Low molecular weight component removal process (S2))
After the polymerization step (S1), a low molecular weight component removing step (S2) is performed to remove the low molecular weight component, and a polyamide resin containing a polyamide resin as a main component is obtained.
An organic layer containing a mixture of a low molecular weight component and a polyamide resin is concentrated by filtration or the like, and then redissolved in an organic solvent such as water / isopropanol. Thereby, a precipitate can be filtered off and the polyamide resin from which the low molecular weight component was removed can be obtained.

As a polyamide resin, what is obtained by condensing the diamine monomer represented by the said General formula (DA1) and the dicarboxylic acid monomer represented by the said General formula (DC1), for example is preferable. That is, as a polyamide resin, what is provided with the structural unit of said general formula (PA2) and (PA3) is preferable, and what has the structural unit of said general formula (PA2) and (PA3) alternately is more preferable.

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

The above-mentioned reaction product of a phenol compound and an aldehyde compound or the reaction product of a phenol compound and a dimethanol compound is not limited.
Specific examples of such phenolic compounds include cresols such as phenol, o-cresol, m-cresol, p-cresol, etc .; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2 , 6-xylenol, 3,4-xylenol, 3,5-xylenol and the like; x-lenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol and the like; isopropylphenol, butylphenol, p-tert- Alkylphenols such as butylphenol; Polyphenols such as resorcinol, catechol, hydroquinone, pyrogallol, phloroglucinol; and biphenyl type phenols such as 4,4'-biphenol. As a phenol compound, 1 type (s) or 2 or more types can be used among the said specific examples.

It will not be limited if it is a compound which has an aldehyde group as an aldehyde compound used for a reaction product of a phenol compound and an aldehyde compound mentioned above.
Specific examples of such aldehyde compounds 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.
As such a dimethanol compound, specifically, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4′-biphenyldimethanol, 3,4′-biphenyldimethanol, 3, 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., bis (alkoxymethyl) compounds, or 1,4-bis (chloromethyl) benzene, 1,3-bis (chloromethyl) Benzene, 1,4-bis (bromomethyl) benzene, 1,3-bis (bromomethyl) benzene, 4,4′-bis (chloromethyl) biphenyl, 3,4′-bis (chloromethyl) biphenyl, 3,3 ′ Bis (halgenoalkyl) compounds such as bis (chloromethyl) biphenyl, 4,4'-bis (bromomethyl) biphenyl, 3,4'-bis (bromomethyl) biphenyl or 3,3'-bis (bromomethyl) biphenyl, And biphenylaralkyl compounds such as 4,4'-bis (methoxymethyl) biphenyl and 4,4'-bis (methoxymethyl) biphenyl. As a dimethanol compound, 1 type (s) or 2 or more types can be used among the said specific examples.

<Hydroxystyrene resin>
The hydroxystyrene resin is not limited, and specifically, a polymerization reaction product or copolymer obtained by polymerizing or copolymerizing one or two 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 obtained by substituting a hydrogen atom of an aromatic ring of hydroxystyrene and styrene with a monovalent organic group. As a monovalent organic group which substitutes a hydrogen atom, For example, Alkyl groups, such as a methyl group, an ethyl group, n-propyl group; Alkenyl groups, such as an allyl group and a vinyl group; Alkynyl groups, such as an ethynyl group; And alkylidene groups such as ethylidene group; cycloalkyl groups such as cyclopropyl group; and heterocyclic groups such as 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 derivative be able to.
In addition, as a norbornene derivative, what substituted the hydrogen atom couple | bonded with norbornene frame | skeleton by the monovalent organic group is mentioned specifically ,. As a monovalent organic group which substitutes a hydrogen atom, For example, Alkyl groups, such as a methyl group, an ethyl group, n-propyl group; Alkenyl groups, such as an allyl group and a vinyl group; Alkynyl groups, such as an ethynyl group; And alkylidene groups such as ethylidene group; cycloalkyl groups such as cyclopropyl group; and heterocyclic groups such as epoxy group oxetanyl group.

The lower limit value of the content of the alkali-soluble resin in the photosensitive resin composition is preferably 30 parts by mass or more, for example, 40 parts by mass, when the total solid content of the photosensitive resin composition is 100 parts by mass. The above content is more preferable, 50 parts by mass or more is further preferable, 60 parts by mass or more is further preferable, and 70 parts by mass or more is particularly preferable. Thereby, the alkali-soluble resin in the photosensitive resin composition can preferably interact with the urea compound in the solvent or the amide compound having a non-cyclic structure. Therefore, the coordination in which the alkali-soluble resin and the metal molecule are more strongly bound can freeze the molecular structure and improve the adhesion.
The upper limit of the content of the alkali-soluble resin in the photosensitive resin composition is preferably 95 parts by mass or less, for example, based on 100 parts by mass of the total solid content of the photosensitive resin composition. It is more preferable that it is a mass part or less, and it is still more preferable that it is 85 mass parts or less.
In addition, in this embodiment, the total solid of the photosensitive resin composition shows the sum total of the component of the photosensitive resin composition except a solvent.

