Precursor having amide bond and photosensitive resin composition

Abstract

To provide a photosensitive resin composition capable of forming a resin film with reduced precipitation of foreign matter and superior uniformity, and a precursor with an amide bond employed in its production.SOLUTION: The present invention provides a precursor having an amide bond, which is a precursor having an amide bond with a repeating unit represented by general formula (1). The mass concentration of NMP is 0.1 ppm or more and 30 ppm or less, and the mass concentration of an alcohol having a carbon number of 2 or more and 6 or less is 0.01% or more and 7.0% or less. (In general formula (1), X and Y are organic groups. R1 is a hydroxyl group, an -O-R3 group, an alkyl group, an acyloxy group, or a cycloalkyl group, and may be identical or different when present in plural. R2 is a hydroxyl group, a carboxyl group, an -O-R3 group, or a -COO-R3 group, and may be identical or different when present in plural.)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a precursor having an amide bond and a photosensitive resin composition.

Background Art

[0002] Conventionally, photosensitive resin compositions including photosensitive polyimide in which photosensitive properties are imparted to a polyimide resin, and photosensitive polybenzoxazole in which a naphthoquinone diazide compound is contained in a polybenzoxazole precursor are known.

[0003] On the other hand, in recent years, new research and development has been progressing in the field of photosensitive resin compositions from the viewpoint of reducing the environmental load on the earth. For example, in Patent Document 1, paying attention to N-methyl-2-pyrrolidone (NMP) known for its high environmental load, even when the NMP content in the photosensitive resin composition is reduced to 0.1% by mass or less, gelation with time is suppressed, and a technique for obtaining a photosensitive resin composition satisfactory in sensitivity and mechanical properties is disclosed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, according to the study by the present inventor, it has been found that a problem of crystallization occurs in a photosensitive polymer precursor that does not contain NMP at all. In particular, low molecular weight compounds by-produced in the production of the photosensitive polymer precursor are likely to cause crystallization. There is concern that the crystallized low molecular weight compounds will precipitate as foreign matters when preparing a varnish of the photosensitive resin composition.

[0006] On the one hand, such a low-molecular compound is decomposed and removed when heated after the varnish is applied to the object. However, the problem is that this removal does not proceed smoothly, and as a result, foreign substances are generated in the resin film obtained from the varnish.

[0007] An object of the present invention is to provide a photosensitive resin composition capable of forming a resin film in which precipitation of foreign substances is suppressed and which is excellent in uniformity, and a precursor having an amide bond used in the production thereof.

Means for Solving the Problems

[0008] Such an object is achieved by the present invention described in the following (1) to (3). (1) A precursor having an amide bond having a repeating unit represented by the general formula (1), wherein the mass concentration of N-methyl-2-pyrrolidone (NMP) is 0.1 ppm or more and 30 ppm or less, and the mass concentration of an alcohol having 2 to 6 carbon atoms is 0.01% or more and 7.0% or less, which is a precursor having an amide bond.

Chemical formula

[0009] (2) The weight average molecular weight Mw is 7,000 or more and 50,000 or less, When the number average molecular weight is Mn, the precursor having an amide bond according to the above (1), wherein the molecular weight distribution Mw / Mn is 1.00 or more and 2.00 or less.

[0010] (3) A precursor having an amide bond according to the above (1) or (2), and a photosensitizer, and a photosensitive resin composition characterized by comprising the same. [Effect of the Invention]

[0011] According to the present invention, a photosensitive resin composition capable of suppressing the precipitation of foreign matters and forming a resin film excellent in uniformity can be obtained.

[0012] Further, according to the present invention, a precursor having an amide bond used in the production of a photosensitive resin composition capable of suppressing the precipitation of foreign matters and forming a resin film excellent in uniformity can be obtained. [Embodiments for Carrying Out the Invention]

[0013] Hereinafter, a precursor having an amide bond according to the present invention (hereinafter, also referred to as "polyamide resin") and a photosensitive resin composition will be described in detail based on preferred embodiments.

[0014] 1. Precursor having an amide bond First, the precursor having an amide bond according to the present embodiment will be described.

[0015] 1.1. Composition The precursor having an amide bond according to the present embodiment has a repeating unit represented by the following general formula (1). In the following description, this precursor is also referred to as "polyamide resin".

[0016] [Chemical formula] (In general formula (1), X and Y are organic groups. R1 is a hydroxyl group, -O-R3, an alkyl group, an acyloxy group, or a cycloalkyl group, and when there are a plurality of them, they may be the same or different from each other. R2 is a hydroxyl group, a carboxyl group, -O-R3, or -COO-R3, and when there are a plurality of them, they may be the same or different from each other. R3 in R1 and R2 is an organic group having 1 to 15 carbon atoms. When R1 does not have a hydroxyl group, at least one of R2 is a carboxyl group. When R2 does not have a carboxyl group, at least one of R1 is a hydroxyl group. m is an integer from 0 to 8, and n is an integer from 0 to 8.)

