TWI832816B - Photosensitive resin composition, resin film and electronic device - Google Patents

Abstract

The photosensitive resin composition of the present invention includes an alkali-soluble resin, a photosensitive agent, and a solvent, and the solvent includes a urea compound or an amide compound with a non-cyclic structure. The structure of the urea compound is preferably a non-cyclic structure. Furthermore, the urea compound is preferably tetramethylurea. In addition, the amide compound with a non-cyclic structure is preferably 3-methoxy-N,N-dimethylpropamide. In addition, the alkali-soluble resin is preferably a polyamide resin.

Description

Photosensitive resin compositions, resin films and electronic devices

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

In the field of photosensitive resin compositions, various technologies have been developed so far for the purpose of obtaining a photosensitive resin composition that can form a cured film that is not fragile and has high heat resistance even when cured at low temperature. As this type of technology, the technology described in Patent Document 1 can be cited.

According to Patent Document 1, it is described that a polyamide having a specific structure is coated with a resin composition containing a compound having a phenolic hydroxyl group, and the film is cured at 200° C. or lower and exhibits a high elongation at break.

Patent Document 1: Japanese Patent Application Publication No. 2007-213032

The inventors of the present invention used the photosensitive resin composition described in Patent Document 1 as a permanent film for an electronic device, and found that aluminum (Al) pads and circuits, that is, copper (Cu) used for input and output of the substrate of the electronic device, were used. ) to study the tightness between the circuit and the permanent film. Furthermore, the so-called permanent film is a cured film obtained by prebaking, exposing and developing a photosensitive resin composition to produce a resin film patterned into a desired shape, and then curing the resin film by post-baking. .

As a result of the above study, it was determined that the cured film formed using the photosensitive resin composition described in Patent Document 1 has insufficient adhesion to the Al pad and the Cu circuit.

Therefore, an object of the present invention is to improve the adhesiveness between a cured film obtained by post-baking a photosensitive resin composition and metals such as Al and Cu.

The present inventors studied the raw material components of the photosensitive resin composition in order to improve the adhesiveness between the cured film of the photosensitive resin composition after post-baking and metals such as Al and Cu. As a result, they found that by including a specific solvent as a raw material component, the adhesiveness between the cured film of the post-baked photosensitive resin composition and metals such as Al and Cu can be improved, and the present invention was completed.

According to the present invention, a photosensitive resin composition is provided, which includes: an alkali-soluble resin; a photosensitive agent; and a solvent, wherein the solvent includes a urea compound or a amide compound with a non-cyclic structure.

Furthermore, according to the present invention, a resin film obtained by curing the above-mentioned photosensitive resin composition can be provided.

Furthermore, according to the present invention, an electronic device provided with the above resin film can be provided.

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

The above objects and other objects, features and advantages will become clearer by the preferred embodiments described below and the accompanying drawings below.

30: Interlayer insulation film

32: Passivation film

34:Top layer wiring

40:Rewiring layer

42:Insulation layer

44:Insulation layer

46:Rewiring

50: UBM layer

52:Bump

100: Electronic devices

FIG. 1 is a cross-sectional view showing an example of the electronic device according to this embodiment.

Hereinafter, this embodiment will be described using drawings as appropriate. Additionally, in all figures In the formula, the same components are marked with the same symbols and their descriptions are omitted.

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

In recent years, with the miniaturization of electronic devices, there is a tendency for metal components such as Al pads and copper circuits of electronic devices to become smaller. Here, when the metal member becomes smaller, the adhesive force between the cured film of the photosensitive resin composition laminated on the metal member and the metal member is low, resulting in peeling of the cured film. When the cured film peels off, a leakage current or the like occurs from the location where the peeling occurs, and there is a problem that the electrical reliability of the electronic device decreases.

The present inventors studied the raw material components of the photosensitive resin composition that can improve the adhesion between the cured film of the post-baked photosensitive resin composition and metals such as Al pads and copper circuits. As a result, it was found that adhesion can be improved by containing a urea compound or a amide compound with a non-cyclic structure as a solvent for the photosensitive resin composition.

The detailed mechanism that can improve the adhesion is not clear, but it can be speculated as follows. As a mechanism for improving the adhesion, it is first thought that the lone electron pair possessed by the urea compound and the amide compound with a non-cyclic structure forms a strong coordination bond with metal atoms such as Al and Cu. Therefore, it is considered that the components contained in the varnish of the photosensitive resin composition before drying are stretched by the coordination bonds formed by the solvent and are strongly bonded to metals such as Al and Cu. Thereafter, when the photosensitive resin composition is prebaked, exposed, and developed to produce a resin film patterned into a desired shape, and then the resin film is post-baked and hardened to produce a cured film, It is presumed that the molecular coordination of the components other than the solvent of the photosensitive resin composition can be frozen in a coordinated state in which the components other than the solvent of the photosensitive resin composition and the metal atoms are strongly bonded. Therefore, it is considered that the adhesion between the post-baked cured film and metals such as Al and Cu can be improved.

Furthermore, it is speculated that the mechanism for forming the above-mentioned strong coordination bond is different in the urea compound and the amide compound with a non-cyclic structure. First, as a premise, it is known that in photosensitive resin compositions, as a solvent As an agent, amide compounds with a cyclic structure such as N-methylpyrrolidone (NMP) are used. Urea compounds have two or more nitrogen atoms with lone electron pairs in their molecular structure due to the urea bond. From this, it is inferred that the coordination bond becomes stronger in proportion to the number of lone electron pairs. Therefore, it is considered that when a urea compound is used, a stronger coordination bond can be formed than a compound used as a solvent for a conventional photosensitive resin composition. Furthermore, it is presumed that the amide compound with a non-cyclic structure can easily form a coordination bond compared with the amide compound with a cyclic structure used in conventional photosensitive resin compositions. This is considered to be because the amide compound with a non-cyclic structure has fewer restrictions on molecular motion than the amide compound with a cyclic structure, and thus has a greater degree of freedom in deformation of the molecular structure. Therefore, it is considered that when a amide compound with a non-cyclic structure is used, a stronger coordination bond can be formed than a compound used in a solvent of a conventional photosensitive resin composition.

From the above, it can be inferred that the photosensitive resin composition of the present embodiment contains a specific compound as a solvent, thereby improving the adhesiveness between the post-baked cured film and metals such as Al and Cu.

Furthermore, in addition to the above-mentioned improvement in the adhesion between the cured film after post-baking and metals such as Al and Cu, urea compounds have less adverse effects on the human body than solvents used in conventional photosensitive resin compositions. It is also beneficial to consider the perspective. Conventionally used amide compounds with cyclic structures such as N-methylpyrrolidone have various adverse effects such as impairment of reproductive function due to their entry into the human body. In addition, considering safety, it is necessary to improve the production of photosensitive resin compositions. Research the steps. However, since urea compounds have little adverse effects on the human body, they are advantageous in aspects such as research that does not require a production step.

Examples of urea compounds that have little adverse effects on the human body include tetramethylurea and the like.

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

(Alkali-soluble resin)

唑樹脂、酚樹脂、羥基苯乙烯樹脂等。作為鹼可溶性樹脂，在上述具體例中，例 如使用聚醯胺樹脂或聚苯并

唑樹脂為較佳。藉此，認為能夠在聚醯胺樹脂的醯胺鍵與尿素化合物或非環狀結構的醯胺化合物之間形成氫鍵等強相互作用。因此，當將感光性樹脂組成物設為硬化膜時，可認為能夠藉由鹼可溶性樹脂和金屬分子更強力地鍵結而成之配位來凍結分子結構。再者，作為鹼可溶性樹脂，能夠包含上述具體例中的一種或兩種以上。 The alkali-soluble resin is not limited and can be selected based on physical properties such as mechanical properties and optical properties required for the resin film. Specific examples of the alkali-soluble resin include polyamide resin, polybenzo

Azole resin, phenol resin, hydroxystyrene resin, etc. As the alkali-soluble resin, in the above specific examples, for example, polyamide resin or polybenzoyl resin is used.

Azole resin is preferred. This makes it possible to form strong interactions such as hydrogen bonds between the amide bond of the polyamide resin and the urea compound or the amide compound with a non-cyclic structure. Therefore, when the photosensitive resin composition is used as a cured film, it is considered that the molecular structure can be frozen by coordination in which the alkali-soluble resin and metal molecules are more strongly bonded. In addition, the alkali-soluble resin can contain one kind or two or more kinds of the above-mentioned specific examples.

唑樹脂> <Polyamide resin, polybenzo

Azole resin>

As the polyamide resin, for example, an aromatic polyamide containing an aromatic ring in the structural unit of the polyamide is preferably used, and one containing a structural unit represented by the following formula (PA1) is more preferably used. As a result, the molecular chains of the polyamide resin are hydrogen-bonded to each other through the amide bond, and the aromatic ring portions are closely arranged molecularly, thereby enabling the alkali-soluble resin to be more strongly bonded to the metal molecules. coordinate to freeze the molecular structure. This coordination is more suitable for improving the adhesion when the solvent contains tetramethylurea as the urea compound. Therefore, from the viewpoint of improving the adhesiveness, it is preferable to include a polyamide resin as the alkali-soluble resin and the solvent to include tetramethylurea as the urea compound.

In addition, in this embodiment, the term "aromatic ring" means a benzene ring; a condensed aromatic ring such as a naphthalene ring, anthracene ring, and pyrene ring; and a heteroaromatic ring such as a pyridine ring and a pyrrole ring. From the viewpoint of forming the above-mentioned compact structure, the polyamide resin of this embodiment preferably contains a benzene ring as an aromatic ring.

唑樹脂的前驅物。包含上述式(PA1)所表示之結構單元之聚醯胺樹脂例如能夠藉由在150℃以上且380℃以下的溫度以30分鐘以上且50小時以下的條件進行熱處理，藉此脫水閉環，形成聚苯并

唑樹脂。此處，上述式(PA1)的結構單元藉由脫水閉環而成為下述式(PBO1)所表示之結構單元。 Polyamide resin-based polybenzoyl containing the structural unit represented by the above formula (PA1)

Precursor of azole resin. The polyamide resin containing the structural unit represented by the above formula (PA1) can be dehydrated and closed by heat treatment at a temperature of 150°C or more and 380°C or less for 30 minutes or less and 50 hours or less, for example, to form a polyamide resin. Benzo

Azole resin. Here, the structural unit of the above formula (PA1) becomes a structural unit represented by the following formula (PBO1) by dehydration and ring closure.