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

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

In each of the above diazoquinone compounds, Q is a structure represented by the following formula (a), the following formula (b) and the following formula (c), or a hydrogen atom. However, at least one of Q of each diazoquinone compound is a structure represented by the following formula (a), the following formula (b) and the following formula (c).
The Q of the diazoquinone 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.

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

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

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

Specific examples of the structure of the urea compound include a cyclic structure and a non-cyclic structure. Among the above specific examples, the structure of the urea compound is preferably a non-cyclic structure. Thereby, the adhesiveness of the hardened | cured material of the photosensitive resin composition, and metals, such as Al and Cu, can be improved. The reason is presumed as follows. It is assumed that the urea compound having an acyclic structure is more likely to form a coordinate bond than the urea compound having a cyclic structure. It is considered that this is because the urea compound having a non-cyclic structure has less restriction of molecular motion as compared with the urea compound having a cyclic structure, and furthermore, the freedom of deformation of the molecular structure is large. Therefore, when a urea compound having an acyclic structure is used, a strong coordination bond can be formed, and adhesion can be improved.

Specific examples of the urea compound include tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone, N, N-dimethylacetamide, tetrabutylurea, N, N′-dimethylpropyleneurea, 3-dimethoxy-1,3-dimethylurea, N, N'-diisopropyl-O-methylisourea, O, N, N'-triisopropylisourea, O-tert-butyl-N, N'-diisopropylisourea, Examples include O-ethyl-N, N'-diisopropylisourea, O-benzyl-N, N'-diisopropylisourea and the like. As a urea compound, it can be used combining 1 type, or 2 or more types among the said specific examples. As the urea compound, among the above specific examples, for example, tetramethylurea (TMU), tetrabutylurea, 1,3-dimethoxy-1,3-dimethylurea, N, N′-diisopropyl-O-methylisourea, O, N , N'-triisopropylisourea, O-tert-butyl-N, N'-diisopropylisourea, O-ethyl-N, N'-diisopropylisourea and O-benzyl-N, N'-diisopropylisourea It is preferable to use 1 type, or 2 or more types selected from the group which consists of, and it is more preferable to use tetramethyl urea (TMU). Thereby, a strong coordination bond can be formed and adhesion can be improved.

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

The photosensitive resin composition according to the present embodiment may contain, as a solvent, a solvent not having a nitrogen atom, in addition to the urea compound and the amide compound having a non-cyclic structure.
Specific examples of solvents that do not have a nitrogen atom include ether solvents, acetate solvents, alcohol solvents, ketone solvents, lactone solvents, carbonate solvents, sulfone solvents, ester solvents, aromatic hydrocarbons A system solvent etc. are mentioned. As a solvent which does not have a nitrogen atom, it is possible to use one or two or more in combination among the above specific examples.
Specific examples of the ether solvents include propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether And diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, 1,3-butylene glycol 3-monomethyl ether and the like.
Specific examples of the acetate solvent include propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate and the like.
Specific examples of the alcohol solvents include tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol, butanediol, isopropyl alcohol and the like.
Specific examples of the ketone solvent include cyclopentanone, cyclohexanone, diacetone alcohol and 2-heptanone.
Specific examples of the lactone solvent include γ-butyrolactone (GBL) and γ-valerolactone.
Specific examples of the carbonate-based solvent include ethylene carbonate and propylene carbonate.
Specific examples of the sulfone-based solvent include dimethylsulfoxide (DMSO), sulfolane and the like.
Specific examples of the ester solvents include methyl pyruvate, ethyl pyruvate, methyl 3-methoxy propionate and the like.
Specific examples of the aromatic hydrocarbon solvent include mesitylene, toluene, xylene and the like.

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

The photosensitive resin composition according to the present embodiment is further added with additives such as an adhesion assistant, a silane coupling agent, a thermal crosslinking agent, a surfactant, an antioxidant, a dissolution accelerator, a filler, a sensitizer and the like. You may
The details of typical additive components are described below.