[0017] In addition, in this specification, a group (atomic group) includes both a group without a substituent and a group with a substituent when it is not specified whether it is substituted or unsubstituted. For example, the "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group with a substituent (substituted alkyl group).

[0018] Also, in this specification, an organic group means, unless otherwise specified, an atomic group obtained by removing one or more hydrogen atoms from an organic compound. For example, a monovalent organic group represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.

[0019] In addition, in this specification, the content of each component in the composition means, unless otherwise specified, the total amount of a plurality of substances present in the composition when there are a plurality of substances corresponding to each component in the composition.

[0020] In general formula (1), as R1 and R2, in order to adjust the solubility of the polyamide resin in an aqueous alkali solution, groups in which a hydroxyl group and a carboxyl group are protected by a protecting group R3 can be used. Specifically, -O-R3 as R1, -O-R3 and -COO-R3 as R2 can be used. Examples of such an organic group having 1 to 15 carbon atoms as R3 include a formyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tertiary butyl group, a tertiary butoxycarbonyl group, a phenyl group, a benzyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, and the like.

[0021] The organic group as X in the above general formula (1) is not particularly limited. For example, an aromatic group composed of a structure such as a benzene ring, a naphthalene ring, and a bisphenol structure; a heterocyclic organic group composed of a structure such as a pyrrole ring and a furan ring; a siloxane group, and the like can be mentioned. More specifically, those represented by the following formula (12) are preferable. These may be used alone or in combination of two or more as necessary.

[0022]

Chemical formula

[0023] Among the groups represented by the above formula (12), those represented by the following formula (13) (some of which have R1 in the general formula (1)) are preferred.

[0024]

Chemical formula

[0025] Among the groups represented by the above formula (13), more preferred are those represented by the following formula (14) (some of which have R1 in the general formula (1)).

[0026]

Chemical formula

[0027] Z in the above formula (12) and formula (13), and R in the above formula (14) 12Specific examples of the alkylene group and the substituted alkylene group as such include -CH2-, -CH(CH3)-, -C(CH3)2-, -CH(CH2CH3)-, -C(CH3)(CH2CH3)-, -C(CH2CH3)(CH2CH3)-, -CH(CH2CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -CH(CH(CH3)2)-, -C(CH3)(CH(CH3)2)-, -CH(CH2CH2CH2CH3)-, -C(CH3)(CH2CH2CH2CH3)-, -CH(CH2CH(CH3)2)-, -C(CH3)(CH2CH(CH3)2)-, -CH(CH2CH2CH2CH2CH3)-, -C(CH3)(CH2CH2CH2CH2CH3)-, -CH(CH2CH2CH2CH2CH2CH3)-, and -C(CH3)(CH2CH2CH2CH2CH2CH3)-, etc. Among these, -CH2-, -CH(CH3)-, and -C(CH3)2- are preferable because they can provide a resin film with more excellent balance and sufficient solubility not only in an alkaline aqueous solution but also in a solvent.

[0028] Also, Y in the above general formula (1) is an organic group, and examples of such organic groups include the same ones as those of X above. For example, aromatic groups composed of structures such as a benzene ring, a naphthalene ring, and a bisphenol structure; heterocyclic organic groups composed of structures such as a pyrrole ring, a pyridine ring, and a furan ring; a siloxane group, etc. More specifically, those represented by the following formula (15) can be preferably cited. These may be used alone or in combination of two or more.

[0029]

Chemical formula

[0030] Among the groups represented by these formulas (15), particularly preferred are those represented by the following formula (16) (some of which have R2 in the general formula (1)).

[0031] Regarding the structure derived from the tetracarboxylic dianhydride in the following formula (16), those in which the positions bonded to the C=O group in the general formula (1) are both meta-positions and those in which they are both para-positions are exemplified, but a structure containing both meta- and para-positions may also be used.

[0032]

Chemical formula

[0033]

Chemical formula

[0034]

Chemical formula

[0035] 1.2. NMP Concentration For the precursor having an amide bond according to this embodiment, the mass concentration of N-methyl-2-pyrrolidone (NMP) is 0.1 ppm or more and 30 ppm or less. Hereinafter, the mass concentration of N-methyl-2-pyrrolidone (NMP) is referred to as "NMP concentration". If the NMP concentration is within the above range, even when low molecular weight compounds such as phenol are by-produced during the production of the polyamide resin, crystallization of the low molecular weight compounds can be suppressed. One of the reasons for such an effect is that NMP has good compatibility with the polyamide resin and by-products. Thereby, when a varnish is prepared using a photosensitive resin composition containing a polyamide resin, precipitation of low molecular weight compounds as foreign substances can be suppressed.

[0036] Also, the NMP concentration is preferably 0.1 ppm or more and 15 ppm or less, more preferably 0.5 ppm or more and 10 ppm or less, and still more preferably 0.7 ppm or more and 5.0 ppm or less.

[0037] If the NMP concentration is below the lower limit value, low molecular weight compounds are likely to crystallize in the photosensitive resin composition containing the polyamide resin. When the low molecular weight compounds crystallize, foreign substances precipitate in the varnish, and the quality of the resin film formed using the varnish deteriorates. On the other hand, since NMP is known to have a high environmental load, when the NMP concentration exceeds the upper limit value, the environmental load of the polyamide resin increases.

