Photosensitive resin composition for permanent film formation, permanent film, and semiconductor device

Abstract

To provide a photosensitive resin composition for permanent film formation which is less likely to generate a foreign matter.SOLUTION: A photosensitive resin composition for permanent film formation includes an alkali-soluble resin (A), a photosensitizer (B), a surfactant (C), an adhesion promoter (D), and an additive (E). The photosensitizer (B) includes a photosensitive diazoqunone compound represented by formula (B-1), and the (E) includes a biphenol compound whose molecular weight is 150-1000.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition for forming a permanent film, a permanent film, and a semiconductor device.

Background Art

[0002] Semiconductor devices have permanent films for applications such as insulating layers and protective layers. Such permanent films can be formed using a photosensitive resin composition.

[0003] For example, Patent Document 1 describes a photosensitive resin composition including a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group and a structural unit having a crosslinkable group, and a fluorine-based surfactant. Patent Document 1 also discloses forming a cured film using this photosensitive resin composition and using this cured film as an interlayer insulating film.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] [[ID=3A]]In a permanent film such as an interlayer insulating film, good durability is required even in a high-temperature and high-humidity environment. For this reason, for the manufactured permanent film, the reliability in a high-temperature and high-humidity environment is verified by various reliability tests.

[0006] In the case of a conventional permanent film, as a result of performing such a reliability test, generation of foreign matter may be recognized. Since such foreign matter may reduce the characteristics of the permanent film, suppressing its generation has become an issue.

[0007] An object of the present invention is to provide a permanent film that hardly generates foreign substances even in a high-temperature and high-humidity environment, a photosensitive resin composition for forming such a permanent film, and a semiconductor device including the permanent film.

Means for Solving the Problems

[0008] Such an object is achieved by the present invention described in the following (1) to (9). (1) An alkali-soluble resin (A), a photosensitizer (B), a surfactant (C), an adhesion promoter (D), an additive (E), and having, the photosensitizer (B) contains a photosensitive diazoquinone compound represented by the formula (B-1), the additive (E) contains a biphenol compound having a molecular weight of 150 or more and 1000 or less, and is a photosensitive resin composition for forming a permanent film.

Chemical formula

[0009] (2) The photosensitive resin composition for forming a permanent film according to claim 1, wherein the alkali-soluble resin (A) is a resin in which a dehydration ring-closing reaction proceeds at a temperature of less than 300°C.

[0010] (3) The photosensitive resin composition for forming a permanent film according to (1) or (2) above, wherein the adhesion promoter (D) contains a silane compound.

[0011] (4) The photosensitive resin composition for forming a permanent film according to (1) or (2) above, wherein the surfactant (C) contains an organically modified dimethylsiloxane represented by the formula (C-1).

Chemical formula

[0012] (5) The photosensitive resin composition for permanent film formation according to the above (1) or (2), wherein the alkali-soluble resin (A) is at least one selected from the group consisting of a polyamide resin, a polybenzoxazole resin, and a polyimide resin.

[0013] (6) The photosensitive resin composition for permanent film formation according to the above (1) or (2), wherein the biphenol compound is phloroglucide.

[0014] (7) When the content of the photosensitive diazoquinone compound represented by the formula (B-1) is Xb1 and the content of the biphenol compound having a molecular weight of 150 or more and 1000 or less is Xe, the ratio Xe / Xb1 of the content Xe to the content Xb1 is 0.10 or more and 0.90 or less. The photosensitive resin composition for permanent film formation according to the above (1) or (2).

[0015] (8) A permanent film characterized by being composed of a cured product of the photosensitive resin composition for permanent film formation according to the above (1) or (2). (9) A semiconductor device characterized by having the permanent film according to the above (8).

Advantages of the Invention

[0016] According to the present invention, a permanent film that hardly generates foreign matter even in a high-temperature and high-humidity environment can be obtained. Further, according to the present invention, a photosensitive resin composition for permanent film formation capable of manufacturing the permanent film can be obtained. Furthermore, according to the present invention, a semiconductor device including the permanent film can be obtained.

Brief Description of the Drawings

[0017]

Figure 1

Embodiments for Carrying Out the Invention

[0018] Hereinafter, the photosensitive resin composition for permanent film formation, the permanent film, and the semiconductor device according to the present invention will be described in detail based on the preferred embodiments shown in the accompanying drawings.

[0019] 1. Photosensitive Resin Composition for Permanent Film Formation The photosensitive resin composition for permanent film formation according to the present embodiment is used to form a resin film such as a permanent film for a semiconductor device. The photosensitive resin composition for permanent film formation according to the present embodiment contains an alkali-soluble resin (A), a photosensitizer (B), a surfactant (C), an adhesion aid (D), and an additive (E).

[0020] Among these, the photosensitizer (B) contains a compound represented by the formula (B-1).

[0021] [Chemical formula]

[0022] In addition, the additive (E) contains a biphenol compound having a molecular weight of 150 to 1000. Such a photosensitive resin composition for permanent film formation can form a resin film that is less likely to generate foreign substances even in a high-temperature and high-humidity environment due to having the above configuration. Therefore, the resin film formed using the photosensitive resin composition for permanent film formation can suppress the occurrence of defects related to foreign substances even when subjected to an accelerated reliability test such as a PCT test (pressure cooker test), and as a result, contributes to the improvement of the quality of the semiconductor device.

[0023] In this specification, a group (atomic group) includes both those having no substituent and those having a substituent when it is not described whether it is substituted or unsubstituted. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[0024] In addition, in this specification, unless otherwise specified, when there are a plurality of substances corresponding to each component in the composition, the content of each component in the composition means the total amount of the plurality of substances present in the composition.

[0025] 1.1. Alkaline-soluble resin (A) The alkaline-soluble resin (A) can be selected according to physical properties such as mechanical properties and thermal properties required for the resin film. Examples of the alkaline-soluble resin (A) include polyamide resin, polybenzoxazole resin, polyimide resin, phenol resin, hydroxystyrene resin, and cyclic olefin resin. Among these, one or a combination of two or more can be used for the alkaline-soluble resin (A). The alkaline-soluble resin (A) preferably contains a polyamide resin, a polybenzoxazole resin, or a polyimide resin, more preferably contains a polyamide resin or a polybenzoxazole resin, and even more preferably contains a polybenzoxazole resin. Thereby, the dispersibility of the alkaline-soluble resin (A) in the photosensitive resin composition for permanent film formation can be improved. In addition, by improving physical properties such as the mechanical strength of the resin film composed of the cured product of the photosensitive resin composition for permanent film formation, the uniformity of the film thickness can be improved, and the occurrence of defects can be suppressed.

[0026] 1.1.1. Polyamide resin, polybenzoxazole resin As the polyamide resin, for example, it is preferable to use an aromatic polyamide containing an aromatic ring in the structural unit of polyamide, and those containing a structural unit represented by the formula (PA1) are more preferable. Thereby, physical properties such as the mechanical strength of the resin film can be improved. Therefore, it is also preferable from the viewpoint of improving the uniformity of the film thickness and suppressing the occurrence of defects.

[0027] Examples of the aromatic ring include a benzene ring; condensed aromatic rings such as a naphthalene ring, an anthracene ring, and a pyrene ring; and heteroaromatic rings such as a pyridine ring and a pyrrole ring. From the viewpoint of mechanical strength and the like, the polyamide resin preferably contains a benzene ring as the aromatic ring.

[0028] [Chemical formula]

[0029] The polyamide resin containing the structural unit represented by formula (PA1) is a precursor of the polybenzoxazole resin. The polyamide resin containing the structural unit represented by formula (PA1) can be dehydrated and cyclized to form a polybenzoxazole resin, for example, by heat treatment at a temperature of 150 °C or higher and 380 °C or lower for 30 minutes or longer and 50 hours or shorter. The structural unit of formula (PA1) becomes the structural unit represented by formula (PBO1) by dehydration and cyclization.

[0030] In addition, the polyamide resin containing the structural unit represented by formula (PA1) is preferably a resin in which the dehydration cyclization reaction proceeds at a temperature of less than 300 °C, more preferably a resin in which the dehydration cyclization reaction proceeds at a temperature of 150 °C or higher and less than 300 °C, still more preferably a resin in which the dehydration cyclization reaction proceeds at a temperature of 150 °C or higher and 280 °C or lower, and particularly preferably a resin in which the dehydration cyclization reaction proceeds at a temperature of 150 °C or higher and 260 °C or lower. By using such a polyamide resin, a photosensitive resin composition for permanent film formation capable of forming a resin film that is less likely to generate foreign substances even in a high-temperature and high-humidity environment can be obtained.

[0031] [Chemical formula]

[0032] When the alkali-soluble resin (A) is a polyamide resin containing a structural unit represented by the formula (PA1), by performing the above heat treatment on the photosensitive resin composition for permanent film formation, dehydration ring closure may occur, and it may be a polybenzoxazole resin. That is, the photosensitive resin composition for permanent film formation after the above heat treatment may contain a polybenzoxazole resin which is the alkali-soluble resin (A). Further, when the alkali-soluble resin (A) is a polyamide resin containing a structural unit represented by the formula (PA1), after producing a permanent film or a semiconductor device described later, by performing the above heat treatment, dehydration ring closure may be performed to obtain a polybenzoxazole resin. When a polybenzoxazole resin is obtained by dehydrating and ring-opening a polyamide resin, mechanical properties, thermal properties, etc. can be improved. Thereby, deformation of the permanent film can be suppressed.