(Adhesive aid)
The photosensitive resin composition according to the present embodiment may further contain a cohesion aid. Specifically as a close_contact | adherence adjuvant, a triazole compound, an aminosilane, or an imide compound can be used. This can further increase the number of lone electron pairs derived from nitrogen atoms. Therefore, inclusions other than the solvent of the photosensitive resin composition can be coordinated with the metal atom, and adhesion can be further improved. As a close_contact | adherence adjuvant, you may use either a triazole compound, an aminosilane, or an imide compound, and you may use together 2 or more types among a triazole compound, an aminosilane, and an imide compound.

Specific examples of the triazole compound include 4-amino-1,2,4-triazole, 4H-1,2,4-triazole-3-amine, 4-amino-3,5-di-2-pyridyl- 4H-1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-methyl-4H-1,2,4-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- It includes 1,2,4-triazole, such as chill-1,2,4-triazole-3-carboxamide. As a triazole compound, it can be used combining 1 type, or 2 or more types among the said specific examples.

Specific examples of the aminosilane include condensates of cyclohexene-1,2-dicarboxylic acid anhydride and 3-aminopropyltriethoxysilane, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride and -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- (trimethoxy) Silyl) 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] diethylene triamine etc. may be mentionedAs the aminosilane, one or more of the above specific examples may be used in combination.

Specific examples of the imide compound include the compounds exemplified below. These can be used 1 type or in combination of 2 or more types.

The lower limit value of the content of the adhesion aiding agent in the photosensitive resin composition is, for example, preferably 0.1 parts by mass or more and 1.0 parts by mass or more with respect to 100 parts by mass of the alkali-soluble resin. The content is more preferably 2.0 parts by mass or more, further preferably 3.0 parts by mass or more. Thereby, the adhesion can be sufficiently enhanced.
In addition, the upper limit value of the content of the adhesion aiding agent in the photosensitive resin composition is, for example, preferably 10 parts by mass or less and 7 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin. It is more preferable that the amount is 5 parts by mass or less. By this, the adhesion aiding agent is suitably dispersed in the photosensitive resin composition, and the adhesion can be improved.

(Silane coupling agent)
The photosensitive resin composition according to the present embodiment may further include a silane coupling agent. As a silane coupling agent, things other than the aminosilane illustrated as an adhesion | attachment adjuvant are mentioned.
Specific examples of the silane coupling agent having a structure different from that of the above-mentioned silane compound include vinyltrimethoxysilane, vinylsilane such as vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3 -Epoxysilanes such as glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; p-styryltrimethoxysilane Styrylsilanes such as: 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and the like Crylsilanes; acrylsilanes such as 3-acryloxypropyltrimethoxysilane; isocyanurate silanes; alkylsilanes; ureidosilanes such as 3-ureidopropyltrialkoxysilane; 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Mercaptosilanes; 3-isocyanate such as isocyanatopropyltriethoxysilane; titanium compounds; aluminum chelates; aluminum / zirconium compounds and the like. As a silane coupling agent, 1 type (s) or 2 or more types can be mix | blended among the said specific examples.

(Heat crosslinker)
The photosensitive resin composition according to the present embodiment may contain a thermal crosslinking agent that can react with the alkali-soluble resin by heat. Thereby, mechanical properties, such as tensile breaking elongation, can be improved about the hardened | cured material which post-baked the photosensitive resin composition. Moreover, it is convenient also from a viewpoint which can improve the sensitivity of the resin film formed of the photosensitive resin composition.
Specific examples of the thermal crosslinking agent include 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol (p-xylene glycol), 1,3,5-benzenetrimethanol, Methylol groups such as 4,4-biphenyldimethanol, 2,6-pyridinedimethanol, 2,6-bis (hydroxymethyl) -p-cresol, 4,4'-methylenebis (2,6-dialkoxymethylphenol) Compounds having a phenol; 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, methyl 2,6-naphthalenedicarboxylate Compounds having an alkoxymethyl group such as 4,4'-methylenebis (2,6-dimethoxymethylphenol); methylolmelamine compounds represented by hexamethylolmelamine, hexabutanolmelamine etc .; alkoxymelamine compounds such as hexamethoxymelamine; Alkoxymethyl glycoluril compounds such as tetramethoxymethyl glycoluril; methylol benzoguanamine compounds, methylol urea compounds such as dimethylol ethylene urea; cyano compounds such as dicyanoaniline, dicyanophenol, cyanophenyl sulfonic acid; 1,4-phenylene diisocyanate And isocyanate 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 novolac resin type epoxy resin; N, N ' And maleimide compounds such as 1,3-phenylenedimaleimide and N, N'-methylenedimaleimide. As a thermal crosslinking agent, it can be used combining 1 type, or 2 or more types among the said specific examples.