[0038] The NMP concentration of the polyamide resin is measured as follows. First, 5 mg of the polyamide resin is set in a pyrolysis furnace, and pyrolysis treatment is performed at 250 ° C for 30 min. The volatile matter is trapped in a cooling section of liquid nitrogen, and heat treatment is performed again for mass spectrum analysis. The quantitative value of the NMP concentration (ppm) is calculated from the peak area value of the NMP-containing standard sample measured in advance.

[0039] · Measurement Conditions Measuring Device: HP6890 (manufactured by Hewlett-Packard) Column: HP-5, length 30 m, film thickness 0.25 μm, inner diameter 0.32 mm, liquid phase 5%-diphenyl-95%-dimethylpolysiloxane Carrier gas: Nitrogen Carrier gas flow rate: 1.0 mL / min Detector: FID (Hydrogen flame ionization detector) Inlet and outlet temperature: 250 °C Detector temperature: 300 °C Temperature rising pattern (column): Hold at 100 °C for 2 minutes, heat up to 300 °C at 5 °C / min, hold at 30 °C for 10 minutes Split ratio: 100 Sample: 1 μL (Epoxy compound: Acetone = 1:40)

[0040] 1.3. Concentration of alcohols having 2 to 6 carbon atoms The precursor having an amide bond according to the present embodiment has a mass concentration of an alcohol having 2 to 6 carbon atoms of 0.01% or more and 7.0% or less. Hereinafter, the mass concentration of an alcohol having 2 to 6 carbon atoms is referred to as "alcohol concentration". If the alcohol concentration is within the above range, when the varnish containing the polyamide resin is applied to an object and then heated, smooth decomposition and removal of low molecular compounds are promoted. Specifically, the boiling points of alcohols having 2 to 6 carbon atoms are about 78 to 157 °C, which are lower than the boiling point of NMP (about 202 °C). Therefore, when the coating film of the varnish is heated, the alcohol and NMP volatilize with a time difference. As a result, the density of the coating film or dry film before curing is optimized, and the decomposition products generated when the low molecular compounds are heated are easily removed from the coating film or dry film. As a result, the generation of foreign matters derived from decomposition products and the like in the resin film can be suppressed. Note that the occurrence of such problems is likely to depend on processing conditions such as the heating time when heating the coating film. If the alcohol concentration is within the above range, the occurrence of the above problems is suppressed, so it is also useful in that it can expand the allowable range of processing conditions, that is, expand the process margin.

[0041] In order to obtain the above effects, it is effective that the number of carbon atoms of the alcohol whose mass concentration is controlled is 2 or more and 6 or less. Specifically, ethanol, propanol, butanol, pentanol, hexanol, etc. can be mentioned. More specifically, examples of propanol include 1-propanol and 2-propanol (isopropyl alcohol, IPA), examples of butanol include 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, etc., examples of pentanol include 1-pentanol, etc., and examples of hexanol include 1-hexanol, etc. Among these, it is particularly effective to control the mass concentration of isopropyl alcohol.

[0042] Also, the alcohol concentration is preferably 0.1% or more and 5.7% or less, more preferably 0.5% or more and 5.0% or less, and even more preferably 1.0% or more and 4.5% or less.

[0043] When the alcohol concentration is below the lower limit value, when the coating film of the varnish is heated, the decomposition products of the low-molecular compounds are not smoothly removed and tend to remain. On the other hand, when the alcohol concentration exceeds the upper limit value, the alcohol concentration in the polyamide resin becomes too high. As a result, the alcohol becomes excessive, and the polyamide resin tends to become sticky. And, thickness unevenness may occur in the resin film, or voids may occur inside. Also, the higher the alcohol concentration, the lower the flash point of the polyamide resin, and the more difficult it is to handle.

[0044] The alcohol concentration of the polyamide resin is measured as follows. First, 0.10 g of polyamide resin is dissolved in 9.90 g of γ-butyrolactone to prepare a 1% concentration solution. Next, the alcohol concentration of this solution is measured by gas chromatography. Specifically, the alcohol content (mass%) is calculated from the area value of the peak corresponding to the alcohol.

[0045] ·Measurement conditions Measuring device: manufactured by Shimadzu Corporation, product name Shimadzu GC-2010 Column: capillary column DB1 (60 mm × 0.25 mm φ × 1 μm) Temperature: 210 °C

[0046] 1.4. Other characteristics The precursor (polyamide resin) having an amide bond according to this embodiment preferably has a weight average molecular weight of 7,000 or more and 50,000 or less, and more preferably 10,000 or more and 30,000 or less. By preparing a photosensitive resin composition using such a polyamide resin, when forming a coating film on a substrate, a composition having sufficient strength and less likely to cause defects such as cracks can be realized.

[0047] The weight average molecular weight is measured by GPC (gel permeation chromatography, manufactured by Tosoh Corporation) and obtained as a value converted with standard polystyrene.