唑樹脂。亦即，進行上述熱處理之感光性樹脂組成物包含作為鹼可溶性樹脂之聚苯并

唑樹脂。 When the alkali-soluble resin of this embodiment is a polyamide resin containing the structural unit represented by the above formula (PA1), for example, the photosensitive resin composition can be subjected to the above-described heat treatment to dehydrate and close the ring to form a polyamide resin. Benzo

Azole resin. That is, the photosensitive resin composition subjected to the above heat treatment contains polybenzo as an alkali-soluble resin.

Azole resin.

唑樹脂。在藉由將聚醯胺樹脂進行脫水開環而形成聚苯并

唑樹脂之情況下，能夠增加拉伸斷裂伸長率、玻璃轉移溫度。藉此，就能夠提高樹脂膜、電子裝置的強度及耐熱性之觀點而言有利。 In addition, when the alkali-soluble resin is a polyamide resin containing a structural unit represented by the above formula (PA1), the above-mentioned heat treatment can be performed after producing the resin film or electronic device described later, thereby dehydrating the ring and forming a polyphenylene glycol. and

Azole resin. Polybenzo is formed by dehydration and ring-opening of polyamide resin.

In the case of azole resin, it can increase the tensile elongation at break and glass transition temperature. This is advantageous from the viewpoint that the strength and heat resistance of the resin film and the electronic device can be improved.

<Manufacturing method of polyamide resin>

The polyamide resin of this embodiment is polymerized as follows, for example.

First, the polyamide is polymerized by polycondensing the diamine monomer and the dicarboxylic acid monomer in the polymerization step (S1). Next, the low molecular weight component is removed through the low molecular weight component removal step (S2) to obtain a polyamide resin containing polyamide as the main component.

(Polymerization step (S1))

In the polymerization step (S1), the diamine monomer and the dicarboxylic acid monomer are polycondensed. The polycondensation method for polymerizing polyamide is not limited, and specific examples include melt polycondensation, chloride chloride method, direct polycondensation, and the like.

Furthermore, instead of the dicarboxylic acid monomer, a compound selected from the group consisting of tetracarboxylic dianhydride, 1,2,4-benzenetricarboxylic anhydride, dichlorinated dicarboxylic acid or active ester type dicarboxylic acid can also be used. . Specific examples of a method for obtaining an active ester-type dicarboxylic acid include reacting a dicarboxylic acid with 1-hydroxy-1,2,3-benzotriazole or the like.

The following describes the diamine monomer and dicarboxylic acid monomer used in the polymerization of the polyamide resin. Furthermore, the diamine monomer and the dicarboxylic acid monomer may be prepared individually by one type, or two or more types may be used in combination.

<Diamine monomer>

The diamine monomer used for polymerization is not limited. For example, a diamine monomer containing an aromatic ring in the structure is preferably used, and a diamine monomer containing a phenolic hydroxyl group in the structure is more preferably used. Here, as the diamine monomer containing a phenolic hydroxyl group in the structure, for example, one represented by the following general formula (DA1) is preferred. By using this diamine monomer as a raw material to produce polyamide resin and controlling the configuration of the polyamide resin, the molecular chains of the polyamide resin can form a closer structure with each other. Therefore, the molecular structure can be frozen and the adhesion can be improved by the coordination of the alkali-soluble resin and the metal molecules that are more strongly bonded.

Furthermore, for example, when a diamine monomer represented by the following general formula (DA1) is used, the polyamide resin contains a structural unit represented by the following general formula (PA2). That is, it is preferable that the polyamide resin of this embodiment contains the structural unit represented by the following general formula (PA2), for example.

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

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

R ⁴ in the above general formulas (DA1) and (PA2) is composed of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. A base formed by one or more atoms in a group.

Furthermore, the R ⁴ series has a 2-price base. Here, the term "bivalent radical" means atomic valence. That is, there are two bonds indicating that R ⁴ is bonded to other atoms.

When R ⁴ in the above general formulas (DA1) and (PA2) contains a carbon atom, R ⁴ is, for example, a group with a carbon number of 1 or more and 30 or less, preferably a group with a carbon number of 1 or more and 10 or less. A group having a carbon number of 1 to 5 is more preferred, and a group having a carbon number of 1 to 3 is still more preferred.

When R ⁴ in the above general formulas (DA1) and (PA2) contains a carbon atom, specific examples of R ⁴ include an alkylene group, an aryl group, a halogen-substituted alkylene group, and a halogen-substituted alkylene group. The extension of aryl and so on.

The alkylene group may be, for example, a linear alkylene group or a branched alkylene group. Specific examples of the linear alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptyl, octyl, nonyl, and Decyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc. Specific examples of the branched alkylene group include -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - and other alkyl methylene; -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 - and other alkyl extensions Ethyl et al.

Specific examples of the aryl group include a phenylene group, a biphenylene group, a naphthylene group, anthracenylene group, and two Or two or more aryl groups bonded to each other, etc.

Specifically, the halogen-substituted alkylene group and the halogen-substituted aryl group may be those obtained by substituting the hydrogen atoms in the above-mentioned alkylene groups and aryl groups with halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms. winner. Among these, those obtained by substituting hydrogen atoms with fluorine atoms are preferably used.

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

R ⁵ ~ R ¹⁰ in the above general formulas (DA1) and (PA2) are each independently hydrogen or an organic group with a carbon number of 1 or more and 30 or less. For example, hydrogen or an organic group with a carbon number of 1 or more and 10 or less are relatively Preferably, hydrogen or an organic group having a carbon number of 1 to 5 is more preferred, hydrogen or an organic group having a carbon number of 1 to 3 is still more preferred, hydrogen or an organic group having a carbon number of 1 to 2 is still more preferred Better. Thereby, the aromatic rings of the polyamide resin can be closely arranged with each other. Therefore, the molecular structure can be frozen by the coordination in which the alkali-soluble resin and the metal molecules are more strongly bonded, and the adhesion can be improved.

Specific examples of the organic group having 1 to 30 carbon atoms in R ⁵ to R ¹⁰ in the general formulas (DA1) and (PA2) include methyl, ethyl, n-propyl, isopropyl, n-propyl, Butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and other alkyl groups; allyl, pentenyl, ethylene alkenyl groups such as ethynyl group; alkylene groups such as methine and ethylene groups; aryl groups such as tolyl, xylyl, phenyl, naphthyl, anthryl and other aryl groups; benzyl, phenethyl and other aromatic groups Alkyl; cycloalkyl such as adamantyl, cyclopentyl, cyclohexyl, cyclooctyl, etc.; alkaryl such as tolyl, xylyl, etc.

Specific examples of the diamine monomer represented by the general formula (DA1) include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-methylene. Bis(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 closely aligned with each other. Therefore, it can be formed by alkali-soluble resin and metal molecules bonded more strongly It coordinates to freeze the molecular structure and improve the tightness. In addition, as the diamine monomer, one type of the above specific examples can be used, or two or more types can be used in combination.

The structural formulas of these diamine monomers are shown below.

<Dicarboxylic acid monomer>

The dicarboxylic acid monomer used for polymerization is not limited. For example, it is preferable to use a dicarboxylic acid monomer containing an aromatic ring in its structure.

As the dicarboxylic acid monomer containing an aromatic ring, for example, one represented by the following general formula (DC1) is preferably used.

Furthermore, for example, when a dicarboxylic acid monomer represented by the following general formula (DC1) is used, the polyamide resin contains a structural unit represented by the following general formula (PA3). That is, it is preferable that the polyamide resin of this embodiment contains the structural unit represented by the following general formula (DC1), for example. Thereby, the aromatic rings of the polyamide resin can be closely arranged with each other. Therefore, the molecular structure can be frozen by the coordination in which the alkali-soluble resin and the metal molecules are more strongly bonded, and the adhesion can be improved.

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

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

R ¹¹ in the above general formulas (DC1) and (PA3) is composed of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. A base formed by one or more atoms in a group.

Furthermore, R ¹¹ is a 2-valent base. Here, the term "bivalent radical" means atomic valence. That is, there are two bonds indicating that R ¹¹ is bonded to other atoms.

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

When R ¹¹ in the above general formulas (DC1) and (PA3) contains a carbon atom, specific examples of R ¹¹ include an alkylene group, an aryl group, a halogen-substituted alkylene group, and a halogen-substituted alkylene group. The extension of aryl and so on.

The alkylene group may be, for example, a linear alkylene group or a branched alkylene group. Specific examples of the linear alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptyl, octyl, nonyl, and Decyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc. Specific examples of the branched alkylene group include -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - and other alkyl methylene; -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 - and other alkyl extensions Ethyl et al.

Specific examples of the aryl group include a phenylene group, a biphenylene group, a naphthylene group, an anthracenylene group, and one in which two or more aryl groups are bonded to each other.

Specifically, as the halogen-substituted alkylene group and the halogen-substituted aryl group, hydrogen atoms in the above-mentioned alkylene group and aryl group can be substituted with halogen atoms such as fluorine atom, chlorine atom, and bromine atom, respectively. By. Among these, it is preferable to use one in which a hydrogen atom is replaced by a fluorine atom.

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

R ¹² to R ¹⁹ in the above general formulas (DC1) and (PA3) are each independently hydrogen or an organic group with a carbon number of 1 or more and 30 or less. For example, hydrogen or an organic group with a carbon number of 1 or more and 10 or less are relatively Preferably, hydrogen or an organic group having a carbon number of 1 to 5 is more preferred, hydrogen or an organic group having a carbon number of 1 to 3 is still more preferred, and hydrogen is still more preferred.

Specific examples of the organic group having a carbon number of 1 to 30 for R ¹² to R ¹⁹ in the general formulas (DC1) and (PA3) include methyl, ethyl, n-propyl, isopropyl, n- Butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and other alkyl groups; allyl, pentenyl, ethylene alkenyl groups such as ethynyl group; alkylene groups such as methine and ethylene groups; aryl groups such as tolyl, xylyl, phenyl, naphthyl, anthryl and other aryl groups; benzyl, phenethyl and other aromatic groups Alkyl; cycloalkyl such as adamantyl, cyclopentyl, cyclohexyl, cyclooctyl, etc.; alkaryl such as tolyl, xylyl, etc.