The upper limit of the content of the thermal crosslinking agent in the photosensitive resin composition is, for example, preferably 20 parts by mass or less, and more preferably 15 parts by mass or less, with respect to 100 parts by mass of the alkali-soluble resin. The content is more preferably 12 parts by mass or less, further preferably 10 parts by mass or less. Thereby, even when the thermal crosslinking agent has a functional group that is solvated such as phenolic hydroxyl group, it is possible to suppress the decrease in chemical resistance after post-baking.
In addition, the lower limit value of the content of the thermal crosslinking agent in the photosensitive resin composition is, for example, preferably 0.1 parts by mass or more, and 1 part by mass or more with respect to 100 parts by mass of the alkali-soluble resin. Is more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and particularly preferably 8 parts by mass or more.

(Surfactant)
The photosensitive resin composition according to the present embodiment may further contain a surfactant.
The surfactant is not particularly limited. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc .; polyoxyethylene octyl phenyl ether, polyoxyethylene Nonionic surfactants such as polyoxyethylene aryl ethers such as nonyl phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate, polyoxyethylene distearate; F top EF 301, F top EF 303, F top EF 352 (Made by Shin Akita Kasei), Megafuck F171, Megafuck F172, Megafuck F173, Megafuck F177, Megafuck F444, Megafuck F 70, Megafuck F471, Megafuck F475, Megafuck F482, Megafuck F477 (manufactured by DIC), Florard FC-430, Florard FC-431, Nobec FC 4430, Nobec FC 442 (made by 3M Japan), Surfron S-381, SURFLON S-382, SURFLON S-383, SURFLON S-393, SURFLON SC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106, Commercially available fluorochemical surfactants such as organosiloxane copolymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth) acrylic acid copolymer polyflow No. 4; 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

Among these, it is preferable to use a fluorine-based surfactant having a perfluoroalkyl group. As the fluorosurfactant having a perfluoroalkyl group, among the above specific examples, Megafuck F171, Megafuck F173, Megafuck F444, Megafuck F470, Megafuck F471, Megafuck F475, Megafuck F482, Megafuck F477 (manufactured by DIC), Surfron S-381, Surfron S-383, Surfron S-393 (manufactured by AGC Seimi Chemical), Nobec FC 4430 and Nobec FC 442 (manufactured by 3M Japan) It is preferable to use

Moreover, as surfactant, silicone type surfactant (for example, polyether modified | denatured dimethylsiloxane etc.) can also be used preferably. Specific examples of silicone surfactants include SH series, SD series and ST series of Toray Dow Corning, BYK series of BIC Chemie Japan, KP series of Shin-Etsu Chemical Co., Ltd. Registered trademark), TSF series of Toshiba Silicone Co., Ltd., and the like.

The upper limit value of the content of the surfactant in the photosensitive resin composition is preferably 1% by mass (10000 ppm) or less with respect to the entire photosensitive resin composition (including the solvent), 0.5 mass It is more preferable that it is less than 5% (5000 ppm) and still more preferably less than or equal to 0.1% by mass (1000 ppm).
The lower limit value of the content of the surfactant in the photosensitive resin composition is not particularly limited, but from the viewpoint of sufficiently obtaining the effect by the surfactant, for example, the entire photosensitive resin composition (solvent And 0.001% by mass (10 ppm) or more.
By appropriately adjusting the amount of surfactant, it is possible to improve the coatability, the uniformity of the coating film, etc. while maintaining the other performance.

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

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

(Preparation of photosensitive resin composition)
The method for preparing the photosensitive resin composition in the present embodiment is not limited, and known methods can be used depending on the components contained in the photosensitive resin composition.
For example, the above components can be prepared by mixing and dissolving in a solvent. Thereby, the photosensitive resin composition made into the varnish can be obtained.

(Photosensitive resin composition)
In the photosensitive resin composition according to the present embodiment, the varnish of the photosensitive resin composition is applied to a surface provided with a metal such as Al and Cu, and then prebaked to form a resin film by drying. Next, the resin film is patterned into a desired shape by exposure and development, and then the resin film is post-baked to be cured to form a cured film.
In addition, when producing the said permanent film, it can be set as heat processing for 30 seconds or more and 1 hour or less, for example as temperature of 90 degreeC or more and 130 degrees C or less as conditions of prebaking. Further, as the post-baking conditions, for example, heat treatment can be performed at a temperature of 150 ° C. to 350 ° C. for 30 minutes to 10 hours.