[0033] 1.1.2. Polyamide resin, polyimide resin Further, as the polyamide resin, for example, one containing a structural unit represented by the formula (PA2) may be used.

[0034] The polyamide resin containing a structural unit represented by the formula (PA2) is a precursor of a polyimide resin. The polyamide resin containing a structural unit represented by the formula (PA2) can be dehydrated and ring-closed to form a polyimide resin, for example, by heat treatment at a temperature of 150°C or higher and 380°C or lower for 30 minutes or longer and 50 hours or shorter. Here, the structural unit of the formula (PA2) becomes a structural unit represented by the formula (PI1) by dehydration ring closure.

[0035] Note that the polyamide resin containing a structural unit represented by the formula (PA2) is preferably a resin in which the dehydration ring closure reaction proceeds at a temperature of less than 300°C, more preferably a resin in which the dehydration ring closure reaction proceeds at a temperature of 150°C or higher and less than 300°C, still more preferably a resin in which the dehydration ring closure reaction proceeds at a temperature of 150°C or higher and 280°C or lower, and particularly preferably a resin in which the dehydration ring closure reaction proceeds at a temperature of 150°C or higher and 260°C or lower. By using such a polyamide resin, a photosensitive resin composition for permanent film formation capable of forming a resin film less likely to generate foreign substances even in a high-temperature and high-humidity environment can be obtained.

[0036] When the alkali-soluble resin (A) is a polyamide resin containing a structural unit represented by the formula (PA2), by performing the above heat treatment on the photosensitive resin composition for forming a permanent film, dehydration ring closure may occur, and it may be a polyimide resin. That is, the photosensitive resin composition for forming a permanent film after the above heat treatment may contain a polyimide resin that is the alkali-soluble resin (A).

[0037] Also, when the alkali-soluble resin (A) is a polyamide resin containing a structural unit represented by the formula (PA2), after producing a permanent film or a semiconductor device described later, by performing the above heat treatment, dehydration ring closure may be carried out, and it may be a polyimide resin.

[0038]

Chemical formula

[0039] In formula (PA2), R B and R C are each independently an organic group having 1 to 30 carbon atoms.

[0040]

Chemical formula

[0041] In formula (PI1), R B and R C are the same as in formula (PA2).

[0042] R B and R C in formula (PA2) and formula (PI1) are specifically preferably organic groups having an aromatic ring.

[0043] Specific examples of the organic group having an aromatic ring include those containing a benzene ring, a naphthalene ring, or an anthracene ring, with those containing a benzene ring being more preferred. This improves the dispersibility of the alkali-soluble resin (A) and enhances the uniformity of the resin film. As a result, a composition capable of forming a resin film less likely to generate foreign matter even in a high-temperature and high-humidity environment can be obtained.

[0044] 1.1.3. Method for producing polyamide resin The above polyamide resin is polymerized, for example, as follows.

[0045] First, in the polymerization step (S1), a polyamide is polymerized by polycondensing a diamine monomer and a dicarboxylic acid monomer. Next, in the low-molecular-weight component removal step (S2), low-molecular-weight components are removed to obtain a polyamide resin mainly composed of polyamide.

[0046] 1.1.3.1. Polymerization step (S1) In the polymerization step (S1), a diamine monomer and a dicarboxylic acid monomer are polycondensed. The method of polycondensation for polymerizing the polyamide is not limited, and specific examples include melt polycondensation, the acid chloride method, direct polycondensation, etc.

[0047] In addition, a method of reacting a compound selected from the group consisting of a dicarboxylic acid monomer, a tetracarboxylic dianhydride, a trimellitic anhydride, and a dicarboxylic acid dichloride, which will be described later, with a compound having a hydroxyl group to obtain an active ester type dicarboxylic acid may be used. That is, this active ester type dicarboxylic acid may be used as a dicarboxylic acid monomer. Examples of the compound having a hydroxyl group include 1-hydroxybenzotriazole or a derivative of this 1-hydroxybenzotriazole. In addition, when obtaining this active ester type dicarboxylic acid, a condensing agent usually used in ordinary ester synthesis, such as dicyclohexylcarbodiimide, can be used. In addition, after adding an acid catalyst such as hydrochloric acid, sulfuric acid, benzenesulfonic acid, or toluenesulfonic acid, heating is performed to remove water generated from the alcohol compound and the carboxylic acid compound while allowing the reaction to proceed to promote esterification and obtain the above active ester type dicarboxylic acid.

[0048] The diamine monomer and the dicarboxylic acid monomer used for the polymerization of the polyamide resin will be described below. Note that only one type of each of the diamine monomer and the dicarboxylic acid monomer may be used, or two or more types of diamine monomers, two or more types of dicarboxylic acid monomers, or both of these may be used.

[0049] (Diamine monomer) The diamine monomer used for the polymerization is not limited. For example, it is preferable to use a diamine monomer containing an aromatic ring in its structure, and it is more preferable to use a diamine monomer containing a phenolic hydroxyl group in its structure. By producing a polyamide resin using such a diamine monomer as a raw material, the conformation of the polyamide resin can be controlled, and the dispersibility when made into a composition can be further improved.

[0050] Here, as the diamine monomer containing a phenolic hydroxyl group in the structure, for example, a compound represented by the formula (DA1) is preferable. By producing a polyamide resin using such a diamine monomer as a raw material, the conformation of the polyamide resin can be controlled, and the molecular chains of the polyamide resin can form a denser structure. Therefore, it is considered that the molecules of the alkali-soluble resin (A) and the metal molecules can be frozen in a more strongly bonded coordination, and the adhesion to the substrate can be improved.

[0051] Note that, for example, when the diamine monomer represented by the formula (DA1) is used, the polyamide resin contains a structural unit represented by the formula (PA3). That is, the polyamide resin preferably contains a structural unit represented by the formula (PA3), for example.

[0052]

Chemical formula

[0053] In the formula (DA1), R 4 is a group formed by one or more atoms 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. R 5 ~R 10 each independently represents hydrogen or an organic group having 1 to 30 carbon atoms.

[0054]

Chemical formula

[0055] In the formula (PA3), R 4 , R 5 ~R 10 is the same as in the formula (DA1).

[0056] R in the formula (DA1) and the formula (PA3) 4is a group formed by one or more atoms 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.

[0057] Note that R 4 is a divalent group. Here, the divalent group indicates the valence. That is, R 4 indicates that there are two bonds by which it binds to other atoms.

[0058] When R in formula (DA1) and formula (PA3) 4 contains a carbon atom, R 4 is, for example, a group having 1 to 30 carbon atoms, preferably a group having 1 to 10 carbon atoms, more preferably a group having 1 to 5 carbon atoms, and even more preferably a group having 1 to 3 carbon atoms.

[0059] When R in formula (DA1) and formula (PA3) 4 contains a carbon atom, examples of R 4 include an alkylene group, an arylene group, a halogen-substituted alkylene group, a halogen-substituted arylene group, and the like.

[0060] The alkylene group may be, for example, a linear alkylene group or a branched alkylene group. Specific examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decanylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and the like. Specific examples of the branched alkylene group include alkylmethylene groups such as -C(CH3)2-, -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-, and the like.

[0061] Examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a group formed by bonding two or more arylene groups to each other.

[0062] As the halogen-substituted alkylene group and the halogen-substituted arylene group, specifically, those obtained by substituting the hydrogen atoms in the above-described alkylene group and arylene group with halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms can be used. Among these, those obtained by substituting hydrogen atoms with fluorine atoms are preferably used.

[0063] R in formula (DA1) and formula (PA3) 4 When it does not contain a carbon atom, examples of R 4 include a group consisting of an oxygen atom or a sulfur atom.

[0064] R in formula (DA1) and formula (PA3) 5 ~R 10 are each independently hydrogen or an organic group having 1 to 30 carbon atoms. For example, it is preferably hydrogen or an organic group having 1 to 10 carbon atoms, more preferably hydrogen or an organic group having 1 to 5 carbon atoms, still more preferably hydrogen or an organic group having 1 to 3 carbon atoms, and particularly preferably hydrogen or an organic group having 1 to 2 carbon atoms. Thereby, the aromatic rings of the polyamide resin can be densely arranged. Therefore, the molecules of the alkali-soluble resin (A) and the metal molecules can be more strongly bonded in a coordinated manner to freeze the molecular structure and improve the adhesion.

[0065] R in formula (DA1) and formula (PA3) 5 ~R 10Specific examples of the organic group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc.; alkenyl groups such as allyl group, pentenyl group, vinyl group, etc.; alkynyl groups such as ethynyl group, etc.; alkylidene groups such as methylidene group, ethylidene group, etc.; aryl groups such as phenyl group, naphthyl group, anthracenyl group, etc.; aralkyl groups such as benzyl group, phenethyl group, etc.; cycloalkyl groups such as adamantyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, etc.; and alkaryl groups such as tolyl group, xylyl group, etc.

[0066] Specific examples of the diamine monomer represented by the formula (DA1) include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-methylenebis(2-amino-3,6-dimethylphenol), 4,4'-methylenebis(2-aminophenol), 1,1-bis(3-amino-4-hydroxyphenyl)ethane, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, etc. By using these diamine monomers, the aromatic rings of the polyamide resin are closely arranged. Therefore, the molecules of the alkali-soluble resin (A) and the metal molecules can be combined in a more strongly bonded coordination to freeze the molecular structure and improve the adhesion. Note that as the diamine monomer, one or more of the above specific examples can be used in combination. The structural formulas of these diamine monomers are shown below.