As the dicarboxylic acid monomer, specifically, diphenyl ether-4,4'-dicarboxylic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, etc. can be used. As the dicarboxylic acid monomer, diphenyl ether-4,4'-dicarboxylic acid or isophthalic acid in the above specific examples is preferably used, and diphenyl ether-4,4'-dicarboxylic acid is more preferably used. . The aromatic rings of the polyamide resin can be closely arranged with each other. Therefore, the molecular structure can be frozen by the coordination in which the alkali-soluble resin and the metal molecules are more strongly bonded, and the adhesion can be improved.

Furthermore, it is preferable to modify the amine group present at the terminal of the polyamide resin simultaneously with the polymerization step (S1) or after the polymerization step (S1). Modification can be performed, for example, by reacting a specific acid anhydride or a specific monocarboxylic acid with a diamine monomer or a polyamide resin. Therefore, it is preferable that the terminal amine group of the polyamide resin of this embodiment is modified with a specific acid anhydride or a specific monocarboxylic acid. Furthermore, the above-mentioned specific acid anhydride and the above-mentioned specific monocarboxylic acid have one or more functional groups selected from the group consisting of alkenyl group, alkynyl group and hydroxyl group. Moreover, it is preferable that the said specific acid anhydride and the specific monocarboxylic acid contain a nitrogen atom, for example. This can improve the adhesiveness between the post-baked photosensitive resin composition and metals such as Al and Cu.

Specific examples of the specific acid anhydride include maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, exo- 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3- Dicarboxylic anhydride, Iconic anhydride, chlorobridged anhydride, 4-ethynyl phthalic anhydride, 4-phenylethynyl phthalic anhydride, 4-hydroxyphthalic anhydride Acid anhydrides, etc. As the specific acid anhydride, one type of the above specific examples can be used, or two or more types can be used in combination.

Furthermore, when the amine group present at the terminal of the polyamide resin is modified with a specific acid anhydride having a ring shape, the specific acid anhydride having a ring shape undergoes ring opening. Here, after modifying the polyamide resin, the structural unit derived from a specific acid anhydride in a ring shape can be ring-closed to form an amide imine ring. Examples of methods for closing the loop include heat treatment.

Furthermore, specific examples of the specific monocarboxylic acid include 5-norbornene-2-carboxylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, and the like. As the above-mentioned specific monocarboxylic acid, one type of the above-mentioned specific examples can be used, or two or more types can be used in combination.

Furthermore, the carboxyl group present at the terminal of the polyamide resin may be modified simultaneously with the polymerization step (S1) or after the polymerization step (S1). Modification can be performed, for example, by reacting a specific heteroaromatic compound containing a nitrogen atom with a dicarboxylic acid monomer or a polyamide resin. Therefore, the polyamide resin of this embodiment is preferably modified by modifying the terminal carboxyl group with a specific heteroaromatic compound containing nitrogen atoms. Furthermore, the above-mentioned specific nitrogen atom-containing heteroaromatic compound has a group selected from the group consisting of 1-(5-1H-triazolyl)methylamine group, 3-(1H-pyrazolyl)amine group, 4-(1H -pyrazolyl)amine, 5-(1H-pyrazolyl)amine, 1-(3-1H-pyrazolyl)methylamino, 1-(4-1H-pyrazolyl)methylamine base, 1-(5-1H-pyrazolyl)methylamino group, (1H-tetrazol-5-yl)amino group, 1-(1H-tetrazol-5-yl)methyl-amino group and 3 -(1H-tetrazol-5-yl)benzene-amine group consisting of one or more functional groups. Thereby, the number of lone electron pairs in the photosensitive resin composition can be increased. Therefore, the adhesiveness between the prebaked and postbaked photosensitive resin composition and metals such as Al can be improved.

Specific examples of the specific nitrogen atom-containing heteroaromatic compound include 5-aminotetrazole and the like.

(Low molecular weight component removal step (S2))

Following the above polymerization step (S1), a low molecular weight component removal step (S2) is performed to remove Low molecular weight components are used to obtain polyamide resin with polyamide resin as the main component.

The organic layer containing the mixture of the low molecular weight component and the polyamide resin is concentrated by filtration or the like, and then dissolved again in an organic solvent such as water/isopropyl alcohol. Thereby, the precipitate is filtered to obtain a polyamide resin from which low molecular weight components have been removed.

As the polyamide resin, for example, one obtained by condensing a diamine monomer represented by the above-mentioned general formula (DA1) and a dicarboxylic acid monomer represented by the above-mentioned general formula (DC1) is preferred. That is, as a polyamide resin, it is preferable that it has the structural unit of the said general formula (PA2) and (PA3), and it is more preferable that it has the structural unit of the said general formula (PA2) and (PA3) alternately.

<Phenolic resin>

Specific examples of the phenol resin include novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, bisphenol novolac resin, and phenol-biphenyl novolac resin; novolak-type phenol resins and soluble phenolic resins. The reaction product of phenolic compounds such as phenol resin and cresol-type phenol resin and aldehyde compounds; the reaction product of phenol compounds such as phenol aralkyl resin and dimethyl alcohol compound, etc. Furthermore, the phenol resin may contain one or two or more types of the above-mentioned specific examples.

The above-mentioned phenolic compound used as a reactant between a phenolic compound and an aldehyde compound or a reactant between a phenolic compound and a dimethyl alcohol compound is not limited.

Specific examples of such phenolic compounds include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, and 2,5-dimethylphenol. Cresol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol and other xylenols; o-ethylphenol, m-ethylphenol, p-ethylphenol and other ethylphenols Classes; alkylphenols such as isopropylphenol, butylphenol, and p-tertiary butylphenol; polyphenols such as resorcinol, catechol, hydroquinone, gallic phenol, and phloroglucinol; 4 , 4'-biphenol and other biphenyl phenols. As the phenol compound, one or two or more types of the above specific examples can be used.

The above-mentioned aldehyde compound used as a reactant between a phenol compound and an aldehyde compound is not limited as long as it is a compound having an aldehyde group.

Specific examples of such aldehyde compounds include formaldehyde, polyformaldehyde, acetaldehyde, benzaldehyde, salical, and the like. As the aldehyde compound, one or two or more types of the above specific examples can be used.

The dimethanol compound used as a reactant for the phenol compound and the dimethanol compound is not limited.

Specific examples of such dimethanol compounds include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4'-biphenyldimethanol, 3,4'-biphenyldimethanol, 3, 3'-biphenyl dimethanol, 2,6-naphthalene dimethanol, 2,6-bis(hydroxymethyl)-p-cresol and other dimethanol compounds; 1,4-bis(methoxymethyl)benzene, 1 ,3-bis(methoxymethyl)benzene, 4,4'-bis(methoxymethyl)biphenyl, 3,4'-bis(methoxymethyl)biphenyl, 3,3'- Bis(methoxymethyl)biphenyl, 2,6-naphthalenedicarboxylic acid methyl ester and other bis(alkoxymethyl) compounds, or 1,4-bis(chloromethyl)benzene, 1,3-bis (Chloromethyl)benzene, 1,4-bis(bromomethyl)benzene, 1,3-bis(bromomethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 3,4'- Bis(chloromethyl)biphenyl, 3,3'-bis(chloromethyl)biphenyl, 4,4'-bis(bromomethyl)biphenyl, 3,4'-bis(bromomethyl)biphenyl Or bis(haloalkyl) compounds such as 3,3'-bis(bromomethyl)biphenyl, 4,4'-bis(methoxymethyl)biphenyl, 4,4'-bis(methoxymethyl) ) biphenyl and other biphenyl aralkyl compounds, etc. As the dimethanol compound, one or two or more types of the above specific examples can be used.

<Hydroxystyrene resin>

The hydroxystyrene resin is not limited, and specifically, one or two or more types selected from the group consisting of hydroxystyrene, hydroxystyrene derivatives, styrene, and styrene derivatives can be polymerized or copolymerized. Polymers or copolymers.

Specific examples of hydroxystyrene derivatives and styrene derivatives include those in which a hydrogen atom contained in the aromatic ring of hydroxystyrene or styrene is substituted with a monovalent organic group. Examples of organic groups substituting monovalent hydrogen atoms include alkyl groups such as methyl, ethyl and n-propyl; alkenyl groups such as allyl and vinyl; alkynyl groups such as ethynyl; methine and ethylene groups. alkylene groups; cycloalkyl groups such as cyclopropyl groups; heterocyclic groups such as epoxy groups and oxetanyl groups; etc.

<Cyclic Olefin Resin>

The cyclic olefin-based resin is not limited, and specifically, a polymerization reaction product or copolymerization reaction product obtained by polymerizing or copolymerizing one or two or more types selected from the group consisting of norbornene and norbornene derivatives can be used. things.

Specific examples of norbornene derivatives include those in which a hydrogen atom bonded to the norbornene skeleton is substituted with a monovalent organic group. Examples of organic groups substituting monovalent hydrogen atoms include alkyl groups such as methyl, ethyl and n-propyl; alkenyl groups such as allyl and vinyl; alkynyl groups such as ethynyl; methine and ethylene groups. alkylene groups; cycloalkyl groups such as cyclopropyl group; heterocyclic groups such as epoxy group and oxycyclobutanyl group, etc.

For example, when the total solid content of the photosensitive resin composition is 100 parts by mass, the lower limit of the alkali-soluble resin content in the photosensitive resin composition is preferably 30 parts by mass or more, and more preferably 40 parts by mass or more. , 50 parts by mass or more is further preferred, 60 parts by mass or more is further preferred, and 70 parts by mass or more is particularly preferred. Thereby, the alkali-soluble resin in the photosensitive resin composition can interact appropriately with the urea compound or the amide compound with a non-cyclic structure in the solvent. Therefore, the molecular structure can be frozen by the coordination in which the alkali-soluble resin and the metal molecules are more strongly bonded, and the adhesion can be improved.

For example, when the total solid content of the photosensitive resin composition is 100 parts by mass, the upper limit of the alkali-soluble resin content in the photosensitive resin composition is preferably 95 parts by mass or less, and 90 parts by mass or less. It is more preferable, and it is still more preferable that it is 85 parts by mass or less.