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

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

The photosensitive resin composition according to the present embodiment is adjusted in viscosity so that the viscosity measured after rotation for 300 seconds at a rotational frequency of 100 rpm and a temperature of 25 ° C. using an E-type viscometer is 50 mPa · s, and the temperature is 25 ° C. The upper limit of the contact angle after 10 seconds of dropping 2 ml to the aluminum foil is, for example, preferably 14 ° or less, more preferably 13 ° or less, and still more preferably 12 ° or less. It is more preferable that the angle is not more than °. When the contact angle is equal to or less than the above numerical range, the compatibility between the varnish of the photosensitive resin composition and the metal such as Al is improved, and the photosensitive resin composition is formed in the fine gaps formed on the metal surface such as Al. It can invade. Thereby, when the photosensitive resin composition is a cured film, an anchor effect is developed between the cured film and a metal such as Al, and the adhesion can be improved.
The viscosity was adjusted by an E-type viscometer so that the viscosity measured after rotation for 300 seconds at a rotational frequency of 100 rpm was 300 mPa · s, and 2 ml was dropped on the aluminum foil at a temperature of 25 ° C for 10 seconds. The lower limit value of the subsequent contact angle may be, for example, 1 ° or more, or 5 ° or more.

It supplements about viscosity adjustment in the case of the measurement of the above-mentioned contact angle.
About the photosensitive resin composition whose viscosity in the measurement method by said E-type viscometer is larger than 50 mPa * s, a viscosity is adjusted to 50 mPa * s using the same solvent as the solvent which the said photosensitive resin composition contains And measure the contact angle. When the photosensitive resin composition contains a mixed solvent, the viscosity is adjusted by the mixed solvent.
Moreover, about the photosensitive resin composition whose viscosity by the said measuring method is smaller than 50 mPa * s, the contact angle in 50 mPa * s-equivalent can be calculated | required as follows.
For example, it is assumed that there is a photosensitive resin composition having a viscosity of 40 mPa · s according to the above measurement method. This is further diluted using the same solvent as the solvent contained in the photosensitive resin composition to prepare a photosensitive resin composition having a viscosity of 30, 20, 10 mPa · s, etc. Then, the relationship between the viscosity and the contact angle of these photosensitive resin compositions having a viscosity of 10 to 40 mPa · s is plotted, and a straight line is drawn by the least squares method to extrapolate the contact angle at a viscosity of 50 mPa · s. . In addition, a plot is performed by at least two points, preferably three or four points.
By the way, as a finding of the present inventors, in the low viscosity region of 50 mPa · s or less, for example, 30 mPa · s and 50 mPa · s, there is almost no difference in the contact angle.

As a result of examining the method in which the present inventor makes the contact angle to copper foil and aluminum foil within the above-mentioned numerical range about the varnish of the photosensitive resin composition, the urea compound contained in the solvent and the amide compound of non-cyclic structure It has been found that it is important to properly control the structure, and the content of the urea compound and the noncyclic compound amide compound in the solvent.
As a structure of the urea compound contained in the solvent and the amide compound of a non-cyclic structure, one having more resonance structure is preferable. Specifically, in the urea bond of a urea compound or the amide bond of an amide compound having an acyclic structure, one having a large number of resonance structures formed by a lone electron pair of nitrogen atom and a ketone site CCO is preferable . The number of resonance structures of the urea compound and the amide compound having a non-cyclic structure is, for example, preferably 2 or more, and more preferably 3 or more. As a result, the electron cloud of the urea compound and the amide compound having a non-cyclic structure spreads, and the electronic state is stabilized. Therefore, it is considered that the surface free energy of the urea compound and the amide compound having a non-cyclic structure can be reduced, and the wettability to Cu can be improved. An example is given as the number of resonant structures. For example, the number of resonance structures of a urea compound such as tetramethylurea (TMU) is three.
The content of the urea compound and the amide compound having a non-cyclic structure in the solvent is preferably 30 parts by mass or more, for example, 100 parts by mass of the solvent, although it depends on the above-mentioned structure. It is more preferable to set it as the mass part or more, further preferable to set it as the 70 mass part or more, and it is further preferable to set it as the 100 mass part. Thereby, the electronic state in a solvent can be stabilized, and a contact angle can be made into the said numerical range.

(Use)
The photosensitive resin composition of the present embodiment is used to form a resin film for an electronic device such as a permanent film or a resist. Among these, from the viewpoint of achieving well-balanced development of adhesion of the photosensitive resin composition and Al pad after pre-baking and generation of residues of the photosensitive resin composition during development, photosensitive resin after post-baking From the viewpoint of improving the adhesion between the cured film of the composition and the metal, as well as from the viewpoint of improving the chemical resistance of the photosensitive resin composition after post-baking, it is preferable to be used for applications using a permanent film .
In the present embodiment, the resin film is a dried film or a cured film of the photosensitive resin composition. That is, the resin film according to the present embodiment is formed by drying or curing the photosensitive resin composition.