[0067] [Chemical formula]

[0068] (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.

[0069] As the dicarboxylic acid monomer containing an aromatic ring, for example, those represented by the formula (DC1) are preferably used. By producing a polyamide resin using such a dicarboxylic acid monomer as a raw material, the conformation of the polyamide resin can be controlled, and the dispersibility in a mixed solvent can be improved. And due to the improved dispersibility, a composition capable of forming a resin film that hardly generates foreign substances even in a high-temperature and high-humidity environment can be obtained.

[0070]

Chemical formula

[0071] In formula (DC1), R 11 is a group formed by one or more atoms 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. R 12 ~R 19 each independently represents hydrogen or an organic group having 1 to 30 carbon atoms.

[0072] For example, when the dicarboxylic acid monomer represented by the formula (DC1) is used, the polyamide resin typically contains a structural unit represented by the formula (PA4). In formula (PA4), R 11 and R 12 ~R 19 are the same as in formula (DC1).

[0073]

Chemical formula

[0074] R 11 in formula (DC1) and formula (PA4) is a group formed by one or more atoms 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.

[0075] In addition, R 11is a divalent group. Here, the divalent group indicates the valence. That is, R 11 indicates that there are two bonds by which it binds to other atoms.

[0076] When R in formula (DC1) and formula (PA4) 11 contains a carbon atom, R 11 is, for example, a group having 1 to 30 carbon atoms, preferably a group having 1 to 10 carbon atoms, more preferably a group having 1 to 5 carbon atoms, and even more preferably a group having 1 to 3 carbon atoms.

[0077] When R in formula (DC1) and formula (PA4) 11 contains a carbon atom, R 11 specifically includes an alkylene group, an arylene group, a halogen-substituted alkylene group, a halogen-substituted arylene group, and the like.

[0078] The alkylene group may be, for example, a linear alkylene group or a branched-chain alkylene group. Specific examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decanylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and the like. Specific examples of the branched-chain alkylene group include alkylmethylene groups such as -C(CH3)2-, -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkyl ethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-, and the like.

[0079] Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a group in which two or more arylene groups are bonded to each other.

[0080] As the halogen-substituted alkylene group and the halogen-substituted arylene group, specifically, those obtained by substituting the hydrogen atoms in the above-described alkylene group and arylene group with halogen atoms such as fluorine atom, chlorine atom, and bromine atom can be used. Among these, those obtained by substituting the hydrogen atoms with fluorine atoms are preferably used.

[0081] R in formula (DC1) and formula (PA4) 11 When it does not contain a carbon atom, examples of R 11 include a group consisting of an oxygen atom or a sulfur atom, etc.

[0082] R in formula (DC1) and formula (PA4) 12 ~R 19 are each independently hydrogen or an organic group having 1 to 30 carbon atoms. For example, it is preferably hydrogen or an organic group having 1 to 10 carbon atoms, more preferably hydrogen or an organic group having 1 to 5 carbon atoms, still more preferably hydrogen or an organic group having 1 to 3 carbon atoms, and particularly preferably hydrogen.

[0083] R in formula (DC1) and formula (PA4) 12 ~R 19 Specific examples of the organic group having 1 to 30 carbon atoms of R

[0084] 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, among the above specific examples, it is preferable to use diphenyl ether 4,4'-dicarboxylic acid or isophthalic acid, and it is more preferable to use diphenyl ether 4,4'-dicarboxylic acid. Thereby, the aromatic rings of the polyamide resin are densely arranged. Therefore, the molecules of the alkali-soluble resin (A) and the metal molecules can be frozen in a more strongly bonded coordination, and the adhesion can be improved.

[0085] Note that it is preferable to modify the amino group present at the end of the polyamide resin simultaneously with the polymerization step (S1) or after the polymerization step (S1). The modification can be 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 polyamide resin has an amino group at the end modified by the above specific acid anhydride or the above specific monocarboxylic acid. The above specific acid anhydride and the above specific monocarboxylic acid have one or more functional groups selected from the group consisting of an alkenyl group, an alkynyl group, and a hydroxyl group. Further, as the above specific acid anhydride and specific monocarboxylic acid, those containing a nitrogen atom are preferable, for example. Thereby, the wettability between the photosensitive resin composition for permanent film formation after post-baking and metals such as Cu and Al can be improved.

[0086] Specific examples of the above-mentioned specific acid anhydrides 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, 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, het acid anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride, and the like. As the specific acid anhydride, one or more of the above specific examples can be used in combination.

[0087] When the amino group present at the terminal of the polyamide resin is modified with a cyclic specific acid anhydride, the cyclic specific acid anhydride undergoes ring opening. Here, after modifying the polyamide resin, a structural unit derived from the cyclic specific acid anhydride may be cyclized to form an imide ring. Examples of the cyclization method include heat treatment and the like.

[0088] Specific examples of the above-mentioned specific monocarboxylic acids include 5-norbornene-2-carboxylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, and the like. As the specific monocarboxylic acid, one or more of the above specific examples can be used in combination.

[0089] Also, the carboxyl groups present at the terminals of the polyamide resin may be modified simultaneously with the polymerization step (S1) or after the polymerization step (S1). The modification can be carried out, for example, by reacting a specific nitrogen atom-containing heteroaromatic compound with a dicarboxylic acid monomer or a polyamide resin. Therefore, it is preferable that the polyamide resin has carboxyl groups at the terminals modified with a specific nitrogen atom-containing heteroaromatic compound. The above specific nitrogen atom-containing heteroaromatic compound is a compound having one or more functional groups selected from the group consisting of 1-(5-1H-triazolyl)methylamino group, 3-(1H-pyrazolyl)amino group, 4-(1H-pyrazolyl)amino group, 5-(1H-pyrazolyl)amino group, 1-(3-1H-pyrazolyl)methylamino group, 1-(4-1H-pyrazolyl)methylamino group, 1-(5-1H-pyrazolyl)methylamino group, (1H-tetrazol-5-yl)amino group, 1-(1H-tetrazol-5-yl)methyl-amino group, and 3-(1H-tetrazol-5-yl)benz-amino group. Thereby, the number of lone pairs of electrons in the photosensitive resin composition for permanent film formation can be increased. Therefore, after pre-baking, the wettability between the photosensitive resin composition for permanent film formation after post-baking and metals such as Cu and Al can be improved.

[0090] Specific examples of the above specific nitrogen atom-containing heteroaromatic compound include 5-aminotetrazole.

[0091] 1.1.3.2. Low molecular weight component removal step (S2) Following the above polymerization step (S'), it is preferable to perform a low molecular weight component removal step (S2) to remove low molecular weight components.

[0092] Specifically, an organic layer containing a mixture of low molecular weight components and a polyamide resin is concentrated by filtration or the like and then redissolved in an organic solvent such as water / isopropanol. Thereby, the precipitate can be filtered off to obtain a polyamide resin from which low molecular weight components have been removed.

[0093] Regarding the polyamide resin, for example, after the above-mentioned low molecular weight component removal step, it is preferable to prepare a photosensitive resin composition for a permanent film which is a varnish without going through a step of completely volatilizing the solvent to become dry. Thereby, it is possible to suppress a decrease in the dispersibility of the polyamide due to the interaction derived from the amide bond between the molecules of the polyamide resin. As a result, a composition capable of forming a resin film that hardly generates foreign matters even in a high temperature and high humidity environment can be obtained.

[0094] 1.2. Photosensitizer (B) The photosensitizer (B) contains a photosensitive diazoquinone compound represented by the formula (B-1). This photosensitive diazoquinone compound is a photoacid generator that generates an acid by absorbing light energy, and contributes to improving the accuracy of the pattern of the resin film and improving the appearance.

[0095] TIFF2025111264000013.tif66170

[0096] Here, as a result of investigations by the present inventors, it has been found that foreign matters generated when a conventional resin film is exposed to a high temperature and high humidity environment are likely to be caused by unreacted substances of the photosensitizer remaining in the resin film or decomposed products of the photosensitizer.

[0097] Therefore, in the photosensitive resin composition for a permanent film according to the present embodiment, a photosensitizer (B) containing a photosensitive diazoquinone compound represented by the formula (B-1) is used. This photosensitive diazoquinone compound has a lower decomposition start temperature during heating than other photosensitizers. For this reason, even if this photosensitive diazoquinone compound remains in the resin film in an unreacted state, it is likely to decompose and volatilize in a heating process such as post-baking. Therefore, even if unreacted substances are generated, they are unlikely to remain in the resin film after passing through the heating process. As a result, generation of foreign matters can be suppressed even when the resin film is exposed to a high temperature and high humidity environment.

[0098] In addition, upon examination of foreign matter generated in conventional resin films, it was also found that hydrophilic substances are extracted onto the surface of the resin film in a high-temperature and high-humidity environment and are likely to aggregate into foreign matter.

[0099] Therefore, in the photosensitive resin composition for permanent film formation according to the present embodiment, in addition to the above photosensitive diazoquinone compound, an additive (E) containing a biphenol compound described later is used in combination. Thereby, even when decomposition products of the photosensitizer and other contained components have hydrophilicity, generation of foreign matter can be suppressed. This effect will be described in detail later.

[0100] In the formula (B-1), Q preferably contains 50% or more, more preferably 60% or more of the structure represented by the above formula (a). Thereby, the above effects become more remarkable.