In addition, in this embodiment, the total solid content of the photosensitive resin composition means the total number of components contained in the photosensitive resin composition except the solvent.

(sensitizer)

As the photosensitizer, a photoacid generator that generates acid by absorbing light energy can be used.

化合物；二氫吡啶化合物等。該等中，使用感光性重氮醌化合物為較佳。藉此，能夠提高感光性樹脂組成物的靈敏度。因此，能夠提高圖案的精度，並能夠改善外觀。再者，作為光酸產生劑，能夠包含上述具體例中的一種或兩種以上。 Specific examples of the photoacid generator include diazoquinone compounds; diaryl ion salts; 2-nitrobenzyl ester compounds; N-iminosulfonate compounds; and amide imine sulfonate compounds. Compound; 2,6-bis(trichloromethyl)-1,3,5-tris

Compounds; dihydropyridine compounds, etc. 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 the photoacid generator, one kind or two or more kinds of the above specific examples can be included.

In addition, when the photosensitive resin composition is a positive type, as the photosensitive agent, in addition to the above-mentioned specific examples, onium salts such as triarylsulfonate salts and sulfonium-borate salts may be used in combination. Thereby, the sensitivity of the photosensitive resin composition can be further improved.

Specific examples of diazoquinone compounds that can be preferably used as photosensitizers are shown below.

(n is an integer from 1 to 5.)

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. Among them, at least one of Q in each diazoquinone compound has a structure represented by the following formula (a), the following formula (b), and the following formula (c).

Q as 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.

When the alkali-soluble resin is 100 parts by mass, the photosensitivity in the photosensitive resin composition The lower limit of the content of the agent is, for example, preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more. Thereby, the photosensitive resin composition can exhibit appropriate sensitivity.

Moreover, when the alkali-soluble resin is 100 parts by mass, the upper limit of the content of the photosensitive agent in the photosensitive resin composition is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less. Thereby, the photosensitive resin composition is suitably hardened and can exhibit adhesion to metals such as Al and Cu after prebaking and postbaking.

(solvent)

The photosensitive resin composition of this embodiment contains a urea compound or an acyclic amide compound as a solvent. As a solvent, it is preferable to contain a urea compound, for example. This can further improve the adhesiveness between the cured product of the photosensitive resin composition and metals such as Al and Cu.

In addition, in this specification, the term "urea compound" means a compound having a urea bond, that is, a urea bond. Moreover, the amide compound means a compound having a amide bond, that is, a amide. In addition, the amide includes first-level amide, second-level amide, and third-level amide.

In addition, in this embodiment, the term "acyclic structure" means that the structure of the compound does not include a cyclic structure such as a carbocyclic ring, an inorganic ring, or a heterocyclic ring. Examples of the structure of a compound that does not have a cyclic structure include a linear structure, a branched structure, and the like.

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

Specific examples of the structure of the urea compound include a cyclic structure, a non-cyclic structure, and the like. As the structure of the urea compound, an acyclic structure is preferred in the above specific examples. This can improve the adhesiveness between the cured product of the photosensitive resin composition and metals such as Al and Cu. The reason for this is presumed to be as follows. It is estimated that urea compounds with acyclic structure are easier to Form coordination bonds. This is considered to be because a urea compound with a non-cyclic structure has fewer restrictions on molecular motion than a urea compound with a cyclic structure, and thus has a greater degree of freedom in deformation of the molecular structure. Therefore, when a urea compound with a non-cyclic structure is used, a strong coordination bond can be formed and the adhesion can be improved.

Specific examples of the urea compound include tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone, tetrabutylurea, N,N'-dimethylacrylamide, 1,3 -Dimethoxy-1,3-dimethylurea, N,N'-diisopropyl-O-methylisourea, O,N,N'-triisopropylisourea, O-tertiary Butyl-N,N'-diisopropylisourea, O-ethyl-N,N'-diisopropylisourea, O-benzyl-N,N'-diisopropylisourea, etc. As the urea compound, one type of the above specific examples can be used, or two or more types can be used in combination. As the urea compound, in the above specific examples, for example, a compound selected from the group consisting of tetramethylurea (TMU), tetrabutylurea, 1,3-dimethoxy-1,3-dimethylurea, and N,N'-dimethylurea is used. Isopropyl-O-methylisourea, O,N,N'-triisopropylisourea, O-tertiary butyl-N,N'-diisopropylisourea, O-ethyl-N , one or two or more of the group consisting of N'-diisopropylisourea and O-benzyl-N,N'-diisopropylisourea is preferred, and tetramethylurea (TMU) is used. Better. This can form strong coordination bonds and improve adhesion.

Specific examples of the amide compound with a non-cyclic structure include 3-methoxy-N, N-dimethylpropionamide, N,N-dimethylformamide, and N,N-dimethyl Propionamide, N,N-diethyl acetamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dibutylformamide, etc.

The photosensitive resin composition of this embodiment may contain a solvent which does not have a nitrogen atom as a solvent in addition to a urea compound and a amide compound with a non-cyclic structure.

Specific examples of the solvent not having a nitrogen atom include ether solvents, acetate solvents, alcohol solvents, ketone solvents, lactone solvents, carbonate solvents, ester solvents, aromatic solvents, etc. Hydrocarbon solvents, etc. As the solvent not having a nitrogen atom, one type of the above specific examples can be used, or two or more types can be used in combination.

Specific examples of the ether solvent include propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, and ethylene glycol. diol Diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, 1,3-butanediol-3-monomethyl ether, etc.

Specific examples of the acetate-based solvent include propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butanediol acetate, and the like. .

Specific examples of the alcohol-based solvent include tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol, butylene glycol, isopropyl alcohol, and the like.

Specific examples of the ketone solvent include cyclopentanone, cyclohexanone, diacetone alcohol, 2-heptanone, and the like.

Specific examples of the lactone solvent include γ-butyrolactone (GBL), γ-valerolactone, and the like.

Specific examples of the carbonate-based solvent include ethyl carbonate, propylene carbonate, and the like.

Specific examples of the above-mentioned sulfonylene-based solvent include dimethylsulfoxide (DMSO), cyclotenine, and the like.

Specific examples of the ester solvent include methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, and the like.

Specific examples of the aromatic hydrocarbon-based solvent include mesitylene, toluene, xylene, and the like.

When the solvent is 100 parts by mass, the lower limit of the content of the urea compound and the amide compound with a non-cyclic structure in the solvent is, for example, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and 30 parts by mass. More than 50 parts by mass is still more preferred, and more than 70 parts by mass is particularly preferred. This can further improve the adhesiveness between the cured product of the photosensitive resin composition and metals such as Al and Cu.

Moreover, when the solvent is 100 parts by mass, the lower limit of the content of the urea compound and the amide compound with a non-cyclic structure in the solvent can be, for example, 100 parts by mass or less. Among the solvents, from the viewpoint of improving adhesion, the content of urea compounds and non-cyclic structural amide compounds is often preferable.

The photosensitive resin composition of this embodiment can further add an adhesive agent and silane. Coupling agents, thermal cross-linking agents, surfactants, antioxidants, dissolution accelerators, fillers, sensitizers and other additives.

Representative added ingredients are described in detail below.

(Adhesive agent)

The photosensitive resin composition of this embodiment may further contain an adhesive agent. As the adhesion aid, specifically, a triazole compound, an aminosilane, or an imine compound can be used. This can further increase the number of lone electron pairs from nitrogen atoms. Therefore, substances contained in the photosensitive resin composition other than the solvent can be coordinated to the metal atoms, and the adhesiveness can be further improved. As the adhesion aid, any one of a triazole compound, an aminosilane, or an imine compound may be used, or two or more types of a triazole compound, an aminosilane, or an imine compound may be used in combination.

Specific examples of the triazole compound include 4-amino-1,2,4-triazole, 4H-1,2,4-triazole-3-amine, and 4-amino-3,5-di- 2-pyridyl-4H-1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-methyl-4H-1,2,4- Triazole-3-amine, 3,4-diamino-4H-1,2,4-triazole, 3,5-diamino-4H-1,2,4-triazole, 1,2,4 -Triazole-3,4,5-triamine, 3-pyridyl-4H-1,2,4-triazole, 4H-1,2,4-triazole-3-carbonylamide, 3,5- Diamino-4-methyl-1,2,4-triazole, 3-pyridyl-4-methyl-1,2,4-triazole, 4-methyl-1,2,4-triazole -3-Formamide and other 1,2,4-triazoles. As the triazole compound, one type of the above specific examples can be used, or two or more types can be used in combination.

Specific examples of the aminosilane include condensates of cyclohexene-1,2-dicarboxylic anhydride and 3-aminopropyltriethoxysilane, and 3,3',4,4'-diphenyl The condensate of ketotetracarboxylic dianhydride and 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2 -(Aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane silane, 3-aminopropyltriethoxysilane, 3-triethoxymethylsilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminosilane Propyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis(3-triethoxysilylpropyl) Second Diamine, N,N'-bis[3-(methyldimethoxymethylsilyl)propyl]ethylenediamine, N,N'-bis[3-(methyldiethoxymethylsilyl) Propyl]ethylenediamine, N,N'-bis[3-(dimethylmethoxymethylsilyl)propyl]ethylenediamine, N-[3-(methyldimethoxymethylsilyl) Propyl]-N'-[3-(trimethoxymethylsilyl)propyl]ethylenediamine, N,N'-bis[3-(trimethoxymethylsilyl)propyl]diaminopropane, N,N'-bis[3-(trimethoxymethylsilyl)propyl]diaminohexane, N,N'-bis[3-(trimethoxymethylsilyl)propyl]diethylenetriamine wait. As the aminosilane, one type of the above specific examples can be used, or two or more types can be used in combination.

Specific examples of the acyl imine compound include the compounds illustrated below. These can be used alone or in combination of two or more.

The lower limit of the content of the adhesion aid in the photosensitive resin composition is, for example, preferably 0.1 parts by mass or more, more preferably 1.0 parts by mass or more, and 2.0 parts by mass, based on 100 parts by mass of the alkali-soluble resin. Parts by weight or more are more preferred, and 3.0 parts by mass or more are still more preferred. This can fully improve the adhesion force.