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

The above-mentioned resist is applied to an object to be masked by the resist, for example, by a method such as spin coating, roll coating, flow coating, dip coating, spray coating or doctor coating, and the photosensitive resin composition is applied. The resin film is obtained by removing the solvent from

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

Electronic device 100 is, for example, a semiconductor chip. In this case, a semiconductor package can be obtained, for example, by mounting the electronic device 100 on the wiring substrate via the bumps 52. The electronic device 100 includes a semiconductor substrate provided with a semiconductor element such as a transistor, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. An interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided on the uppermost layer of the multilayer wiring layers. Top layer interconnection 34 is made of, for example, aluminum Al. Further, a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34. An opening for 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 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and on the rewiring 46; Have. In the insulating layer 42, an opening connected to the uppermost layer wiring 34 is formed. The rewiring 46 is formed in the opening provided on the insulating layer 42 and in the insulating layer 42, and is connected to the uppermost layer wiring 34. The insulating layer 44 is provided with an opening connected to the rewiring 46.

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

Note that the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like as long as the object of the present invention can be achieved are included in the present invention.

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

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

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

(Alkali-soluble resin 1)
Alkali-soluble resin 1 which is a polyamide resin was synthesized by the following procedure.
In a four-neck glass separable flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet, 206.58 g of diphenyl ether-4,4'-dicarboxylic acid represented by the following formula (DC2) A mixture of dicarboxylic acid derivatives obtained by reacting (0.800 mol) with 216.19 g (1.600 mol) of 1-hydroxy-1,2,3-benzotriazole monohydrate (170.20 g (0 .346 mol), 4.01 g (0.047 mol) of 5-aminotetrazole, and 45.22 g (0.196 mol) of 4,4'-methylenebis (2-aminophenol) represented by the following formula (DA2): 56.24 g (0.196 mol) of 4,4′-methylenebis (2-amino-3,6 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, it was made to react 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 are added to the separable flask and reacted with stirring at 90 ° C. for 2 hours. After the reaction, the reaction was terminated by cooling to 23.degree.
The filtrate obtained by filtering the reaction mixture in the separable flask was poured into a solution of water / isopropanol = 7/4 (volume ratio). Thereafter, the precipitate was separated by filtration, sufficiently washed with water, and dried under vacuum to obtain an alkali-soluble resin 1. The weight average molecular weight Mw of the obtained alkali soluble resin 1 was 18081.

<Photosensitizer>
Next, details of the photosensitizer used in each of the examples and the comparative examples will be described.

(Photosensitizer 1)
Photosensitizer 1 which is a diazoquinone compound was synthesized by the following procedure.
11.04 g (0.026 mol) of phenol represented by the following formula (P-1) in a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet pipe; 18.81 g (0.070 mol) of 2-naphthoquinone-2-diazide-5-sulfonyl chloride and 170 g of acetone were added and stirred for dissolution.
Then, while cooling the flask with a water bath so that the temperature of the reaction solution does not exceed 35 ° C., a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly dropped. The reaction was allowed to proceed for 3 hours at room temperature, 1.05 g (0.017 mol) of acetic acid was added, and the reaction was allowed to proceed for another 30 minutes. The reaction mixture was then filtered, and the filtrate was poured into a mixed solution of water / acetic acid (990 mL / 10 mL). The precipitate was then collected by filtration, washed thoroughly with water and then dried under vacuum. Thus, Photosensitizer 1 represented by the structure of the following formula (Q-1) was obtained.

<Solvent>
The following solvents 1-3 were used as solvents.
Solvent 1: tetramethyl urea (TMU), which is a linear urea compound
Solvent 2: γ-butyrolactone (GBL)
Solvent 3: N-methyl pyrrolidone (NMP) which is an amide compound in a cyclic form

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

The details of the method for synthesizing adhesion assistant 2 which is a condensate of carboxylic acid anhydride and 3-aminopropyltriethoxysilane will be described below.
In an appropriately 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), and a thermostatic bath Adjusted to 30.degree. Subsequently, 3-aminopropyltriethoxysilane (62 g, 280 mmol) was charged into the dropping funnel and added dropwise to the solution over 60 minutes. After completion of the dropwise addition, the mixture was stirred under conditions of 30 ° C. for 18 hours to obtain adhesion assistant 2 represented by the following formula (S2).

<Thermal crosslinker>
The following thermal crosslinking agent 1 was used as a thermal crosslinking agent.
Thermal cross-linking agent 1: para-xylene glycol (Ihara Nikkei, PXG)

<Surfactant>
The following surfactant 1 was used as a surfactant.
Surfactant 1: Fluorinated surfactant (FC4430 manufactured by 3M Japan Co., Ltd.)

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

The following evaluations were performed on the photosensitive resin compositions of Example 1-3 and Comparative example 1.