[0101] In addition to the compound represented by the formula (B-1), the photosensitizer (B) may also contain the following compounds. Specifically, diazoquinone compounds; diaryliodonium salts; 2-nitrobenzyl ester compounds; N-iminosulfonate compounds; imidosulfonate compounds; 2,6-bis(trichloromethyl)-1,3,5-triazine compounds; dihydropyridine compounds and the like can be mentioned. The photosensitizer (B) can contain one or more of the above specific examples. In the photosensitizer (B), the ratio of the compound represented by the formula (B-1) is preferably 60% by mass or more, more preferably 80% by mass or more.

[0102] When the photosensitive resin composition for permanent film formation is a positive type, in addition to the above specific examples, the photosensitizer (B) may also contain onium salts such as triarylsulfonium salts; sulfonium borate salts and the like. Thereby, the sensitivity of the photosensitive resin composition for permanent film formation can be further improved. Hereinafter, diazoquinone compounds will be exemplified using chemical formulas.

[0103]

Chemical formula

[0104]

Chem.

[0105]

Chem.

[0106]

Chem.

[0107]

Chem.

[0108] In each of the above diazoquinone compounds, Q is a structure represented by formula (a), formula (b) and formula (c) or a hydrogen atom. However, at least one of Qs of each diazoquinone compound is a structure represented by formula (a), formula (b) and formula (c).

[0109] Preferably, Q of the diazoquinone compound contains formula (a) or formula (b). Thereby, the transparency of the photosensitive resin composition for permanent film formation can be improved. Therefore, the appearance of the photosensitive resin composition for permanent film formation can be improved.

[0110]

Chem.

[0111] In the photosensitive resin composition for forming a permanent film, the lower limit of the content of the photosensitizer (B) is 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 when the alkali-soluble resin (A) is 100 parts by mass. Thereby, the photosensitive resin composition for forming a permanent film has appropriate sensitivity. The upper limit of the content of the photosensitizer (B) in the photosensitive resin composition for forming a permanent film is preferably 30 parts by mass or less, more preferably 20 parts by mass or less when the alkali-soluble resin (A) is 100 parts by mass. Thereby, it is possible to prevent the photosensitive resin composition for forming a permanent film from being repelled by the metal material present on the substrate surface of the semiconductor device. <00>

[0112] 1.3. Surfactant (C) Desirable physical properties of the surfactant (C) include high polarity and low surface tension reducing ability. By using a surfactant (C) with high polarity, the compatibility between the alkali-soluble resin (A) and other components including the solvent described below can be enhanced, and thus the coating film performance when forming a coating film using the photosensitive resin composition for forming a permanent film can be improved. In addition, by reducing the surface tension reducing ability, the wettability with respect to the metal material can be enhanced, and the coating film performance when forming a coating film using the photosensitive resin composition for forming a permanent film can be improved.

[0113] Examples of the surfactant (C) include nonionic surfactants such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; fluorosurfactants commercially available under names such as Ftop EF301, Ftop EF303, Ftop EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, Megafac F477 (manufactured by DIC Corporation), Fluorad FC-430, Fluorad FC-431, Novec FC4430, Novec FC4432 (manufactured by 3M Japan Ltd.), Surflon S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.); organosiloxane copolymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic acid-based copolymers Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

[0114] As the surfactant (C), silicone surfactants (such as polyether-modified dimethylsiloxane, etc.) can also be preferably used. Specific examples of the silicone surfactants include the SH series, SD series, and ST series of Toray Dow Corning, the BYK series of BYK Chemie Japan, the KP series of Shin-Etsu Chemical Co., Ltd., the Disform (registered trademark) series of NOF Corporation, the TSF series of Toshiba Silicone Co., Ltd., and the like.

[0115] The surfactant (C) preferably contains, in particular, an organically modified dimethylsiloxane represented by the formula (C-1). Thereby, even when the photosensitive resin composition for permanent film formation absorbs moisture, the function of the surfactant (C) is less likely to deteriorate, and the dissolution state (dispersion state) of each component can be maintained. As a result, it is possible to suppress the occurrence of unintended reactivity in the photosensitive resin composition for permanent film formation to generate reaction products, or the decrease in the solubility of the components to generate precipitates. And while enhancing the storage stability of the photosensitive resin composition for permanent film formation, a photosensitive resin composition for permanent film formation capable of forming a resin film less likely to generate foreign substances even in a high-temperature and high-humidity environment can be obtained.

[0116]

Chemical formula

[0117] In the formula (C-1), X represents a polyether (polyoxyalkylene) group, a polyester group, or an aralkyl group, and m and n each represent an integer of 1 or more and 100 or less. When X in the formula (C-1) is a polyether group, a polyether group represented by the formula (2-1) is preferably used as X.

[0118]

Chemical formula

[0119] In the formula (2-1), R 20 represents an alkyl group having 1 to 6 carbon atoms, and R 21 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyl ether group having 1 to 6 carbon atoms, or an unsaturated alkyl ether group having 1 to 6 carbon atoms, EO represents an ethylene oxide group, and PO represents a propylene oxide group. o represents an integer of 1 or more, and p represents an integer of 0 or more. The order of EO and PO may be random.

[0120] As a result, a photosensitive resin composition for forming a permanent film can be obtained, which particularly enhances the storage stability of the photosensitive resin composition for forming a permanent film and can form a resin film that is less likely to generate foreign matter even in a high-temperature and high-humidity environment.

[0121] When X in formula (C-1) contains a propylene oxide group, the lower limit of the molar ratio of the propylene oxide group to the total molar amount of the ethylene oxide group and the propylene oxide group is preferably 1% or more, more preferably 10% or more, and even more preferably 20% or more. On the other hand, the upper limit of the molar ratio of the propylene oxide group is preferably 99% or less, more preferably 90% or less, and even more preferably 80% or less. By setting the molar ratio of the propylene oxide group within the above range, the wettability with the metal can be improved.

[0122] When X in formula (C-1) is a polyester group, as X, a polyester group represented by formula (2-2) is preferably used.

[0123]

Chemical formula

[0124] In formula (2-2), R 22 , R 23 , R 24 and R 25 each independently represent an alkyl group having 1 to 20 carbon atoms, and r represents an integer of 1 or more.

[0125] When X in formula (C-1) is an aralkyl group, as X, an aralkyl group represented by formula (2-3) is preferably used.

[0126]

Chemical formula

[0127] In formula (2-3), R 26 represents an alkyl group having 1 to 30 carbon atoms.

[0128] The lower limit of the ratio of m to the total of m and n represented by formula (C-1) is preferably 0.5% or more, more preferably 1% or more, still more preferably 5% or more, and particularly preferably 10% or more. On the other hand, the upper limit of the ratio of m is preferably 60% or less, more preferably 50% or less, still more preferably 40% or less, and particularly preferably 30% or less. By setting the ratio of m within the above range, the wettability with the metal can be improved.

[0129] The content of the surfactant (C) in the photosensitive resin composition for permanent film formation is not particularly limited, but the lower limit value of the content is preferably 0.001% by mass (10 ppm) or more, more preferably 0.01% by mass (100 ppm) or more, from the viewpoint of sufficiently obtaining the effect of the surfactant, based on the total including the solvent of the photosensitive resin composition for permanent film formation. Further, the upper limit value of the content is preferably 1% by mass (10,000 ppm) or less, more preferably 0.5% by mass (5,000 ppm) or less, still more preferably 0.1% by mass (1,000 ppm) or less, based on the total including the solvent of the photosensitive resin composition for permanent film formation. By setting the content of the surfactant (C) within the above range, the effect as a surfactant of enhancing the compatibility between the alkali-soluble resin (A) and other components including the solvent can be further enhanced.

[0130] 1.4. Adhesion Aid (D) Specific examples of the adhesion aid (D) include triazole compounds, silane compounds, or imide compounds, and silane compounds are particularly preferably used. By using these, the affinity between the photosensitive resin composition for permanent film formation and metal members such as Cu and Al can be improved.

[0131] Specific examples of the triazole compound include 1,2,4-triazoles such as 4-amino-1,2,4-triazole, 4H-1,2,4-triazol-3-amine, 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-methyl-4H-1,2,4-triazol-3-amine, 3,4-diamino-4H-1,2,4-triazole, 3,5-diamino-4H-1,2,4-triazole, 1,2,4-triazole-3,4,5-triamine, 3-pyridyl-4H-1,2,4-triazole, 4H-1,2,4-triazole-3-carboxamide, 3,5-diamino-4-methyl-1,2,4-triazole, 3-pyridyl-4-methyl-1,2,4-triazole, 4-methyl-1,2,4-triazole-3-carboxamide. As the triazole compound, one or a combination of two or more of the above specific examples can be used.