Moreover, the upper limit of the content of the adhesion aid in the photosensitive resin composition is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and 5 parts by mass or less based on 100 parts by mass of the alkali-soluble resin. For further improvement. Thereby, the adhesion assistant is appropriately dispersed in the photosensitive resin composition, and the adhesion force can be improved.

(silane coupling agent)

The photosensitive resin composition of this embodiment may further contain a silane coupling agent. Examples of the silane coupling agent include those other than the aminosilane exemplified as the adhesion aid.

Specific examples of the silane coupling agent having a structure different from the above-mentioned silane compound include vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane; 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethyl Epoxysilanes such as oxysilane and 3-glycidoxypropyltriethoxysilane; styrylsilane such as p-styryltrimethoxysilane; 3-methacryloxypropylmethyldimethyl Methoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane Oxysilane and other methacrylic silane; 3-acryloxypropyltrimethoxysilane and other acrylic silane; isocyanate silane; alkyl silane; 3-ureidopropyltrialkoxysilane and other ureido silane; Mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate silanes such as 3-isocyanatepropyltriethoxysilane; titanium compounds; aluminum chelates; Aluminum/zirconium based compounds, etc. As the silane coupling agent, one or two or more types of the above specific examples can be blended.

(thermal cross-linking agent)

The photosensitive resin composition of this embodiment may contain a thermal crosslinking agent capable of reacting with an alkali-soluble resin by heat. Thereby, it is possible to provide a cured product after post-baking the photosensitive resin composition. Mechanical properties of high tensile elongation at break. Furthermore, it is also advantageous from the viewpoint that the sensitivity of the resin film formed of the photosensitive resin composition can be improved.

Specific examples of the thermal cross-linking agent include 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol (p-xylene glycol), and 1,3,5-benzenedimethanol. Trimethanol, 4,4-biphenyl dimethanol, 2,6-pyridine dimethanol, 2,6-bis(hydroxymethyl)-p-cresol, 4,4'-methylene bis(2,6-di Compounds with hydroxymethyl groups such as alkoxymethylphenol); phenols such as pentahydroxybiphenyl (phloroglucide); 1,4-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl) methyl)benzene, 4,4'-bis(methoxymethyl)biphenyl, 3,4'-bis(methoxymethyl)biphenyl, 3,3'-bis(methoxymethyl)biphenyl Benzene, 2,6-naphthalenedicarboxylic acid methyl ester, 4,4'-methylenebis(2,6-dimethoxymethylphenol) and other compounds with alkoxymethyl groups; with hexahydroxymethyl Hydroxymethyl melamine compounds represented by melamine and hexabutyl melamine; alkoxy melamine compounds such as hexamethoxy melamine; alkoxy methyl acetylene urea compounds such as tetramethoxy methyl acetylene urea; hydroxymethyl benzo Guanamine compounds, dimethylolethylene urea and other hydroxymethylurea compounds; cyano compounds such as dicyananiline, dicyanophenol, cyanobenzenesulfonic acid and other cyano compounds; 1,4-phenylene diisocyanate, 3,3 '-Dimethyldiphenylmethane-4,4'-diisocyanate and other isocyanate compounds; ethylene glycol diepoxypropyl ether, bisphenol A diepoxypropyl ether, isocyanatotriglycidyl ether Ester, bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, phenol novolak resin epoxy resin and other epoxy group-containing compounds; N, N Maleimide compounds such as '-1,3-phenylenedimaleimide, N,N'-methylenedimaleimide, etc. As the thermal cross-linking agent, one type of the above specific examples can be used, or two or more types can be used in combination.

The upper limit of the content of the thermal crosslinking agent in the photosensitive resin composition is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 12 parts by mass or less based on 100 parts by mass of the alkali-soluble resin. Preferably, it is more preferably 10 parts by mass or less. Thereby, even when the thermal crosslinking agent has a solvating functional group such as a phenolic hydroxyl group, it is possible to suppress the decrease in chemical resistance after post-baking.

Moreover, the lower limit of the content of the thermal crosslinking agent in the photosensitive resin composition is, for example, preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and more than 3 parts by mass, based on 100 parts by mass of the alkali-soluble resin. In order to be more preferable, it is further more preferable that it is 5 parts by mass or more, and it is especially preferable that it is 8 parts by mass or more.

(surfactant)

The photosensitive resin composition of this embodiment may further contain a surfactant.

The surfactant is not limited, and specific examples include polyoxyethylene alkyl ethers such as polyoxyethylene dodecyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl ether; Polyoxyethylene aryl ethers such as phenyl ether and polyoxyethylene nonylphenyl ether; non-ionic systems such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate Surfactants: EFTOP EF301, EFTOP EF303, EFTOP EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACE F444, MEGAFACE F470, MEGAFACE F471, MEGAFACE F475, MEGAFACE F482, MEGA FACE SURFLON SC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106, (manufactured by AGC SEIMI CHEMICAL) and other commercially available fluorine-based surfactants; organic silicone Alkane copolymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic copolymer Polyflow No. 57, 95 (manufactured by KYOEISHA CHEMICAL Co., Ltd.), etc.

Among these, it is preferable to use a fluorine-based surfactant having a perfluoroalkyl group. As the fluorine-based surfactant having a perfluoroalkyl group, one selected from the group consisting of MEGAFACE F171, MEGAFACE F173, MEGAFACE F444, MEGAFACE F470, MEGAFACE F471, MEGAFACE F475, MEGAFACE F482, and MEGAFACE F477 (manufactured by DIC Corporation) in the above specific examples is used. One or more of SURFLON S-381, SURFLON S-383, SURFLON S-393 (manufactured by AGC SEIMI CHEMICAL), NOVEC FC4430 and NOVEC FC4432 (manufactured by 3M Japan) is preferred.

In addition, as the surfactant, a polysiloxane-based surfactant (for example, polyether-modified dimethylsiloxane, etc.) can be suitably used. Specific examples of polysilicone-based surfactants include Dow Corning Toray's SH series, SD series, and ST series, BYK Japan's BYK series, Shin-Etsu Chemical Co., Ltd.'s KP series, and NOF Co., Ltd. DISFOAM (registered trademark) series, Toshiba Silicones Co., Ltd.'s TSF series, etc.

The upper limit of the content of the surfactant in the photosensitive resin composition is preferably 1% by mass (10000ppm) or less, and more preferably 0.5% by mass (5000ppm) or less relative to the entire photosensitive resin composition (including solvent). The best, 0.1 mass % (1000 ppm) or less is even more preferable.

In addition, the lower limit of the content of the surfactant in the photosensitive resin composition is not particularly limited, but from the viewpoint of fully obtaining the effect of the surfactant, for example, relative to the entire photosensitive resin composition (including the solvent) , above 0.001 mass% (10ppm).

By appropriately adjusting the amount of surfactant, other properties can be maintained, and coatability or coating film uniformity can be improved.

(Antioxidant)

The photosensitive resin composition of this embodiment may further contain an antioxidant. As the antioxidant, one or more types selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and thioether antioxidants can be used. Antioxidants can inhibit oxidation of the resin film formed of the photosensitive resin composition.

、2,2’-亞甲基雙(4-甲基-6-三級丁基-6-丁基酚)、2,-2’-亞甲基雙(4-乙基-6-三級丁基酚)、雙〔3,3-雙(4-羥基-3-三級丁基苯基)丁酸〕乙二醇酯、4,4’-亞丁基雙(6-三級丁基-間甲酚)、2,2’-亞乙基雙(4,6-二-三級丁基酚)、2,2’-亞乙基雙(4-二級丁基-6-三級丁基酚)、1,1,3-三(2-甲基-4-羥基-5-三級丁基苯基)丁烷、雙〔2-三級丁基-4-甲基-6-(2-羥基-3-三級丁基-5-甲基苄基)苯基〕對苯二甲酸酯、1,3,5-三(2,6-二甲基-3-羥基-4-三級丁基苄基)三聚異氰酸酯、1,3,5-三(3,5-二-三級丁基-4-羥基苄基)-2,4,6-三甲基苯、1,3,5-三〔(3,5-二-三級丁基-4-羥基苯基)丙醯氧基乙基〕三聚異氰酸酯、四〔亞甲基-3-(3,5-二-三級丁基-4-羥基苯基)丙酸酯〕甲烷、2-三級丁基-4-甲基-6-(2-丙烯醯氧基-3-三級丁基-5-甲基苄基)酚、3,9-雙(1,1-二甲基-2-羥乙基)-2,4,8,10-四氧雜螺[5,5]十一烷-雙〔β-(3-三級丁基-4-羥基-5-甲基苯基)丙酸酯〕、三乙二醇雙〔β-(3-三級丁基-4-羥基-5-甲基苯基)丙酸酯〕、1,1’-雙(4-羥基苯基)環己烷、2,2’-亞甲基雙(4-甲基-6-三級丁基酚)、2,2’-亞甲基雙(4-乙基-6-三級丁基酚)、2,2’-亞甲基雙(6-(1-甲基環己基)-4-甲基酚)、4,4’-亞丁基雙(3-甲基-6-三級丁基酚)、3,9-雙(2-(3-三級丁基-4-羥基-5-甲基苯基丙醯氧基)1,1-二甲基乙基)-2,4,8,10-四氧雜螺(5,5)十一烷、4,4’-硫代雙(3-甲基-6-三級丁基酚)、4,4’-雙(3,5-二-三級丁基-4-羥基苄基)硫化物、4,4’-硫代雙(6-三級丁基-2-甲基酚)、2,5-二-三級丁基氫醌、2,5-二-三級戊基氫醌、2-三級丁基-6-(3-三級丁基-2-羥基-5-甲基苄基)-4-甲基苯基丙 烯酸酯、2,4-二甲基-6-(1-甲基環己基)、苯乙烯化苯酚、2,4-雙((辛硫基)甲基)-5-甲基酚等。 Examples of phenolic antioxidants include neopentyritol-tetrakis[3-(3,5-di-tertiary butyl-4-hydroxyphenyl)propionate] and 3,9-bis{2-[3 -(3-tertiary butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}2,4,8,10-tetraxaspiro[5 ,5]Undecane, octadecyl-3-(3,5-di-tertiary butyl-4-hydroxyphenyl)propionate, 1,6-hexanediol-bis[3-(3 ,5-di-tertiary butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-tri(3,5-di-tertiary butyl- 4-hydroxybenzyl)benzene, 2,6-di-tertiary butyl-4-methylphenol, 2,6-di-tertiary butyl-4-ethylphenol, 2,6-diphenyl- 4-Octadecyloxyphenol, stearyl (3,5-di-tertiary butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tertiary butyl- 4-hydroxybenzyl)phosphonate, thiodiethylene glycol bis[(3,5-di-tertiary butyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6 -tertiary butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-tertiary butyl-4-hydroxyphenoxy)-symmetric tri