[0048] Also, the molecular weight distribution Mw / Mn of the polyamide resin according to this embodiment is preferably 1.00 or more and 2.00 or less, and more preferably 1.30 or more and 1.70 or less. By preparing a photosensitive resin composition using such a polyamide resin, a photosensitive resin composition with good sensitivity can be realized. Here, Mw is the weight average molecular weight of the polyamide resin, and Mn is the number average molecular weight of the polyamide resin. The number average molecular weight Mn is measured by GPC (gel permeation chromatography, manufactured by Tosoh Corporation) and obtained as a value converted with standard polystyrene.

[0049] Also, the ratio of the NMP concentration (unit: ppm) to the alcohol concentration (unit: %) is defined as the "NMP / alcohol ratio (unit: ppm / %)". For the precursor having an amide bond according to this embodiment, this NMP / alcohol ratio is preferably 0.05 or more and 50.00 or less, more preferably 0.10 or more and 10.00 or less, and even more preferably 0.20 or more and 5.00 or less. By setting the NMP / alcohol ratio within the above range, it is possible to obtain a uniform resin film in which the precipitation of foreign substances in the resin film is particularly suppressed and the occurrence of thickness unevenness, voids, etc. is suppressed.

[0050] In addition, when the NMP / alcohol ratio is less than the lower limit value, there is a risk that foreign substances associated with the crystallization of low-molecular compounds may easily occur or the uniformity of the resin film may decrease. On the other hand, when the NMP / alcohol ratio exceeds the upper limit value, there is a risk that decomposition products of low-molecular compounds may easily remain or excess NMP may be generated, resulting in insufficient contribution to the reduction of the environmental load.

[0051] The adjustment of the NMP concentration and the alcohol concentration in the precursor (polyamide resin) having an amide bond according to the above-described embodiment may be adjusted by adjusting the amounts of NMP and alcohol used during the production of the precursor having an amide bond described later, or may be adjusted by adding NMP and alcohol after producing the precursor having an amide bond.

[0052] 2. Method for producing a precursor (polyamide resin) having an amide bond The above-mentioned precursor having an amide bond is polymerized, for example, as follows. 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 precursor having an amide bond mainly composed of polyamide.

[0053] 2.1. Polymerization step (S1) In the polymerization step (S1), a diamine monomer and a dicarboxylic acid monomer are polycondensed. The method of polycondensation for polymerizing polyamide is not limited, and specifically, examples include melt polycondensation, acid chloride method, direct polycondensation, etc.

[0054] In addition, a method of reacting a compound selected from the group consisting of the compounds listed as the dicarboxylic acid monomers described below, tetracarboxylic dianhydrides, trimellitic anhydrides, and dicarboxylic acid dichlorides, 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 also be used as the dicarboxylic acid monomer. Examples of the compound having a hydroxyl group include 1-hydroxybenzotriazole or derivatives 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. Alternatively, after adding an acid catalyst such as hydrochloric acid, sulfuric acid, benzenesulfonic acid, or toluenesulfonic acid, heating is performed to remove the water generated from the alcohol compound and the carboxylic acid compound while allowing the reaction to proceed to promote esterification and obtain the above-mentioned active ester type dicarboxylic acid.

[0055] The diamine monomer and the dicarboxylic acid monomer used for polymerizing the precursor having an amide bond 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.

[0056] (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 precursor having an amide bond using such a diamine monomer as a raw material, the conformation of the precursor having an amide bond can be controlled, and the dispersibility when made into a composition can be further improved.

[0057] Here, as the diamine monomer containing a phenolic hydroxyl group in its structure, for example, a compound represented by the formula (DA1) is preferable. By producing a precursor having an amide bond using such a diamine monomer as a raw material, the conformation of the precursor having an amide bond can be controlled, and the molecular chains of the precursor having an amide bond can form a denser structure. Therefore, it is considered that the molecules of the alkali-soluble resin (A) and the metal molecules can be more strongly bound in a coordinated manner to freeze the molecular structure and improve the adhesion to the substrate.

[0058] In addition, for example, when the diamine monomer represented by the formula (DA1) is used, the precursor having an amide bond contains a structural unit represented by the formula (PA3). That is, the precursor having an amide bond preferably contains a structural unit represented by the formula (PA3), for example.

[0059] [Chemical formula] 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.

[0060] [Chemical formula] In the formula (PA3), R4 , R 5 ~R 10 is the same as formula (DA1).

[0061] R in formula (DA1) and formula (PA3) 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.

[0062] In addition, 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.

[0063] R in formula (DA1) and formula (PA3) 4 When R 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.

[0064] R in formula (DA1) and formula (PA3) 4 When R 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.

[0065] As the alkylene group, for example, a linear alkylene group or a branched alkylene group may be used. 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-; and alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-.

[0066] Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and those in which two or more arylene groups are bonded to each other.

[0067] As the halogen-substituted alkylene group and the halogen-substituted arylene group, specifically, those obtained by substituting a hydrogen atom in the above-described alkylene group and arylene group with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom can be used. Among these, those in which a hydrogen atom is substituted with a fluorine atom are preferably used.