[0132] As silane compounds, specifically, vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styryl silanes such as p-styryltrimethoxysilane; methacryl silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic silanes such as 3-acryloxypropyltrimethoxysilane; isocyanurate silane; alkyl silane; ureido silanes such as 3-ureidopropyltrialkoxysilane; mercapto silanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate silanes such as 3-isocyanatopropyltriethoxysilane, etc.;Condensates of cyclohexene-1,2-dicarboxylic anhydride and 3-aminopropyltriethoxysilane, condensates of 3,3’,4,4’-benzophenonetetracarboxylic dianhydride and 3-aminopropyltriethoxysilane, condensates of 4,4’-oxydiphthalic anhydride and 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N,N’-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N’-bis-(3-triethoxysilylpropyl)ethylenediamine, N,N’-bis[3-(methyldimethoxysilyl)propyl]ethylenediamine, N,N’-bis[3-(methyldiethoxysilyl)propyl]ethylenediamine, N,N’-bis[3-(dimethoxymethylsilyl)propyl]ethylenediamine, N-[3-(methyldimethoxysilyl)propyl]-N’-[3-(trimethoxysilyl)propyl]ethylenediamine, N,N’-bis[3-(trimethoxysilyl)propyl]diaminopropane, N,N’-bis[3-(trimethoxysilyl)propyl]diaminohexane, N,N’-bis[3-(trimethoxysilyl)propyl]diethylenetriamine and other aminosilane compounds such as these can be mentioned. As the silane compound, one or a combination of two or more of the above specific examples can be used.;

[0133] Examples of the imide compound include the compounds exemplified below. These can be used alone or in combination of two or more.;

[0134]

Chemical formula

[0135] The lower limit of the content of the adhesion promoter (D) in the photosensitive resin composition for forming a permanent film is preferably 0.1 part by mass or more, more preferably 1.0 part by mass or more, still more preferably 2.0 part by mass or more, and particularly preferably 3.0 part by mass or more with respect to 100 parts by mass of the alkali-soluble resin (A). The upper limit of the content of the adhesion promoter (D) in the photosensitive resin composition for forming a permanent film is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 25 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A).

[0136] By setting the content of the adhesion promoter (D) within the above range, the adhesion promoter is preferably dispersed in the photosensitive resin composition for forming a permanent film, the adhesion of the photosensitive resin composition for forming a permanent film to the adherend can be improved, and a photosensitive resin composition for forming a permanent film capable of forming a resin film less likely to generate foreign substances even in a high-temperature and high-humidity environment can be obtained.

[0137] The adhesion promoter (D) may contain a titanium coupling agent, an aluminum coupling agent, or a zirconium coupling agent.

[0138] 1.5. Additive (E) The additive (E) contains a biphenol compound having a molecular weight of 150 or more and 1000 or less. This biphenol compound may have at least 2 hydroxyl groups per molecule, preferably has 2 to 7 hydroxyl groups, and more preferably has 2 to 6 hydroxyl groups. Thereby, the biphenol compound has good hydrophilicity and has an action of attracting the moisture contained in the resin film. For this reason, even when the resin film formed using the photosensitive resin composition for forming a permanent film is exposed to a high-temperature and high-humidity environment, the extraction of hydrophilic substances to the surface can be suppressed. As a result, the generation of foreign substances in the resin film in a high-temperature and high-humidity environment can be suppressed.

[0139] In addition, when the number of hydroxyl groups per molecule is less than the lower limit value, the action of attracting moisture is reduced, and the generation of foreign matters cannot be sufficiently suppressed in the resin film in a high-temperature and high-humidity environment. On the other hand, when the number of hydroxyl groups per molecule exceeds the upper limit value, the hydrophilicity of the biphenol compound becomes excessive and it becomes easy to absorb moisture. Therefore, depending on the storage environment, the storage stability of the photosensitive resin composition for permanent film formation may decrease.

[0140] The molecular weight of the biphenol compound is 150 or more and 1000 or less, preferably 200 or more and 500 or less, and more preferably 200 or more and 400 or less. Thereby, the biphenol compound has good solubility in the solvent. For this reason, the above effects can be uniformly enjoyed in the resin film.

[0141] In addition, when the molecular weight is less than the lower limit value, in the biphenol compound, the action of attracting moisture contained in the resin film cannot be sufficiently obtained. On the other hand, when the molecular weight exceeds the upper limit value, the solubility of the biphenol compound in the solvent decreases, so that the effect of suppressing the generation of foreign matters may become uneven.

[0142] Examples of the biphenol compound include 2,2'-biphenol and 4,4'-biphenol, and isomers thereof. These biphenol compounds may have a substituent. Examples of this substituent include a hydroxyl group, a halogen, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, or an organic group having an aromatic structure having 6 to 20 carbon atoms. Examples of such biphenol compounds include, but are not limited to, the following compounds.

[0143]

Chemical formula

[0144] As the biphenol compound, one or more of the above specific examples can be blended. The biphenol compound is more preferably phloroglucide. Phloroglucide has five hydroxyl groups per molecule, has appropriate hydrophilicity, and is also well dissolved in a solvent containing an organic solvent. As a result, the generation of foreign matters can be particularly suppressed.

[0145] The lower limit of the content of the additive (E) in the photosensitive resin composition for forming a permanent film is 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 with respect to 100 parts by mass of the alkali-soluble resin (A). The upper limit of the content of the additive (E) in the photosensitive resin composition for forming a permanent film is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A). Thereby, while suppressing the decrease in the chemical resistance of the resin film due to the addition of the additive (E), the above effects, that is, the effect of suppressing the generation of foreign matters in a high temperature and high humidity environment can be enjoyed.

[0146] In addition, when the content of the additive (E) is less than the lower limit value, there is a possibility that the effect of suppressing the generation of foreign matters in the resin film cannot be enjoyed. On the other hand, when the content of the additive (E) exceeds the upper limit value, the chemical resistance of the resin film may decrease.

[0147] Further, let the content of the photosensitive diazoquinone compound represented by the formula (B-1) be Xb1, and the content of the biphenol compound having a molecular weight of 150 or more and 1000 or less be Xe. The ratio Xe / Xb1 of the content Xe to the content Xb1 is preferably 0.10 or more and 0.90 or less, more preferably 0.30 or more and 0.60 or less, and still more preferably 0.35 or more and 0.50 or less. If the ratio Xe / Xb1 is within the above range, the balance between the content Xb1 and the content Xe can be optimized. Thereby, the occurrence of excess and deficiency of both can be suppressed, and the above effects, that is, the effect of suppressing the generation of foreign matters in a high temperature and high humidity environment can be more surely enjoyed.

[0148] In addition, when the ratio Xe / Xb1 is lower than the lower limit value, the content of Xe is relatively insufficient, and there is a risk that the above-mentioned action by the biphenol compound may not be sufficiently exhibited. On the other hand, when the ratio Xe / Xb1 exceeds the upper limit value, the content of Xb1 is relatively insufficient, and there is a risk that the above-mentioned action by the photosensitive diazoquinone compound may not be sufficiently exhibited.

[0149] 1.6. Thermal crosslinking agent (F) The photosensitive resin composition for permanent film formation may contain a thermal crosslinking agent (F) capable of reacting with the alkali-soluble resin (A) by heat. Thereby, for the cured product obtained by post-baking the photosensitive resin composition for permanent film formation, mechanical properties such as tensile elongation at break can be improved. In addition, the sensitivity of the resin film formed by the photosensitive resin composition for permanent film formation can be improved.

[0150] As the heat crosslinking agent (F), specifically, compounds having a methylol group such as 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol (paraxylene glycol), 1,3,5-benzenetrimethanol, 4,4-biphenyldimethanol, 2,6-pyridinedimethanol, 2,6-bis(hydroxymethyl)-p-cresol, 4,4'-methylenebis(2,6-dialkoxymethylphenol); compounds having an alkoxymethyl group such as 1,4-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl)benzene, 4,4'-bis(methoxymethyl)biphenyl, 3,4'-bis(methoxymethyl)biphenyl, 3,3'-bis(methoxymethyl)biphenyl, methyl 2,6-naphthalenedicarboxylate, 4,4'-methylenebis(2,6-dimethoxymethylphenol); methylol melamine compounds represented by hexamethylol melamine, hexabutanol melamine, etc.; alkoxymelamine compounds such as hexamethoxymelamine; alkoxymethyl glycoluril compounds such as tetramethoxymethyl glycoluril; methylol benzoguanamine compounds, methylol urea compounds such as dimethylol ethylene urea; cyano compounds such as dicyanoaniline, dicyanophenol, cyanophenylsulfonic acid; isocyanate compounds such as 1,4-phenylene diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; epoxy group-containing compounds such as ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, triglycidyl isocyanurate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene-based epoxy resin, biphenyl type epoxy resin, phenol novolak resin type epoxy resin; maleimide compounds such as N,N'-1,3-phenylene dimaleimide, N,N'-methylenebis maleimide, etc. As the heat crosslinking agent, one or more of the above specific examples can be used in combination.

[0151] The lower limit of the content of the thermal crosslinking agent (F) in the photosensitive resin composition for forming a permanent film is preferably 0.1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and particularly preferably 6 parts by mass or more with respect to 100 parts by mass of the alkali-soluble resin (A). The upper limit of the content of the thermal crosslinking agent (F) in the photosensitive resin composition for forming a permanent film is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A). Thereby, even when the thermal crosslinking agent (F) has a solvating functional group such as a phenolic hydroxyl group, it is possible to suppress a decrease in chemical resistance after post-baking.

[0152] 1.7. Dissolution regulator The photosensitive resin composition for forming a permanent film may contain a dissolution regulator. Thereby, the solubility of the solid content of the photosensitive resin composition for forming a permanent film in a solvent can be adjusted. As a result, a photosensitive resin composition for forming a permanent film capable of forming a resin film that hardly generates foreign matters can be obtained.