(viscosity)
Regarding the varnish of the photosensitive resin composition of Example 1-3 and Comparative Example 1, the viscosity was measured after rotation for 300 seconds at a rotational frequency of 100 rpm and a temperature of 25 ° C. using an E-type viscometer (TVE-22H manufactured by Toki Sangyo Co., Ltd.) It was measured. The evaluation results are shown in Table 1 below. Here, the unit of viscosity is mPa · s.

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

(Adhesiveness)
Using the photosensitive resin compositions of Example 1-3 and Comparative Example 1, the adhesion between the post-baking photosensitive resin composition and aluminum (Al) was evaluated as follows.
First, a silicon wafer was prepared as a substrate. Next, titanium (Ti) is coated on the substrate to a thickness of 0.05 μm (500 Å), Al is sputtered on Ti to a thickness of 0.3 μm (3000 Å), and then Al The varnish of the photosensitive resin composition was coated on the above using a spin coater. Next, after prebaking at a temperature of 120 ° C. for 4 minutes using a hot plate, it was further post baked at a temperature of 220 ° C. for 1 hour in a nitrogen atmosphere using an oven to obtain a 7 μm thick cured film. Here, the cured film is in close contact with Al. That is, the laminated structure which a base material, Ti, Al, and a cured film laminate in this order was obtained. The adhesion was evaluated based on JIS D 0202 using this laminated structure. Specifically, the cured film and Al were scratched and singulated so that 100 squares of 1 mm square could be formed from the side where the cured film exists in the laminated structure. Then, cellophane adhesive tape was attached to the cured film. One minute after adhesion, the cellophane adhesive tape was peeled off from the cured film. After peeling, the number of squares in which the cured film and Al remained without peeling and the number of peeled squares were counted among 100 squares, and this was regarded as the evaluation result of PCT by 0 h. The PCT process 0h indicates that the accelerated test has not been performed. The evaluation results are shown in Table 1 below. Table 1 shows the number of peeled squares.
In the above, after the cellophane adhesive tape was attached to the cured film, it was left at a temperature of 125 ° C., a humidity of 100%, and a pressure of 2.3 atm for a specific time, and the cellophane adhesive tape was peeled from the cured film. After peeling, among the 100 squares, the number of squares in which the cured film and Al remained without peeling and the number of peeled squares were counted. This is the result of the PCT process evaluating for a specific time. As the time of the PCT process, evaluation was performed for each of 48 h, 100 h, 150 h, 200 h and 300 h. The evaluation results are shown in Table 1 below. Table 1 shows the number of peeled squares.
Furthermore, the adhesion of the photosensitive resin composition and copper (Cu) after post-baking was evaluated. Specifically, instead of sputtering Al to a thickness of 0.05 μm (500 Å) on Ti, copper (Cu) is sputtered to a thickness of 0.5 μm (300 Å), The adhesion of the photosensitive resin composition described above and aluminum (Al) was evaluated in the same manner as the evaluation. The evaluation results are shown in Table 1 below.
The evaluation results of the adhesion show that the smaller the number, that is, the smaller the number of the peeled squares, the higher the adhesion between the cured film and Al or Cu.
The PCT process is intended for an accelerated test, and was performed to evaluate the long-term adhesion between the post-baking photosensitive resin composition and Al and Cu.

As shown in Table 1 above, it was confirmed that the photosensitive resin composition of each example had a smaller contact angle with metals such as Cu and Al and better conformability compared with the photosensitive resin composition of Comparative Example 1 . Moreover, the cured film obtained by post-baking the photosensitive resin composition of each Example is more suitable for metals such as Cu and Al compared with the cured film obtained by post-baking the photosensitive resin composition of each comparative example. It has been confirmed that the adhesion is improved.

Moreover, in addition to the said Example 1-3, coating can be suitably performed also with respect to the photosensitive resin composition with few compounding quantities of a solvent, and adhesiveness improves like Example 1-3. In order to confirm, the photosensitive resin composition of Example 4-7 was prepared. The method of preparing the photosensitive resin composition of Example 4-7 was the same as that of Example 1-3 described above. The blend ratio of Example 4-7 is shown in Table 2 below.
In addition, the compounding ratio of each raw material shown to following Table 2 is described by the mass part.
The prepared photosensitive resin composition of Example 4-7 was evaluated for viscosity and adhesion in the same manner as in Example 1-3 described above. Here, the coating could be performed without any problem as in Example 1-3. The evaluation results are shown in Table 2 below.