[0068] R in formula (DA1) and formula (PA3) 4 When it does not contain a carbon atom, examples of R 4 include a group composed of an oxygen atom or a sulfur atom, and the like.

[0069] R in formula (DA1) and formula (PA3) 5 ~R 10is, independently, hydrogen or an organic group having 1 to 30 carbon atoms, and for example, 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, aromatic rings of the precursor having an amide bond can be closely arranged. Therefore, the molecules of the alkali-soluble resin (A) and the metal molecules can be bonded in a stronger coordination to freeze the molecular structure and improve the adhesion.

[0070] R in formula (DA1) and formula (PA3) 5 ~R 10 Specific 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; alkenyl groups such as allyl group, pentenyl group, vinyl group; alkynyl groups such as ethynyl group; alkylidene groups such as methylidene group, ethylidene group; aryl groups such as phenyl group, naphthyl group, anthracenyl group; aralkyl groups such as benzyl group, phenethyl group; cycloalkyl groups such as adamantyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group; and alkaryl groups such as tolyl group, xylyl group.

[0071] Examples of the diamine monomer represented by 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, and the like. By using these diamine monomers, the aromatic rings of the precursor having an amide bond are 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. 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.

[0072] [Chemical formula]

[0073] (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.

[0074] As the dicarboxylic acid monomer containing an aromatic ring, for example, those represented by formula (DC1) are preferably used. By producing a precursor having an amide bond using such a dicarboxylic acid monomer as a raw material, the conformation of the precursor having an amide bond 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.

[0075] [Chemical formula] In formula (DC1), R 11is 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.

[0076] For example, when the dicarboxylic acid monomer represented by the formula (DC1) is used, the precursor having an amide bond typically contains a structural unit represented by the formula (PA4). In the formula (PA4), R 11 , R 12 ~R 19 is the same as in the formula (DC1).

[0077]

Chemical formula

[0078] R in the formula (DC1) and the formula (PA4) 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.

[0079] In addition, R 11 is a divalent group. Here, the divalent group indicates the valence. That is, it indicates that there are two bonds by which R 11 binds to other atoms.

[0080] When R 11 in the formula (DC1) and the formula (PA4) contains a carbon atom, R 11 is, for example, a group having 1 to 30 carbon atoms, preferably a group having 1 to 10 carbon atoms, more preferably a group having 1 to 5 carbon atoms, and even more preferably a group having 1 to 3 carbon atoms.

[0081] When R 11 in the formula (DC1) and the formula (PA4) contains a carbon atom, R11 Specific examples include an alkylene group, an arylene group, a halogen-substituted alkylene group, a halogen-substituted arylene group, and the like.

[0082] As the alkylene group, for example, a linear alkylene group or a branched alkylene group may be used. 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-; and alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-.

[0083] Specific 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.

[0084] As the halogen-substituted alkylene group and the halogen-substituted arylene group, specifically, those obtained by substituting a hydrogen atom in the above-described alkylene group and arylene group with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom can be used. Among these, those obtained by substituting a hydrogen atom with a fluorine atom are preferably used.

[0085] In formula (DC1) and formula (PA4), when R 11 does not contain a carbon atom, examples of R 11 specifically include a group consisting of an oxygen atom or a sulfur atom.

[0086] In formula (DC1) and formula (PA4), R12 ~R 19 is, independently of each other, hydrogen or an organic group having 1 to 30 carbon atoms, and is preferably, for example, 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.

[0087] R in formula (DC1) and formula (PA4) 12 ~R 19 Specific examples of the organic group having 1 to 30 carbon atoms of ~R 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.

[0088] Specific examples of the dicarboxylic acid monomer include diphenyl ether 4,4'-dicarboxylic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, etc. 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 more preferably to use diphenyl ether 4,4'-dicarboxylic acid. Thereby, the aromatic rings of the precursors having amide bonds 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.

[0089] Incidentally, it is preferable to modify the amino group present at the terminal of the precursor having an amide bond simultaneously with the polymerization step (S1) or after the polymerization step (S1). The modification can be carried out, for example, by reacting a specific acid anhydride or a specific monocarboxylic acid with a diamine monomer or a polyamide resin. Therefore, it is preferable that the precursor having an amide bond has an amino group at the terminal modified with the specific acid anhydride or the specific monocarboxylic acid. The specific acid anhydride and the 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 specific acid anhydride and the specific monocarboxylic acid, those containing a nitrogen atom are preferable, for example. Thereby, the wettability between the photosensitive resin composition after post-baking and a metal such as Cu or Al can be improved.

[0090] Specific examples of the specific acid anhydride include maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 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 a combination of two or more of the above specific examples can be used.

[0091] Incidentally, when the amino group present at the terminal of the precursor having an amide bond is modified with a cyclic specific acid anhydride, the cyclic specific acid anhydride is ring-opened. Here, after modifying the precursor having an amide bond, 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.