[0153] Examples of the dissolution regulator include silane compounds other than the above-described silane compounds, and particularly, silane coupling agents having a hydrophobic functional group and a hydrolyzable group are preferably used. Examples of the hydrophobic functional group include an alkyl group, a cycloalkyl group, a phenyl group, and the like. Examples of such silane coupling agents include hexyltrimethoxysilane, decyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, cyclohexylmethyldimethoxysilane, and the like.

[0154] The lower limit of the content of the dissolution regulator in the photosensitive resin composition for permanent film formation is preferably 0.1 part by mass or more, more preferably 1.0 part by mass or more, and even more preferably 1.5 part by mass or more with respect to 100 parts by mass of the alkali-soluble resin (A). The upper limit of the content of the dissolution regulator in the photosensitive resin composition for permanent film formation is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A). Thereby, a photosensitive resin composition for permanent film formation capable of forming a resin film less likely to generate foreign matters even in a high-temperature and high-humidity environment can be obtained.

[0155] 1.8. Antioxidant The photosensitive resin composition for permanent film formation may contain an antioxidant. As the antioxidant, one or more selected from phenolic antioxidants, phosphorus antioxidants, and thioether antioxidants can be used. The antioxidant can suppress the oxidation of the resin film formed by the photosensitive resin composition for permanent film formation.

[0156] As phenolic antioxidants, there are pentaerythrityl - tetrakis〔3-(3,5 - di - t - butyl - 4 - hydroxyphenyl)propionate〕, 3,9 - bis{2 - 〔3-(3 - t - butyl - 4 - hydroxy - 5 - methylphenyl)propionyloxy〕-1,1 - dimethylethyl}2,4,8,10 - tetraoxaspiro〔5,5〕undecane, octadecyl - 3-(3,5 - di - t - butyl - 4 - hydroxyphenyl)propionate, 1,6 - hexanediol - bis〔3-(3,5 - di - t - butyl - 4 - hydroxyphenyl)propionate〕, 1,3,5 - trimethyl - 2,4,6 - tris(3,5 - di - t - butyl - 4 - hydroxybenzyl)benzene, 2,6 - di - t - butyl - 4 - methylphenol, 2,6 - di - t - butyl - 4 - ethylphenol, 2,6 - diphenyl - 4 - octadecyloxyphenol, stearyl(3,5 - di - t - butyl - 4 - hydroxyphenyl)propionate, distearyl(3,5 - di - t - butyl - 4 - hydroxybenzyl)phosphonate, thiodiethylene glycol bis〔(3,5 - di - t - butyl - 4 - hydroxyphenyl)propionate〕, 4,4’ - thiobis(6 - t - butyl - m - cresol), 2 - octylthio - 4,6 - di(3,5 - di - t - butyl - 4 - hydroxyphenoxy)-s - triazine, 2,2’ - methylenebis(4 - ethyl - 6 - t - butylphenol), bis〔3,3 - bis(4 - hydroxy - 3 - t - butylphenyl)butyric acid〕glycol ester, 4,4’ - butylidenebis(6 - t - butyl - m - cresol), 2,2’ - ethylidenebis(4,6 - di - t - butylphenol), 2,2’ - ethylidenebis(4 - s - butyl - 6 - t - butylphenol), 1,1,3 - tris(2 - methyl - 4 - hydroxy - 5 - t - butylphenyl)butane, bis〔2 - t - butyl - 4 - methyl - 6-(2 - hydroxy - 3 - t - butyl - 5 - methylbenzyl)phenyl〕terephthalate, 1,3,5 - tris(2,6 - dimethyl - 3 - hydroxy - 4 - t - butylbenzyl)isocyanurate, 1,3,5 - tris(3,5 - di - t - butyl - 4 - hydroxybenzyl)-2,4,6 - trimethylbenzene, 1,3,5 - tris〔(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl] isocyanurate, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2-t-butyl-4-methyl-6-(2-acryloyloxy-3-t-butyl-5-methylbenzyl)phenol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane-bis[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], triethylene glycol bis[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], 1,1'-bis(4-hydroxyphenyl)cyclohexane, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(6-(1-methylcyclohexyl)-4-methylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis(2-(3-t-butyl-4-hydroxy-5-methylphenylpropionyloxy)1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide, 4,4'-thiobis(6-t-butyl-2-methylphenol), 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-dimethyl-6-(1-methylcyclohexyl)phenol, styrenated phenol, 2,4-bis((octylthio)methyl)-5-methylphenol, etc.

[0157] Examples of phosphorus-based antioxidants include bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl) phosphite, tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4'-biphenylene diphosphonite, 3,5-di-t-butyl-4-hydroxybenzyl phosphonate-diethyl ester, bis-(2,6-dicumylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-t-butylphenyl) octyl phosphite, tris(mixed mono- and di-nonylphenyl) phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methoxycarbonylethyl-phenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-octadecyloxycarbonylethylphenyl)pentaerythritol diphosphite, and the like.

[0158] Examples of thioether-based antioxidants include dilauryl-3,3'-thiodipropionate, bis(2-methyl-4-(3-n-dodecyl)thiopropionyloxy)-5-t-butylphenyl) sulfide, distearyl-3,3'-thiodipropionate, pentaerythritol-tetrakis(3-lauryl) thiopropionate, and the like.

[0159] 1.9. Solvent (G) The photosensitive resin composition for forming a permanent film may contain a solvent (G). Examples of the solvent (G) include various organic solvents.Examples of the solvent (G) include amide solvents such as N-methyl-2-pyrrolidone (NMP), 3-methoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N,N-dimethylpropionamide, N,N-diethylacetamide, 3-butoxy-N,N-dimethylpropanamide, and N,N-dibutylformamide; urea solvents such as N,N-dimethylacetamide, tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone, tetrabutylurea, N,N'-dimethylpropyleneurea, 1,3-dimethoxy-1,3-dimethylurea, N,N'-diisopropyl-O-methylisourea, O,N,N'-triisopropylisourea, O-tert-butyl-N,N'-diisopropylisourea, and O-ethyl-N,N'-diisopropylisourea; ether solvents such as propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, and 1,3-butylene glycol-3-monomethyl ether; acetate solvents such as propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, and methyl-1,3-butylene glycol acetate; alcohol solvents such as tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol, butanediol, and isopropyl alcohol; ketone solvents such as cyclopentanone, cyclohexanone, diacetone alcohol, and 2-heptanone; lactone solvents such as γ-butyrolactone (GBL) and γ-valerolactone; carbonate solvents such as ethylene carbonate and propylene carbonate; sulfone solvents such as dimethyl sulfoxide (DMSO) and sulfolane; ester solvents such as methyl pyruvate, ethyl pyruvate, and methyl 3-methoxypropionate; and aromatic hydrocarbon solvents such as mesitylene, toluene, and xylene, etc.As the solvent (G), one or a combination of two or more of the above specific examples can be used.

[0160] As the solvent (G), it is preferable to use in combination one or more selected from the group consisting of amide solvents and urea solvents and one or more selected from the group consisting of acetate solvents and lactone solvents among the above specific examples. Thereby, the dispersibility of the alkali-soluble resin (A) can be particularly improved.

[0161] The lower limit of the content of the solvent (G) in the photosensitive resin composition for permanent film formation is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more of the whole photosensitive resin composition for permanent film formation. Also, the upper limit of the content of the solvent (G) in the photosensitive resin composition for permanent film formation is preferably 95% by mass or less, more preferably 90% by mass or less of the whole photosensitive resin composition for permanent film formation. Thereby, a photosensitive resin composition for permanent film formation capable of improving the dispersibility in the photosensitive resin composition for permanent film formation and forming a resin film less likely to generate foreign matters even in a high-temperature and high-humidity environment can be obtained.

[0162] 1.10. Other Components The photosensitive resin composition for permanent film formation may contain additives such as fillers and sensitizers in addition to the above respective constituent components.

[0163] The filler is appropriately selected according to the mechanical properties and thermal properties required for the resin film formed by the photosensitive resin composition for permanent film formation.

[0164] Specific examples of the filler include inorganic fillers and organic fillers. Specific examples of the inorganic filler include silica such as fused crushed silica, fused spherical silica, crystalline silica, secondary aggregated silica, and fine silica powder; metal compounds such as alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, silicon carbide, aluminum hydroxide, magnesium hydroxide, and titanium white; talc; clay; mica; and glass fiber. Among the above specific examples, one or more of the inorganic fillers can be used in combination.

[0165] Specific examples of the organic filler include organosilicon powder and polyethylene powder. Among the above specific examples, one or more of the organic fillers can be used in combination.

[0166] 1.11. Method for Preparing Photosensitive Resin Composition for Permanent Film Formation The method for preparing the photosensitive resin composition for permanent film formation is not limited, and a known method is used according to the constituent components.

[0167] For example, each of the above constituent components can be prepared by mixing and dissolving them in a solvent. Thereby, a varnish-like photosensitive resin composition for permanent film formation can be obtained.

[0168] Further, from the viewpoint of suppressing the moisture absorption of the photosensitive resin composition for permanent film formation as much as possible, the preparation of the photosensitive resin composition for permanent film formation is preferably carried out under a nitrogen atmosphere.

[0169] 2. Permanent Film Next, the permanent film according to the embodiment will be described.

[0170] A cured product is obtained by drying or curing the photosensitive resin composition for permanent film formation according to the embodiment. The permanent film according to the embodiment is composed of this cured product. Thereby, a permanent film that hardly generates foreign substances even in a high-temperature and high-humidity environment can be obtained. Such a permanent film is used in semiconductor devices. Examples of the permanent film of the semiconductor device include a protective film such as a buffer coat film, an interlayer film such as an insulating film for rewiring, and a dam material.