, 2,2'-methylenebis(4-methyl-6-tertiary butyl-6-butylphenol), 2,-2'-methylenebis(4-ethyl-6-tertiary Butylphenol), bis[3,3-bis(4-hydroxy-3-tertiary butylphenyl)butyrate]ethylene glycol ester, 4,4'-butylene bis(6-tertiary butyl- m-cresol), 2,2'-ethylene bis (4,6-di-tertiary butylphenol), 2,2'-ethylene bis (4-di-butyl-6-tertiary butyl phenol) phenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tertiary butylphenyl)butane, bis[2-tertiary butyl-4-methyl-6-( 2-Hydroxy-3-tertiary butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4- Tertiary butylbenzyl)tripolyisocyanate, 1,3,5-tris(3,5-di-tertiary butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1, 3,5-tris[(3,5-di-tertiary butyl-4-hydroxyphenyl)propyloxyethyl]tripolyisocyanate, tetrakis[methylene-3-(3,5-di- Tertiary butyl-4-hydroxyphenyl)propionate]methane, 2-tertiary butyl-4-methyl-6-(2-propenyloxy-3-tertiary butyl-5-methyl Benzyl)phenol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraxaspiro[5,5]undecane-bis[β -(3-tertiary butyl-4-hydroxy-5-methylphenyl)propionate], triethylene glycol bis[β-(3-tertiary butyl-4-hydroxy-5-methylbenzene base) propionate], 1,1'-bis(4-hydroxyphenyl)cyclohexane, 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), 2, 2'-methylenebis(4-ethyl-6-tertiary butylphenol), 2,2'-methylenebis(6-(1-methylcyclohexyl)-4-methylphenol), 4,4'-butylene bis(3-methyl-6-tertiary butylphenol), 3,9-bis(2-(3-tertiary butyl-4-hydroxy-5-methylphenylpropanol) Cyloxy)1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, 4,4'-thiobis(3-methyl- 6-tertiary butylphenol), 4,4'-bis(3,5-di-tertiary butyl-4-hydroxybenzyl) sulfide, 4,4'-thiobis(6-tertiary butyl) base-2-methylphenol), 2,5-di-tertiary butylhydroquinone, 2,5-di-tertiary amylhydroquinone, 2-tertiary butyl-6-(3-tertiary butyl 2-Hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2,4-dimethyl-6-(1-methylcyclohexyl), styrenated phenol, 2,4 -Bis((octylthio)methyl)-5-methylphenol, etc.

Examples of phosphorus-based antioxidants include bis(2,6-di-tertiary butyl-4-methylphenyl)nepententerythritol diphosphite and tris(2,4-di-tertiary butylbenzene). phosphite), tetrakis(2,4-di-tertiary butyl-5-methylphenyl)-4,4'-biphenyl diphosphite, 3,5-di-tertiary butyl Diethyl-4-hydroxybenzylphosphate, bis-(2,6-diisopropylphenyl)nepenterythritol diphosphite, 2,2-methylene bis(4, 6-Di-tertiary butylphenyl)octyl phosphate, tris(mixed mono- and di-nonylphenyl phosphite), bis(2,4-di-tertiary butylphenyl)nepentyltetrakis Alcohol diphosphite, bis(2,6-di-tertiary butyl-4-methoxycarbonylethyl-phenyl)neopenterythritol diphosphite, bis(2,6-di-tertiary Butyl-4-octadecyloxycarbonylethylphenyl) neopentylerythritol diphosphite, etc.

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

(filler)

The photosensitive resin composition of this embodiment may further contain a filler. As a filler, an appropriate filling material can be selected based on the mechanical properties and thermal properties required for the resin film made of the photosensitive resin composition.

Specific examples of fillers include inorganic fillers, organic fillers, and the like.

Specific examples of the inorganic filler include silica such as fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, and finely powdered silica; alumina, nitride Silicon, aluminum nitride, boron nitride, titanium oxide, silicon carbide, aluminum hydroxide, magnesium hydroxide, titanium white and other metal compounds; talc; clay; mica; glass fiber, etc. As the inorganic filler, one type of the above specific examples can be used, or two or more types can be used in combination.

Specific examples of the organic filler include organic polysiloxane powder, polyethylene powder, and the like. do As an organic filler, one type of the above specific examples can be used, or two or more types can be used in combination.

(Preparation of photosensitive resin composition)

The method for preparing the photosensitive resin composition in this embodiment is not limited, and a known method can be used depending on the components contained in the photosensitive resin composition.

For example, it can be prepared by mixing and dissolving each of the above components with a solvent. Thereby, a photosensitive resin composition as a varnish can be obtained.

(Photosensitive resin composition)

The photosensitive resin composition of this embodiment can be used by applying the varnish of the photosensitive resin composition to a surface provided with metal such as Al or Cu, and then drying it by prebaking to form a resin. The film is then exposed and developed to pattern the resin film into a desired shape, and then the resin film is cured by post-baking to form a cured film.

Furthermore, when producing the permanent film, prebaking conditions can be, for example, heat treatment at a temperature of 90° C. or more and 130° C. or less for 30 seconds or more and 1 hour or less. Moreover, as a post-baking condition, for example, it can be heat treatment at a temperature of 150 degreeC or more and 350 degreeC or less, and 30 minutes or more and 10 hours or less.

The viscosity of the photosensitive resin composition of this embodiment can be set appropriately according to the desired thickness of the resin film. The viscosity of the photosensitive resin composition can be adjusted by adding a solvent. Furthermore, during adjustment, the contents of the urea compound and the non-cyclic amide compound in the solvent need to be maintained constant.

The upper limit of the viscosity of the photosensitive resin composition of this embodiment can be, for example, 2000 mPa. s or less, it can also be 1800mPa. s or less, it can also be 1500mPa. s or less. In addition, depending on the desired thickness of the resin film, the lower limit of the viscosity of the photosensitive resin composition of this embodiment may be, for example, 10 mPa. s or above, it can also be 50mPa. s or above.

In addition, in this embodiment, the viscosity of the photosensitive resin composition can be measured by, for example, an E-type viscometer starting rotation at a temperature of 25° C. for 300 seconds.

The viscosity of the photosensitive resin composition of this embodiment measured after rotating for 300 seconds with an E-type viscometer at a rotation frequency of 100 rpm and a temperature of 25°C was 50 mPa. Adjust the viscosity in the same way as 25°C. The upper limit of the contact angle after 10 seconds of adding 2 mL to the copper foil is preferably 71° or less, more preferably 69° or less, and 65° or less. It is better, below 62° is even better, and below 57° is especially good. When the contact angle is below the above numerical range, the affinity between the varnish of the photosensitive resin composition and metals such as Cu is improved, and the photosensitive resin composition can penetrate into the fine gaps created on the surface of metals such as Cu. Thereby, when the photosensitive resin composition is used as a cured film, an anchoring effect can be exhibited between the cured film and metal such as Cu, and the adhesion force can be improved.

In addition, the viscosity measured by an E-type viscometer after rotating for 300 seconds at a rotation frequency of 100 rpm and a temperature of 25°C was 50 mPa. The viscosity is adjusted in the s method. The lower limit of the contact angle after 10 seconds of dropping 2 mL onto the copper foil at a temperature of 25°C can be, for example, 40° or more, or 45° or more.

The viscosity of the photosensitive resin composition of this embodiment measured after rotating for 300 seconds with an E-type viscometer at a rotation frequency of 100 rpm and a temperature of 25°C was 50 mPa. Adjust the viscosity by using the method s. The upper limit of the contact angle after 10 seconds of adding 2 mL to the aluminum foil at a temperature of 25°C is preferably 14° or less, more preferably 13° or less, and further preferably 12° or less. , 11° or less is better. When the contact angle is below the above numerical range, the affinity between the varnish of the photosensitive resin composition and metals such as Al is improved, and the photosensitive resin composition can penetrate into the fine gaps created on the surface of metals such as Al. Thereby, when the photosensitive resin composition is used as a cured film, an anchoring effect can be exhibited between the cured film and metals such as Al, and the adhesion force can be improved.

In addition, the viscosity measured by an E-type viscometer after rotating for 300 seconds at a rotation frequency of 100 rpm and a temperature of 25°C was 50 mPa. The viscosity is adjusted in the s method. The lower limit of the contact angle after 10 seconds of dropping 2 mL onto the aluminum foil at a temperature of 25°C can be, for example, 1° or more, or 5° or more.

Additional explanation on viscosity adjustment when measuring the above contact angle.

For the viscosity in the measurement method based on the above-mentioned E-type viscometer is greater than 50mPa. s photosensitive resin group To form a product, use the same solvent as that contained in the photosensitive resin composition, and adjust the viscosity to 50 mPa. s to measure the contact angle. Furthermore, when the photosensitive resin composition contains a mixed solvent, the viscosity is adjusted by the mixed solvent.

Also, for the viscosity based on the above measurement method is less than 50mPa. For the photosensitive resin composition of s, the equivalent viscosity of 50mPa can be calculated as follows. s is the contact angle.

For example, assume that the viscosity based on the above measurement method is 40mPa. s photosensitive resin composition. The photosensitive resin composition is further diluted with the same solvent as the solvent contained in the photosensitive resin composition, and the viscosity is made to be 30, 20, and 10 mPa. s and other photosensitive resin compositions. And, plot the viscosity 10~40mPa. The relationship between the viscosity and the contact angle of the photosensitive resin composition of s is a straight line drawn by the least squares method, and the extrapolation is equivalent to a viscosity of 50mPa. Find the contact angle of s. Furthermore, the plotting is performed at a minimum of 2 points, preferably 3 points or 4 points.

Incidentally, as the present inventors discovered, at 50 mPa. In the low viscosity area below s, such as 30mPa. s and 50mPa． s, there is almost no difference in contact angle.