[0092] Specific examples of the specific monocarboxylic acid include 5-norbornene-2-carboxylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, etc. As the specific monocarboxylic acid, one or more of the above specific examples can be used in combination.

[0093] Also, simultaneously with the polymerization step (S1) or after the polymerization step (S1), the carboxyl group present at the terminal of the precursor having an amide bond may be modified. The modification can be carried out, for example, by reacting a specific nitrogen atom-containing heteroaromatic compound with a dicarboxylic acid monomer or a precursor having an amide bond. Therefore, it is preferable that the precursor having an amide bond has a terminal carboxyl group modified by a specific nitrogen atom-containing heteroaromatic compound. The 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 can be increased. Therefore, the wettability between the photosensitive resin composition after pre-baking and post-baking and metals such as Cu and Al can be improved.

[0094] Specific examples of the specific nitrogen atom-containing heteroaromatic compound include 5-aminotetrazole, etc.

[0095] 2.2. Low Molecular Weight Component Removal Step (S2) Following the polymerization step (S1), it is preferable to perform a low molecular weight component removal step (S2) to remove low molecular weight components.

[0096] Specifically, after concentrating an organic layer containing a mixture of a low molecular weight component and a precursor having an amide bond by filtration or the like, it is redissolved in an organic solvent such as water / isopropanol. Thereby, the precipitate is filtered off, and a precursor having an amide bond from which the low molecular weight component has been removed can be obtained.

[0097] Regarding the precursor having an amide bond, for example, after the above-described low molecular weight component removal step, it is preferable to prepare a photosensitive resin composition that is a varnish without going through a step in which the solvent completely volatilizes and becomes 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 precursor having an amide bond. As a result, a composition capable of forming a resin film that hardly generates foreign matter even in a high temperature and high humidity environment can be obtained.

[0098] 3. Photosensitive Resin Composition Next, the photosensitive resin composition according to the present embodiment will be described. The photosensitive resin composition according to the present embodiment contains the precursor having an amide bond according to the above-described embodiment and a photosensitizer. Further, in the photosensitive resin composition according to the present embodiment, if necessary, the following components, as well as additives such as an antioxidant, a filler, a surfactant, a photopolymerization initiator, a terminal capping agent, and a sensitizer may be added.

[0099] 3.1. Alkaline Soluble Resin (A) The photosensitive resin composition according to the present embodiment contains an alkaline soluble resin (A). This alkaline soluble resin (A) may contain, in addition to the above-described precursor having an amide bond (polyamide resin), other resins having alkaline solubility.

[0100] Examples of the resin having the above-described alkaline solubility include phenolic resins, phenol aralkyl resins, hydroxystyrene resins, methacrylic acid resins, acrylic resins such as methacrylic acid ester resins, and cyclic olefin resins.

[0101] 3.2. Photosensitizer (B) When the photosensitive resin composition is used as a so-called positive type, as a photosensitizer, for example, a photosensitive diazoquinone compound, a diaryliodonium salt, a triarylsulfonium salt or an onium salt such as a sulfonium borate salt, a 2-nitrobenzyl ester compound, an N-iminosulfonate compound, an imidosulfonate compound, a 2,6-bis(trichloromethyl)-1,3,5-triazine compound, or a photoacid generator such as a dihydropyridine compound can be used.

[0102] Among these, the photosensitizer (B) preferably 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.

[0103] JPEG2025091826000015.jpg67170

[0104] This photosensitive diazoquinone compound has a lower decomposition start temperature during heating than other photosensitizers. Therefore, even if this photosensitive diazoquinone compound remains in the resin film in the state of unreacted substances, 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, even when the resin film is exposed to a high-temperature and high-humidity environment, the generation of foreign matters can be suppressed.

[0105] In addition to the above photosensitive diazoquinone compound, it is preferable to use in combination an additive (E) containing a biphenol compound described later. Thereby, even when the decomposition products of the photosensitizer and other contained components have hydrophilicity, the generation of foreign matters can be suppressed.

[0106] 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.

[0107] 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, and more preferably 80% by mass or more.

[0108] When the photosensitive resin composition 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 can be further improved. Hereinafter, diazoquinone compounds will be exemplified using chemical formulas.

[0109]

Chem.

[0110]

Chem.

[0111]

Chem.

[0112]

Chem.

[0113]

Chem.

[0114] In each of the above diazoquinone compounds, Q is a structure represented by formula (a), formula (b) or formula (c) or a hydrogen atom. However, at least one of Q in each diazoquinone compound is a structure represented by formula (a), formula (b) and formula (c).

[0115] As Q of the diazoquinone compound, it is preferable to include formula (a) or formula (b). Thereby, the transparency of the photosensitive resin composition can be improved. Therefore, the appearance of the photosensitive resin composition can be improved.

[0116]

Chemical formula

[0117] The lower limit of the content of the photosensitizer (B) in the photosensitive resin composition 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 has appropriate sensitivity. The upper limit of the content of the photosensitizer (B) in the photosensitive resin composition is preferably 30 parts by mass or less, more preferably 20 parts by mass or less when the alkali-soluble resin (A) is 100 parts by mass. Thereby, it can be suppressed that the photosensitive resin composition is repelled by the metal material present on the substrate surface of the semiconductor device.