[0171] The permanent film described above is composed of a cured product obtained by, for example, pre-baking, exposing, and developing a photosensitive resin composition for forming a permanent film, patterning it into a desired shape, and then post-baking it to harden it.

[0172] Furthermore, when the photosensitive resin composition for forming a permanent film is applied, it is preferably applied by slit coating, which allows a more uniform coating film to be formed on the substrate.

[0173] The thickness of the permanent film is not particularly limited, but is, for example, about 2 to 30 μm, and preferably about 5 to 20 μm.

[0174] After coating the photosensitive resin composition for forming a permanent film, various methods such as heating can be used to remove the solvent. However, when used in panel level packaging, it is preferable to apply reduced pressure drying in view of the relatively large area. In other words, it is preferable to dry the panel coated with the photosensitive resin composition for forming a permanent film under a reduced pressure environment (for example, an environment of 30 Pa or less). In addition, reduced pressure drying has the advantage of reducing microbubbles that may be generated during coating.

[0175] When pre-baking is performed, the conditions are, for example, 70 to 160° C. and about 5 seconds to 30 minutes.

[0176] For the exposure, electromagnetic waves or particle beams of various wavelengths can be used. For example, ultraviolet rays such as g-rays and i-rays, visible light, lasers, X-rays, electron beams, etc. are used. Ultraviolet rays such as g-rays or i-rays are preferred. The exposure dose is appropriately set depending on the sensitivity of the photosensitive resin composition for forming a permanent film, and is, for example, 30 to 3000 mJ / cm. 2 That's about it.

[0177] Regarding development, various developers can be applied. For example, alkali developers such as alkali metal carbonates, alkali metal hydroxides, and tetramethylammonium hydroxide, organic developers such as dimethylformamide, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl acetate can be mentioned. Among these, alkali developers are preferred, and particularly, an aqueous solution of tetramethylammonium hydroxide is preferred. As the supply method of the developer, methods such as spraying, paddling, and dipping can be mentioned. From the perspective of processing large-area panels, the spraying method is preferred.

[0178] The conditions of post-baking (curing conditions) are not particularly limited, but for example, it is 80 to 300 °C for 30 to 300 minutes.

[0179] 3. Semiconductor device Next, the semiconductor device according to the embodiment will be described.

[0180] FIG. 1 is a cross-sectional view showing a semiconductor device (semiconductor device according to the embodiment) including a permanent film according to the embodiment.

[0181] The semiconductor device 100 shown in FIG. 1 includes the above-mentioned permanent film. Specifically, among the insulating layer 42 and the insulating layer 44 of the semiconductor device 100, the above-mentioned permanent film is used for one or more of them. Thereby, the occurrence of defects related to foreign matters is suppressed even in a high-temperature and high-humidity environment, and a high-quality semiconductor device 100 can be obtained.

[0182] The semiconductor device 100 is, for example, a semiconductor chip. In this case, a semiconductor package can be obtained by mounting the semiconductor device 100 on a wiring board via bumps 52. The semiconductor device 100 shown in FIG. 1 includes a semiconductor substrate (not shown) provided with semiconductor elements such as transistors, a multilayer wiring layer including an interlayer insulating film 30 and a topmost layer wiring 34 provided on the semiconductor substrate, a passivation film 32, a redistribution layer 40, a UBM layer 50, and bumps 52.

[0183] The interlayer insulating film 30 and the topmost layer wiring 34 are provided at the uppermost part of the multilayer wiring layer. The topmost layer wiring 34 is made of, for example, aluminum. Also, a passivation film 32 is provided on the interlayer insulating film 30 and on the topmost layer wiring 34. An opening is provided in a part of the passivation film 32 where the topmost layer wiring 34 is exposed.

[0184] A rewiring layer 40 is provided on the passivation film 32. The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and on the rewiring 46. An opening for connecting to the topmost layer wiring 34 is formed in the insulating layer 42. The rewiring 46 is formed on the insulating layer 42 and within the opening provided in the insulating layer 42, and is connected to the topmost layer wiring 34. An opening for connecting to the rewiring 46 is provided in the insulating layer 44.

[0185] A bump 52 is formed within the opening provided in the insulating layer 44 via a UBM layer 50 (Under Bump Metallurgy). The semiconductor device 100 is connected to a wiring board or the like via the bump 52.

[0186] When applying the permanent film to one or more of the insulating layer 42 and the insulating layer 44, for example, after patterning a coating film formed of a photosensitive resin composition for forming a permanent film by exposing it to ultraviolet light and developing it, this is heat-cured to form the insulating layer 42 or the insulating layer 44. That is, a coating film forming step of applying a photosensitive resin composition for forming a permanent film to form a coating film, an exposure step of exposing the formed coating film, a developing step of developing the exposed coating film, and a heating step of heating and curing the coating film remaining after development to form a permanent film, thereby forming the permanent film and using it as the insulating layer 42 or the insulating layer 44.

[0187] 4. Effects Exhibited by the Embodiment As described above, the photosensitive resin composition for permanent film formation according to the embodiment includes an alkali-soluble resin (A), a photosensitizer (B), a surfactant (C), an adhesion aid (D), and an additive (E). Further, the photosensitizer (B) contains a photosensitive diazoquinone compound represented by the formula (B-1), and the additive (E) contains a biphenol compound having a molecular weight of 150 or more and 1000 or less.

[0188]

Chemical formula

[0189] According to such a configuration, since the photosensitizer (B) and the additive (E) each contain a predetermined compound, a photosensitive resin composition for permanent film formation capable of producing a permanent film that is less likely to generate foreign substances even in a high-temperature and high-humidity environment can be obtained. Such a permanent film can suppress the occurrence of defects related to foreign substances even when subjected to an accelerated reliability test such as a PCT test (pressure cooker test).

[0190] Further, in the photosensitive resin composition for permanent film formation according to the embodiment, the alkali-soluble resin (A) is preferably a resin in which a dehydration ring-closure reaction proceeds at a temperature of less than 300°C.

[0191] According to such a configuration, a photosensitive resin composition for permanent film formation capable of forming a resin film that is less likely to generate foreign substances even in a high-temperature and high-humidity environment can be obtained. [[ID=@22]]

[0192] Further, in the photosensitive resin composition for permanent film formation according to the embodiment, the adhesion aid (D) may contain a silane compound.

[0193] According to such a configuration, a photosensitive resin composition for permanent film formation with particularly improved affinity for metal members such as Cu and Al can be obtained. Also, a resin film with particularly suppressed generation of foreign substances even in a high-temperature and high-humidity environment can be obtained.

[0194] In addition, in the photosensitive resin composition for forming a permanent film according to the above embodiment, the surfactant (C) may contain an organically modified dimethylsiloxane represented by the formula (C-1).

[0195]

Chemical formula

[0196] According to such a configuration, a photosensitive resin composition for forming a permanent film can be obtained that has high storage stability and is less likely to generate foreign substances even in a high-temperature and high-humidity environment.

[0197] In addition, in the photosensitive resin composition for forming a permanent film according to the above embodiment, the alkali-soluble resin (A) may be at least one selected from the group consisting of a polyamide resin, a polybenzoxazole resin, and a polyimide resin.

[0198] According to such a configuration, the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition for forming a permanent film can be improved. In addition, by improving physical properties such as the mechanical strength of the permanent film composed of the cured product of the photosensitive resin composition for forming a permanent film, the uniformity of the film thickness can be improved, and the occurrence of defects can be suppressed.

[0199] In addition, in the photosensitive resin composition for forming a permanent film according to the above embodiment, the biphenol compound may be phloroglucide

[0200] According to such a configuration, the biphenol compound has appropriate hydrophilicity and is also well dissolved in a solvent containing an organic solvent. As a result, the generation of foreign substances can be particularly suppressed.

[0201] Further, in the photosensitive resin composition for permanent film formation according to the above embodiment, when the content of the photosensitive diazoquinone compound represented by the formula (B-1) is Xb1 and the content of the biphenol compound having a molecular weight of 150 or more and 1000 or less is Xe, the ratio Xe / Xb1 of the content Xe to the content Xb1 is preferably 0.10 or more and 0.90 or less.

[0202] According to such a configuration, the occurrence of excess and deficiency of both is suppressed, and the effect of suppressing the generation of foreign substances in a high-temperature and high-humidity environment can be more reliably obtained.

[0203] Further, the permanent film according to the above embodiment is composed of a cured product of the photosensitive resin composition for permanent film formation according to the above embodiment.

[0204] According to such a configuration, a permanent film that hardly generates foreign substances even in a high-temperature and high-humidity environment can be obtained.

[0205] Further, the semiconductor device according to the above embodiment has the permanent film according to the above embodiment. According to such a configuration, the occurrence of defects related to foreign substances is suppressed even in a high-temperature and high-humidity environment, and a high-quality semiconductor device can be obtained.

[0206] As described above, the photosensitive resin composition for permanent film formation, the permanent film, and the semiconductor device according to the present invention have been described based on the above embodiments. However, the present invention is not limited to the above embodiments. For example, the photosensitive resin composition for permanent film formation, the permanent film, and the semiconductor device according to the present invention may be those in which each part of the above embodiment is replaced with an arbitrary configuration having the same function, or those in which an arbitrary component is added to the above embodiment.