The inventors of the present invention studied a method of setting the contact angle with copper foil and aluminum foil within the above-mentioned numerical range for a varnish of a photosensitive resin composition. As a result, they found that appropriately controlling the urea compound and acyclic compounds contained in the solvent The structure of the amide compound with a cyclic structure and the content of the urea compound and the amide compound with a non-cyclic structure in the solvent are important.

As for the structure of the urea compound or the amide compound with a non-cyclic structure contained in the solvent, those with more resonance structures are preferred. Specifically, the urea bond of the urea compound or the amide bond of the non-cyclic amide compound is preferably the one with the largest number of resonance structures formed by the lone electron pair of the nitrogen atom and the ketone site C=O. The number of resonance structures of the urea compound and the non-cyclic amide compound is, for example, preferably 2 or more, and more preferably 3 or more. Thereby, the electron cloud of the urea compound and the amide compound with a non-cyclic structure is diffused, and the electronic state is stabilized. Therefore, it is considered that the surface free energy of urea compounds and non-cyclic amide compounds can be reduced and the wettability with respect to Cu can be improved. as the number of resonant structures Give an example. For example, the number of resonance structures of urea compounds such as tetramethylurea (TMU) is three.

In addition, the content of the urea compound and the non-cyclic amide compound in the solvent also depends on the above-mentioned structure. For example, when the solvent is 100 parts by mass, 30 parts by mass or more is preferred, and 50 parts by mass or more is preferred. It is more preferable, 70 parts by mass or more is still more preferable, and 100 parts by mass is still more preferable. Thereby, the electronic state in the solvent can be stabilized, and the contact angle can be set within the above numerical range.

(use)

The photosensitive resin composition of this embodiment is used to form resin films for electronic devices such as permanent films and resists. Among them, from the viewpoint of improving the adhesion between the prebaked photosensitive resin composition and the Al pad and suppressing the generation of residues of the photosensitive resin composition during development in a good balance, the photosensitivity after postbaking is improved. From the viewpoint of the adhesion between the cured film of the permanent resin composition and the metal and the improvement of the chemical resistance of the post-baked photosensitive resin composition, it is preferred for applications using permanent films.

In addition, in this embodiment, the resin film refers to the dry film or cured film of the photosensitive resin composition. That is, the resin film of this embodiment is what dried or hardened the photosensitive resin composition.

The permanent film is composed of a resin film obtained by prebaking, exposing and developing the photosensitive resin composition and patterning it into a desired shape, and then postbaking and hardening the composition. Permanent films can be used as protective films, interlayer films, dam materials, etc. for electronic devices.

The above-mentioned resist is composed of, for example, a resin film obtained by applying the photosensitive resin composition to the resist by spin coating, roller coating, flow coating, dip coating, spray coating, blade coating, etc. Remove the solvent from the photosensitive resin composition on the object covered with the agent.

An example of the electronic device according to this embodiment is shown in FIG. 1 .

The electronic device 100 of this embodiment can be an electronic device provided with the above-mentioned resin film. Specifically, one or more of the group consisting of the passivation film 32, the insulating layer 42, and the insulating layer 44 in the electronic device 100 can be a resin film. Here, the resin film is preferably the above-mentioned permanent film.

The electronic device 100 is, for example, a semiconductor chip. In this case, for example, the electronic device 100 is mounted on the wiring substrate via the bumps 52 to obtain a semiconductor package. The electronic device 100 includes a semiconductor substrate on which semiconductor elements such as transistors are provided, and a multilayer wiring layer (not shown) on the semiconductor substrate. The interlayer insulating film 30 and the uppermost wiring 34 provided on the interlayer insulating film 30 are provided in the uppermost layer among the multilayer wiring layers. The uppermost layer wiring 34 is made of aluminum Al, for example. Furthermore, a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34 . An opening exposing the uppermost layer wiring 34 is provided in a part of the passivation film 32 .

A rewiring layer 40 is provided on the passivation film 32 . The rewiring layer 40 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 the rewiring 46 . An opening connected to the uppermost layer wiring 34 is formed in the insulating layer 42 . The rewiring 46 is formed on the insulating layer 42 and disposed in the opening of the insulating layer 42 to be connected to the uppermost layer wiring 34 . The insulating layer 44 is provided with an opening connected to the rewiring 46 .

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

In addition, the present invention is not limited to the above-mentioned embodiments, and modifications, improvements, etc. within the scope that can achieve the object of the present invention are included in the present invention.

[Example]

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

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

<Alkali-soluble resin>

First, the alkali-soluble resin used in each Example and each Comparative Example will be described in detail.

(Alkali-soluble resin 1)

The alkali-soluble resin 1, which is a polyamide resin, is synthesized by the following steps.

Diphenyl ether-4,4'-dicarboxylic acid 206.58 represented by the following formula (DC2) was placed in a four-neck glass detachable flask equipped with a thermometer, a stirrer, a raw material input port and a dry nitrogen gas introduction tube. 170.20g (0.346mol) of a mixture of dicarboxylic acid derivatives obtained by reacting g (0.800mol) with 216.19g (1.600mol) of 1-hydroxy-1,2,3-benzotriazole monohydrate, 5 -Aminotetrazole 4.01g (0.047mol), 45.22g (0.196mol) of 4,4'-methylenebis(2-aminophenol) represented by the following formula (DA2) and the following formula (DA3) The represented 4,4'-methylenebis(2-amino-3,6-dimethylphenol) 56.24g (0.196mol). Thereafter, 578.3 g of N-methyl-2-pyrrolidone was added to the separable flask to dissolve each raw material component. Next, the reaction was carried out at 90° C. for 5 hours using an oil bath. Next, 24.34g (0.141mol) of 4-ethynyl phthalic anhydride and 121.7g of N-methyl-2-pyrrolidone were added to the above-mentioned separable flask, and the mixture was stirred at 90° C. for 2 hours. After the reaction, the reaction was completed after cooling to 23°C.

The filtrate obtained by filtering the reaction mixture in the separable flask was put into a solution of water/isopropyl alcohol = 7/4 (volume ratio). Thereafter, the precipitate was filtered, thoroughly washed with water, and then dried under vacuum to obtain alkali-soluble resin 1. The weight average molecular weight Mw of the obtained alkali-soluble resin 1 was 18,081.

<Photosensitizer>

Next, the photosensitizer used in each Example and Comparative Example will be described in detail.

(sensitizer 1)

Photosensitizer 1, which is a diazoquinone compound, was synthesized by the following steps.

Put 11.04g (0.026mol) of phenol represented by the following formula (P-1) and 1,2-naphthoquinone- 18.81g (0.070mol) of 2-diazide-5-sulfonyl chloride and 170g of acetone were stirred to dissolve them.

Next, while cooling the flask in a water bath so that the temperature of the reaction solution would not become 35° C. or higher, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise. After reacting at room temperature for 3 hours in this state, 1.05 g (0.017 mol) of acetic acid was added, and the reaction was continued for 30 minutes. Next, after filtering the reaction mixture, the filtrate was added to a mixed solution of water/acetic acid (990 mL/10 mL). Next, the precipitate was collected by filtration, thoroughly washed with water, and then dried under vacuum. Thereby, the photosensitive agent 1 represented by the structure of the following formula (Q-1) was obtained.

<Solvent>

As the solvent, the following solvents 1 to 3 are used.

． Solvent 1: Tetramethylurea (TMU), a linear urea compound

． Solvent 2: γ-butyrolactone (GBL)

． Solvent 3: N-methylpyrrolidone (NMP) which is a cyclic amide compound

<Close bonding agent>

As an adhesion aid, use the following adhesion aids 1 to 3.

． Adhesion aid 1: N,N'-bis[3-(trimethoxymethylsilyl)propyl]ethane-1,2-diamine (Shin) which is an aminosilane represented by the following formula (S1) -X-12-5263HP manufactured by Etsu Chemical Co., Ltd.)

． Adhesion aid 2: A condensate of carboxylic acid anhydride and 3-aminopropyltriethoxysilane, which is an aminosilane represented by the following formula (S2) and is synthesized by the method described below.

Hereinafter, a method for synthesizing the adhesion aid 2 which is a condensate of carboxylic anhydride and 3-aminopropyltriethoxysilane will be described in detail.

In a reaction vessel of appropriate size equipped with a stirrer and cooling tube, dissolve cyclohexene-1,2-dicarboxylic anhydride (45.6g, 300mmol) in N-methyl-2-pyrrolidone (970g), and Adjust to 30°C in a constant temperature bath. Next, 3-aminopropyltriethoxysilane (62 g, 280 mmol) was placed in a dropping funnel and added dropwise to the solution over 60 minutes. After completion of the dropwise addition, the mixture was stirred at 30° C. for 18 hours to obtain the close contact aid 2 represented by the following formula (S2).

<Thermal cross-linking agent>

As the thermal cross-linking agent, the following thermal cross-linking agent 1 is used.

． Thermal cross-linking agent 1: p-xylene glycol (IHARANIKKEI CHEMICAL INDUSTRY Co., Ltd. PXG manufactured by our company)

<Surfactant>

As the surfactant, the following surfactant 1 was used.

． Surfactant 1: Fluorine-based surfactant (FC4430 manufactured by 3M Japan)

(Preparation of Photosensitive Resin Compositions of Each Example and Comparative Example)

The photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 were prepared as follows.

First, prepare each of the above raw material components. Next, if two or more solvents are used, the solvents are mixed according to the blending ratio shown in Table 1 below to prepare a mixed solvent. Next, each raw material except the solvent was added to the solvent or mixed solvent and stirred, and then filtered through a PTFE membrane filter with a pore size of 0.2 μm, thereby obtaining the photosensitive resin composition of each example and each comparative example. Varnish.

In addition, the blending ratio of each raw material shown in Table 1 below is described in parts by mass.

The photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 were evaluated as follows.

(viscosity)

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

(contact angle)

The contact angle of the varnish was evaluated as follows using the varnish of the photosensitive resin composition of Examples 1 to 3 and Comparative Example 1.

First, prepare a smooth copper foil as a base material. Next, the contact angle 10 seconds after dropping 2 mL of the varnish of the photosensitive resin composition onto the base material at a temperature of 25° C. was evaluated using the droplet method. Furthermore, a contact angle meter (DROPMASTER-501 manufactured by Kyowa Interface Science) was used for measurement.