[0118] 3.3. Surfactant (C) The photosensitive resin composition may contain a 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 later can be enhanced, and thus the coating film performance when forming a coating film using the photosensitive resin composition can be improved. In addition, by reducing the surface tension reducing ability, the wettability to the metal material can be enhanced, and the coating film performance when forming a coating film using the photosensitive resin composition can be improved.

[0119] As the surfactant (C), for example, 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; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Fluorosurfactants commercially available under names such as F-Top EF301, F-Top EF303, F-Top 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 copolymer Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned.

[0120] As the surfactant (C), silicone surfactants (such as polyether-modified dimethylsiloxane, etc.) can also be preferably used. Specifically, as the silicone surfactants, the SH series, SD series, and ST series of Toray Dow Corning, the BYK series of Big 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 can be mentioned.

[0121] The surfactant (C) preferably contains, in particular, an organically modified dimethylsiloxane represented by the formula (C-1). Thereby, even when the photosensitive resin composition absorbs moisture, the function of the surfactant (C) is less likely to deteriorate, and the dissolution state (dispersion state) of each constituent component can be maintained. As a result, it is possible to suppress the occurrence of unintended reactivity in the photosensitive resin composition to generate reaction products, or the decrease in the solubility of the constituent components to generate precipitates. And a photosensitive resin composition capable of enhancing the storage stability of the photosensitive resin composition and forming a resin film less likely to generate foreign matters even in a high-temperature and high-humidity environment can be obtained.

[0122]

Chemical formula

[0123]

Chemical formula

[0124] Thereby, a photosensitive resin composition capable of particularly enhancing the storage stability of the photosensitive resin composition and forming a resin film less likely to generate foreign matters even in a high-temperature and high-humidity environment can be obtained.

[0125] 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.

[0126] When X in formula (C-1) is a polyester group, as X, a polyester group represented by formula (2-2) is preferably used.

[0127]

Chemical formula

[0128] When X in formula (C-1) is an aralkyl group, as X, an aralkyl group represented by formula (2-3) is preferably used.

[0129]

Chemical formula

[0130] 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, even 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, even 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.

[0131] The content of the surfactant (C) in the photosensitive resin composition is not particularly limited. However, from the perspective of sufficiently obtaining the effect of the surfactant, the lower limit of the content is preferably 0.001% by mass (10 ppm) or more, more preferably 0.01% by mass (100 ppm) or more, based on the total including the solvent of the photosensitive resin composition. Also, the upper limit of the content is preferably 1% by mass (10,000 ppm) or less, more preferably 0.5% by mass (5,000 ppm) or less, and even more preferably 0.1% by mass (1,000 ppm) or less, based on the total including the solvent of the photosensitive resin composition. 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.

[0132] 3.4. Adhesion Aid (D) The photosensitive resin composition may contain an adhesion aid (D). Specific examples of the adhesion aid (D) include triazole compounds, aminosilane compounds, or imide compounds, and aminosilane compounds are particularly preferably used. By using these, the affinity between the photosensitive resin composition and metal members such as Cu and Al can be improved.

[0133] 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.

[0134] As the aminosilane compound, specifically, 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 the like can be mentioned. As the aminosilane compound, one or more of the above specific examples can be used in combination.

[0135] As the imide compound, the compounds exemplified below can be mentioned. These can be used alone or in combination of two or more.

[0136] [Chemical formula]

[0137] The adhesion aid (D) preferably contains a compound represented by formula (D-1). [Chemical formula]

[0138] The compound represented by formula (D-1) particularly improves the affinity between the photosensitive resin composition and metal members such as Cu and Al. Thereby, a photosensitive resin composition capable of forming a more reliable resin film can be obtained.

[0139] The lower limit of the content of the adhesion aid (D) in the photosensitive resin composition 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 aid (D) in the photosensitive resin composition 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).

[0140] By setting the content of the adhesion aid (D) within the above range, the adhesion aid is preferably dispersed in the photosensitive resin composition, the adhesion of the photosensitive resin composition to the adherend can be improved, and a photosensitive resin composition capable of forming a resin film that hardly generates foreign substances even in a high-temperature and high-humidity environment can be obtained.

[0141] The adhesion aid (D) may contain a coupling agent. Examples of the coupling agent include silane-based compounds having a hydrolyzable group (silane coupling agents) other than the above-described aminosilane compounds.

[0142] 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. can be mentioned. As the silane coupling agent, one or more of the above specific examples can be blended.

[0143] The adhesion aid (D) may contain a titanium coupling agent, an aluminum coupling agent, or a zirconium coupling agent.

[0144] 3.5. Additive (E) The photosensitive resin composition may contain an additive (E). Examples of the additive (E) include biphenol compounds 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 2 to 7 hydroxyl groups, and more preferably 2 to 6 hydroxyl groups. Thereby, the biphenol compound has good hydrophilicity and has the effect of attracting moisture contained in the resin film. For this reason, even when the resin film formed using the photosensitive resin composition is exposed to a high-temperature and high-humidity environment, it is possible to suppress the extraction of hydrophilic substances to the surface. As a result, it is possible to suppress the generation of foreign substances in the resin film in a high-temperature and high-humidity environment.