Examples

[0207] Next, specific examples of the present invention will be described. 5. Preparation of Photosensitive Resin Composition for Permanent Film Formation Using each constituent shown in Table 1, varnish-like photosensitive resin compositions for permanent film formation of each example and each comparative example were prepared. The details of each constituent described in Table 1 are as follows.

[0208] ·Alkali-soluble resin a1: A polybenzoxazole precursor having a structure represented by the formula (A-1) (a resin that undergoes dehydration and ring closure when heated at 150°C to 260°C to become polybenzoxazole)

[0209]

Chemical formula

[0210] ·Method for producing alkali-soluble resin a1 258.2 g (1 mol) of diphenyl ether-4,4'-dicarboxylic acid and 270.3 g (2 mol) of 1-hydroxybenzotriazole were dissolved in N-methylpyrrolidone (1500 g), and then 412.7 g (2 mol) of dicyclohexylcarbodiimide dissolved in N-methylpyrrolidone (412 g) was added dropwise over 2 hours while maintaining the internal temperature at 0 to 5°C. After the addition was complete, the internal temperature was returned to room temperature, and the mixture was further stirred for 12 hours to react. After the reaction was completed, the precipitated dicyclohexylcarbodiurea was removed by filtration, 4000 g of pure water was added dropwise to the obtained filtrate to precipitate crystals. These crystals were collected by filtration, washed with 8000 ml of isopropyl alcohol, and then dried under vacuum to obtain 467 g of a dicarboxylic acid derivative.

[0211] 40.87 g (0.083 mol) of the obtained dicarboxylic acid derivative and 36.63 g (0.1 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane were placed in a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, and N-methylpyrrolidone (180.8 g) was added and dissolved. Then, while flowing nitrogen, the temperature was raised to 75°C using an oil bath, and the reaction was carried out at 75°C for 12 hours.

[0212] Next, 5.58 g (0.034 mol) of 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride dissolved in N-methylpyrrolidone (13.0 g) was added, and after further stirring for 3 hours, the mixture was cooled to room temperature to terminate the reaction.

[0213] Next, after filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropyl alcohol = 3 / 1, the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum to obtain a precursor having an amide bond with a repeating unit of formula (A-1) (an alkali-soluble resin a1 that undergoes dehydration ring closure when heated at 150 °C to 260 °C to become polybenzoxazole).

[0214] · Photosensitizer b1: A compound having a structure represented by formula (NQD-5)

[0215]

Chemical formula

[0216] · Method for producing photosensitizer b1 Into a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas introduction tube, 11.04 g (0.026 mol) of the compound represented by formula (P-1), 18.81 g (0.070 mol) of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, and 170 g of acetone were placed and stirred to dissolve them.

[0217]

Chemical formula

[0218] Next, while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 °C, 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, 1.05 g (0.017 mol) of acetic acid was added and the reaction was continued for another 30 minutes. Then, after filtering the reaction mixture, the filtrate was poured into a mixed solution of water / acetic acid (990 mL / 10 mL). Then, the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum. Thereby, photosensitizer b1 having a structure represented by formula (NQD-5) was obtained.

[0219] · Photosensitizer b2: A compound having a structure represented by formula (NQD-4)

[0220] [Chemistry]

[0221] · Surfactant c1: Polyether-modified polydimethylsiloxane (manufactured by BYK-Chemie Japan, BYK-349) · Surfactant c2: Fluorine-based surfactant (manufactured by 3M Japan, FC4430)

[0222] · Adhesion promoter d1: 3-Methacryloxypropyltrimethoxysilane · Adhesion promoter d2: 3-Glycidoxypropyltriethoxysilane · Adhesion promoter d3: KBM-503P manufactured by Shin-Etsu Chemical Co., Ltd.

[0223] · Additive e1: Phloroglucide (5 hydroxyl groups in one molecule) · Additive e2: 4,4'-Dihydroxybiphenyl (2 hydroxyl groups in one molecule) · Thermal crosslinking agent f1: PXG (p-Xylene glycol)

[0224] · Solvent g1: NMP (N-Methyl-2-pyrrolidone) · Solvent g2: GBL (γ-Butyrolactone)

[0225] 6. Evaluation of the photosensitive resin composition for permanent film formation The prepared photosensitive resin composition for permanent film formation was evaluated for the following items.

[0226] 6.1. Generation state of foreign substances in the solder reflow test For the photosensitive resin compositions for permanent film formation in each example and each comparative example, coating was performed on a Si substrate using a coater-developer (ACT-12, manufactured by Tokyo Electron Limited). Next, pre-baking was carried out at a temperature of 120 °C for 4 minutes using a hot plate. Thereby, a pre-baked resin dry film was obtained. Pattern masking was applied to the pre-baked resin dry film, and broad-band exposure was performed using a broad-band mask aligner. After exposure, development treatment was carried out using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide as a developer to remove the pattern masking. Thereby, a patterned resin dry film with a film thickness of 5 μm was obtained. Thereafter, post-baking was carried out at a temperature of 250 °C for 4 hours in a nitrogen atmosphere to cure the resin dry film, and a resin film with a film thickness of 4 μm was obtained.

[0227] Next, the photosensitive resin composition for permanent film formation was coated again on the obtained resin film, and a patterned resin dry film with a film thickness of 5 μm was obtained in the same manner as above. Thereafter, post-baking was carried out at a temperature of 250 °C for 4 hours in a nitrogen atmosphere to obtain a resin film with a film thickness of 4 μm. Thus, a test piece for the reflow heat resistance test was obtained.

[0228] Next, the obtained test piece was subjected to a baking treatment of being left in an environment at a temperature of 125 °C and a relative humidity of 100% for 24 hours.

[0229] Next, the test piece after the baking treatment was subjected to a high-temperature and high-humidity test of being left in an environment at a temperature of 85 °C and a relative humidity of 85% for 168 hours.

[0230] Next, the test piece after the high-temperature and high-humidity test was put into an infrared furnace and subjected to a solder reflow test in which heating at a temperature of 255 °C for 10 seconds was performed 3 times.

[0231] Next, the test piece after the solder reflow test was observed under an optical microscope at an enlarged magnification. Then, in the observation image obtained from a rectangular imaging range of 40 μm × 60 μm, foreign matters (particles) with a maximum length of 0.5 μm or more were detected and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.

[0232] A: No foreign objects were observed. B: 1 to 3 foreign objects were observed. C: 4 or more foreign objects were observed.

[0233] 6.2. Occurrence status of foreign objects after PCT test First, the test piece after the solder reflow test in 6.1 was placed in a pressure cooker container, and a pressure cooker test (PCT test) was conducted at a temperature of 125 °C, a pressure of 2.2×10 5 Pa for 168 hours.

[0234] Next, the test piece after the PCT test was observed under an optical microscope at an enlarged magnification. Then, in the observation image obtained from a rectangular imaging range of 40 μm × 60 μm, foreign objects (particles) with a maximum length of 0.5 μm or more were detected and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.

[0235] A: No foreign objects were observed. B: 1 to 3 foreign objects were observed. C: 4 or more foreign objects were observed.

[0236]

Table 1

[0237] From the results shown in Table 1, the following was confirmed. · By using photosensitizer b1 (NQD-5) and additive (E) in combination, a resin film with suppressed generation of foreign objects was obtained even after the PCT test. · When at least one of photosensitizer b1 (NQD-5) and additive (E) was not used, good results were not obtained.

Explanation of symbols

[0238] 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 Semiconductor device

Claims

1. An alkali-soluble resin (A), a photosensitizer (B), a surfactant (C), an adhesion promoter (D), an additive (E), and having, the photosensitizer (B) contains a photosensitive diazoquinone compound represented by formula (B-1), the additive (E) contains a biphenol compound having a molecular weight of 150 or more and 1000 or less, and is a photosensitive resin composition for permanent film formation. 【Chemical 1】

2. The photosensitive resin composition for permanent film formation according to claim 1, wherein the alkali-soluble resin (A) is a resin in which a dehydration ring-closing reaction proceeds at a temperature of less than 300°C.

3. The photosensitive resin composition for permanent film formation according to claim 1 or 2, wherein the adhesion promoter (D) contains a silane compound.

4. The photosensitive resin composition for permanent film formation according to claim 1 or 2, wherein the surfactant (C) contains an organically modified dimethylsiloxane represented by formula (C-1). 【Chemical 2】 (In formula (C-1), X represents a polyether group, a polyester group or an aralkyl group, and m and n each represent an integer of 1 or more and 100 or less.)

5. The photosensitive resin composition for permanent film formation according to claim 1 or 2, wherein the alkali-soluble resin (A) is one or more selected from the group consisting of a polyamide resin, a polybenzoxazole resin and a polyimide resin.

6. The photosensitive resin composition for permanent film formation according to claim 1 or 2, wherein the biphenol compound is phloroglucide.

7. When the content of the photosensitive diazoquinone compound represented by formula (B-1) is Xb1 and the content of the biphenol compound having a molecular weight of 150 or more and 1000 or less is Xe, the ratio Xe / Xb1 of the content Xe to the content Xb1 is 0.10 or more and 0.90 or less. The photosensitive resin composition for permanent film formation according to claim 1 or 2.

8. A permanent film characterized by being composed of a cured product of the photosensitive resin composition for permanent film formation according to claim 1 or 2.

9. A semiconductor device characterized by having the permanent film according to claim 8.

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