Moreover, the thing which used the smooth aluminum foil as a base material instead of the said smooth copper foil was also evaluated.

Each evaluation result is shown in Table 1 below. Here, the unit of contact angle is °. Here, in Table 1 below, a description of "-" means that evaluation was not performed.

Furthermore, when measured by an E-type viscometer after rotating at a rotation frequency of 100 rpm and a temperature of 25°C for 300 seconds, the viscosity of the varnish of each photosensitive resin composition of Examples 1 to 3 and Comparative Example 1 was 50 mPa. s.

(Tightness)

Using the photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1, the adhesiveness between the post-baked photosensitive resin composition and aluminum (Al) was evaluated in the following manner.

First, a silicon wafer is prepared as a base material. Next, titanium (Ti) is coated on the base material to a thickness of 0.05 μm (500Å), Al is sputtered onto Ti to a thickness of 0.3 μm (3000Å), and then a spin coater is used to The varnish of the photosensitive resin composition is coated on Al. Next, a hot plate was used to pre-bake at a temperature of 120° C. for 4 minutes, and then an oven was used to post-bake at a temperature of 220° C. for 1 hour in a nitrogen atmosphere to obtain a cured film with a thickness of 7 μm. Here, the cured film is in close contact with Al. That is, a laminated structure is obtained in which the base material, Ti, Al, and cured film are laminated in this order. Using this laminated structure, the adhesion was evaluated in accordance with JIS D 0202. Specifically, from the side where the cured film exists in the multilayer structure, the cured film and Al were scratched to form 100 squares of 1 mm square, and then separated into individual pieces. Next, a cellophane tape was attached to the cured film. After adhering for 1 minute, peel the cellophane tape from the cured film. After peeling, among 100 squares, the number of squares in which the cured film and Al were not peeled off and the number of squares after peeling were calculated, and this was used as the evaluation result of the PCT program of 0h. The so-called PCT program 0h means that no accelerated test has been performed. The evaluation results are shown in Table 1 below. Table 1 shows the number of squares after peeling.

Moreover, in the above, after the cellophane tape is attached to the cured film, it is left at a temperature of 125° C., a humidity of 100%, and an air pressure of 2.3 atm for a specific time, and then the cellophane tape is peeled off from the cured film. After peeling off, among 100 squares, calculate the number of squares that remain without peeling off the cured film and Al and the number of squares after peeling off. The number of squares. Consider this an evaluation result of the PCT procedure for a specific time. As the PCT procedure time, 48h, 100h, 150h, 200h, and 300h were evaluated respectively. The evaluation results are shown in Table 1 below. Table 1 shows the number of squares after peeling.

Further, the adhesion between the post-baked photosensitive resin composition and copper (Cu) was evaluated. Specifically, instead of sputtering Al onto Ti to have a thickness of 0.05 μm (500Å), copper (Cu) was sputtered to have a thickness of 0.5 μm (300Å). Other than that, the evaluation was performed in the same manner. The method was used to evaluate the adhesion between the photosensitive resin composition and aluminum (Al). The evaluation results are shown in Table 1 below.

In addition, the adhesiveness evaluation results all showed small values, which means that the smaller the number of squares after peeling, the higher the adhesiveness between the cured film and Al and Cu.

In addition, the PCT procedure is performed for the purpose of accelerating testing and for evaluating the long-term adhesion between the post-baked photosensitive resin composition and Al and Cu.

As shown in Table 1 above, it was confirmed that the photosensitive resin composition of each example has a smaller contact angle and better affinity for metals such as Cu and Al than the photosensitive resin composition of Comparative Example 1. Furthermore, it was confirmed that the cured film obtained by post-baking the photosensitive resin composition of each example is better than the cured film obtained by post-baking the photosensitive resin composition of each comparative example. The tightness is improved.

Moreover, in addition to the above-mentioned Examples 1 to 3, it was confirmed that the photosensitive resin composition with a small blending amount of the solvent can be appropriately coated, and the adhesiveness was improved similarly to Examples 1 to 3, so it was prepared Photosensitive resin compositions of Examples 4 to 7. The preparation method of the photosensitive resin compositions of Examples 4 to 7 is the same as that of the above-mentioned Examples 1 to 3. The blending ratios of Examples 4 to 7 are shown in Table 2 below.

In addition, the blending ratio of each raw material shown in Table 2 below is described in parts by mass.

For the photosensitive resin compositions prepared in Examples 4 to 7, the viscosity and adhesiveness were evaluated in the same manner as in Examples 1 to 3 above. Here, coating can be performed without any problem in the same manner as in Examples 1 to 3. The evaluation results are shown in Table 2 below.

As described above, it was confirmed that the photosensitive resin compositions of Examples 4 to 7 contained a smaller blending amount of the solvent than the photosensitive resin compositions of Examples 1 to 3, but could be coated without any problem. , similar to the photosensitive resin compositions of Examples 1 to 3, the adhesiveness to metals such as Cu and Al after post-baking was demonstrated.

Further evaluation was performed on the following Examples 8 to 13 and Comparative Example 2. Examples 8 to 13 contain a non-cyclic amide compound as a solvent.

First, each raw material component shown in Table 3 was prepared. Next, if two or more solvents are used, the solvents are mixed according to the blending ratio shown in Table 3 below to prepare a mixed solvent.

Next, each raw material except the solvent was added to the solvent or mixed solvent and stirred, and then filtered through a PTFE membrane filter with a pore size of 0.2 μm, thereby obtaining a varnish of the photosensitive resin composition.

In addition, the blending ratio of each raw material in Table 3 is parts by mass.

Among the raw material components shown in Table 3, solvent 4 is the following. Other raw material components are the same as those described in Table 1 or Table 2.

． Solvent 4: 3-methoxy-N,N-dimethylpropamide, which is an amide compound with a non-cyclic structure

Regarding the photosensitive resin composition in Table 3, the viscosity and adhesiveness were evaluated in the same manner as in Examples 1 to 3. Here, coating can be performed without any problem in the same manner as in Examples 1 to 3.

In addition, regarding Examples 11 to 13, the contact angle was measured using the same method as Examples 1 to 3.

The evaluation results are shown in Table 3.

As shown in Table 3, even when a amide compound with a non-cyclic structure is used as a solvent, the adhesion to metals such as Cu and Al after post-baking is remarkably good.

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

30‧‧‧Interlayer insulation film

32‧‧‧ Passivation film

34‧‧‧Top layer wiring

40‧‧‧Rewiring layer

42‧‧‧Insulation layer

44‧‧‧Insulation layer

46‧‧‧Rewiring

50‧‧‧UBM layer

52‧‧‧Bump

100‧‧‧Electronic devices

Claims (13)

A photosensitive resin composition, which includes: an alkali-soluble resin; a photosensitive agent; and a solvent. The alkali-soluble resin is a polyamide containing structural units represented by the following general formula (PA2) and the following general formula (PA3) Resin, the solvent contains a urea compound, the structure of the urea compound is a non-cyclic structure, and the content of the urea compound in 100 parts by mass of the solvent is more than 30 parts by mass,

In the above general formula (PA2), R ⁴ is one of the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. Or a radical formed by two or more atoms; R ⁵ ~ R ¹⁰ each independently represent hydrogen or an organic radical with a carbon number of 1 to 30,

In the above general formula (PA3), R ¹¹ is one selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. Or a group formed by two or more atoms; R ¹² ~ R ¹⁹ each independently represent hydrogen or an organic group with a carbon number of 1 to 30. The organic group is selected from alkyl, alkenyl, alkynyl, and alkylene. Any one of the group consisting of aryl, aryl, aralkyl, cycloalkyl and alkaryl. For example, the photosensitive resin composition of Item 1 of the patent scope is applied for, wherein the photosensitive resin composition is used to form a permanent film, and the permanent film is an interlayer film, a surface protective film or a dam material. For example, the photosensitive resin composition of claim 1 or 2, wherein the content of the urea compound in the solvent is 50 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the solvent. For example, in the photosensitive resin composition of claim 3, the urea compound is tetramethylurea. For example, if the photosensitive resin composition of claim 1 or 2 is applied for, when the total solid content of the photosensitive resin composition is 100 parts by mass, 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. For example, the photosensitive resin composition of claim 1 or 2 of the patent scope, wherein the photosensitive agent is a diazoquinone compound. For example, the photosensitive resin composition of claim 1 or 2, wherein the photosensitive resin composition further includes an adhesive agent, and the adhesive agent is a triazole compound, an aminosilane or an imine compound. For example, for the photosensitive resin composition in the patent application scope 1 or 2, the viscosity measured by an E-type viscometer after rotating for 300 seconds at a rotation frequency of 100 rpm and a temperature of 25°C is 50 mPa. The viscosity of the photosensitive resin composition was adjusted in the method s, and the contact angle after 10 seconds after adding 2 mL dropwise to the copper foil at a temperature of 25°C was 70° or less. For example, the photosensitive resin composition in the patent scope 1 or 2 of the application, wherein the viscosity of the photosensitive resin composition measured by an E-type viscometer after starting to rotate at a temperature of 25°C for 300 seconds is 50 mPa. s or more and 2000mPa. s or less. A photosensitive resin composition, which includes: an alkali-soluble resin; a photosensitive agent; and a solvent, the solvent includes a amide compound with a non-cyclic structure, the alkali-soluble resin is selected from the group consisting of polyamide resin, polybenzo

One or more of the group consisting of azole resin, polyimide resin, phenol resin, hydroxystyrene resin and cyclic olefin resin, and the content of the non-cyclic amide compound in 100 parts by mass of the solvent is 10 More than parts by mass. For example, the photosensitive resin composition of item 10 of the patent application, wherein the non-cyclic amide compound is selected from the group consisting of 3-methoxy-N,N-dimethylpropionamide and N,N-dimethylpropamide. Methylformamide, N,N-dimethylpropionamide, N,N-diethylacetamide, 3-butoxy-N,N-dimethylpropionamide and N,N-dibutylmethane At least any one of the group consisting of amide. A resin film formed by hardening the photosensitive resin composition of any one of claims 1 to 11. An electronic device provided with the resin film of Item 12 of the patent application.