As mentioned above, although the photosensitive resin composition of Example 4-7 had a small compounding quantity of the solvent compared with the photosensitive resin composition of Example 1-3, coating is performed without a problem. It was confirmed that the adhesion to metals such as Cu and Al after post-baking was exhibited as in the case of the photosensitive resin composition of Example 1-3.

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

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

The viscosity and adhesion of the photosensitive resin compositions shown in Table 3 were evaluated in the same manner as in Example 1-3. Here, the coating could be performed without any problem as in Example 1-3.
In Examples 11-13, the contact angle was measured by the same method as in Example 1-3.
The evaluation results are shown in Table 3.

As shown in Table 3, the adhesion to metals such as Cu and Al after post-baking was remarkably good also when using an amide compound having a non-cyclic structure as a solvent.

This application claims priority based on Japanese Patent Application No. 2017-129670 filed on June 30, 2017, the entire disclosure of which is incorporated herein.

Claims (15)

1. Alkali-soluble resin,
   A photosensitizer,
   A solvent, and
   The photosensitive resin composition in which the said solvent contains a urea compound or the amide compound of a non-cyclic structure.
2. The photosensitive resin composition according to claim 1, wherein
   The photosensitive resin composition is used to form a permanent film,
   The photosensitive resin composition, wherein the permanent film is an interlayer film, a surface protective film, or a dam material.
3. It is the photosensitive resin composition of Claim 1 or 2, Comprising:
   The photosensitive resin composition whose content of the said urea compound in the said solvent and the amide compound of the said non-cyclic structure is 10 mass parts or more and 100 mass parts or less with respect to 100 mass parts of said solvents.
4. The photosensitive resin composition according to any one of claims 1 to 3, wherein
   The solvent contains the urea compound,
   The photosensitive resin composition whose structure of the said urea compound is a non-cyclic structure.
5. The photosensitive resin composition according to claim 4, wherein
   The photosensitive resin composition whose said urea compound is tetramethyl urea.
6. The photosensitive resin composition according to any one of claims 1 to 5, wherein
   The photosensitive resin composition, wherein the alkali-soluble resin is at least one selected from the group consisting of a polyamide resin, a polybenzoxazole resin, a polyimide resin, a phenol resin, a hydroxystyrene resin, and a cyclic olefin resin.
7. 7. The photosensitive resin composition according to claim 6, wherein
   The alkali soluble resin comprises the polyamide resin,
   The said polyamide resin is a photosensitive resin composition containing the structural unit represented by following formula (PA1).
   

   
8. It is the photosensitive resin composition according to claim 7, which is
   The said polyamide resin is a photosensitive resin composition containing the structural unit represented by following General formula (PA2) and following General formula (PA3).
   

   

   (In the above general formula (PA2), R ⁴ 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, bromine atom 1 R ^{5 to} R ¹⁰ each independently represent hydrogen or an organic group having 1 to 30 carbon atoms.
   

   

   (In the above general formula (PA3), R ¹¹ is selected from the group consisting of hydrogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, chlorine atom, fluorine atom, bromine atom 1 R ^{12 to} R ¹⁹ each independently represent hydrogen or an organic group having 1 to 30 carbon atoms.
9. The photosensitive resin composition according to any one of claims 1 to 8, wherein
   The photosensitive resin composition, wherein the content of the alkali-soluble resin in the photosensitive resin composition is 30 parts by mass or more and 95 parts by mass or less, based on 100 parts by mass of the total solid content of the photosensitive resin composition. .
10. It is the photosensitive resin composition of any one of Claim 1 to 9, Comprising:
    The photosensitive resin composition whose said photosensitive agent is a diazoquinone compound.
11. The photosensitive resin composition according to any one of claims 1 to 10, wherein
    The photosensitive resin composition further contains a cohesion aid,
    The photosensitive resin composition, wherein the adhesion assistant is a triazole compound, an aminosilane or an imide compound.
12. The photosensitive resin composition according to any one of claims 1 to 11, wherein
    A composition obtained by adjusting the viscosity of the photosensitive resin composition so as to have a viscosity of 50 mPa · s measured after rotating for 300 seconds at a rotational frequency of 100 rpm and a temperature of 25 ° C. by an E-type viscometer at a temperature of 25 ° C. The photosensitive resin composition whose contact angle after 10 seconds of dripping 2 ml to foil is 70 degrees or less.
13. The photosensitive resin composition according to any one of claims 1 to 12, wherein
    The photosensitive resin composition whose viscosity of the said photosensitive resin composition 300 seconds after a rotation start at 25 degreeC in temperature measured using E-type viscosity meter is 50 mPa * s or more and 2000 mPa * s or less.
14. A resin film obtained by curing the photosensitive resin composition according to any one of claims 1 to 13.
15. An electronic device comprising the resin film according to claim 14.

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