[0145] In addition, when the number of hydroxyl groups per molecule is less than the lower limit value, the effect 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 may decrease.

[0146] 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.

[0147] In addition, when the molecular weight is less than the lower limit value, in the biphenol compound, the effect of attracting the 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 be uneven.

[0148] 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.

[0149]

Chemical formula

[0150] 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 soluble in a solvent containing an organic solvent.

[0151] The lower limit of the content of the additive (E) in the photosensitive resin composition 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 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.

[0152] 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.

[0153] 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.

[0154] 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 possibility that the above-described 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 possibility that the above-described action by the photosensitive diazoquinone compound may not be sufficiently exhibited.

[0155] 3.6. Thermal crosslinking agent (F) The photosensitive resin composition may contain a thermal crosslinking agent (F) capable of reacting with the alkali-soluble resin (A) by heat. Thereby, mechanical properties such as tensile elongation at break of the cured product obtained by post-baking the photosensitive resin composition can be improved. In addition, the sensitivity of the resin film formed from the photosensitive resin composition can be improved.

[0156] 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.

[0157] The lower limit of the content of the thermal crosslinking agent (F) in the photosensitive resin composition 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 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.

[0158] 3.7. Dissolution regulator The photosensitive resin composition may contain a dissolution regulator. Thereby, the solubility of the solid content of the photosensitive resin composition in the solvent can be adjusted. As a result, a photosensitive resin composition capable of forming a resin film that is less likely to generate foreign matters can be obtained.

[0159] 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.

[0160] The lower limit of the content of the dissolution regulator in the photosensitive resin composition 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 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 capable of forming a resin film less likely to generate foreign matters even in a high-temperature and high-humidity environment can be obtained.

[0161] 3.8. Antioxidant The photosensitive resin composition may contain an antioxidant. As the antioxidant, one or more selected from phenolic antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants can be used. The antioxidant can suppress the oxidation of the resin film formed by the photosensitive resin composition.

[0162] Examples of phenolic antioxidants include 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. can be mentioned.,

[0163] 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'-biphenylenediphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis-(2,6-dicumylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-t-butylphenyl) octyl phosphite, tris(mixed mono- and di-nonylphenyl) phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methoxycarbonylethyl-phenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-octadecyloxycarbonylethylphenyl)pentaerythritol diphosphite, and the like.

[0164] 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.

[0165] 3.9. Solvent (G) The photosensitive resin composition 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.As the solvent (G), one or a combination of two or more of the above specific examples can be used.

[0166] 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.

[0167] The lower limit of the content of the solvent (G) in the photosensitive resin composition 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. Also, the upper limit of the content of the solvent (G) in the photosensitive resin composition is preferably 95% by mass or less, more preferably 90% by mass or less of the whole photosensitive resin composition. Thereby, a photosensitive resin composition capable of improving the dispersibility in the photosensitive resin composition and forming a resin film less likely to generate foreign matters even in a high-temperature and high-humidity environment can be obtained.

[0168] 3.10. Other Components The photosensitive resin composition may contain additives such as fillers and sensitizers in addition to the above-described respective constituent components.

[0169] The filler is appropriately selected according to the mechanical properties and thermal properties required for the resin film formed by the photosensitive resin composition.

[0170] Specific examples of the filler include inorganic fillers or organic fillers. Specific examples of the above inorganic filler include silica such as molten crushed silica, molten spherical silica, crystalline silica, secondary aggregated silica, and fine silica; 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. As the inorganic filler, one or a combination of two or more of the above specific examples can be used.

[0171] Specific examples of the organic filler include organosilicon powder, polyethylene powder, etc. One or a combination of two or more of the above specific examples can be used as the organic filler.

[0172] 4. Use The photosensitive resin composition according to this embodiment becomes a resin film by curing. The obtained resin film is used as a permanent film such as a protective film, an interlayer film, a dam material, etc. Thereby, for an electronic device provided with the resin film as a permanent film, problems based on foreign matters, etc. of the resin film can be suppressed, and the reliability can be improved.

[0173] 5. Effects Exhibited by the Embodiment As described above, the precursor having an amide bond according to the embodiment is a precursor having an amide bond having a repeating unit represented by the general formula (1), wherein the mass concentration of N-methyl-2-pyrrolidone (NMP) is 0.1 ppm or more and 30 ppm or less, and the mass concentration of an alcohol having 2 to 6 carbon atoms is 0.01% or more and 7.0% or less.

[0174] [Chemical formula] (In the general formula (1), X and Y are organic groups. R1 is a hydroxyl group, -O-R3, an alkyl group, an acyloxy group, or a cycloalkyl group, and when there are a plurality of them, they may be the same or different from each other. R2 is a hydroxyl group, a carboxyl group, -O-R3, or -COO-R3, and when there are a plurality of them, they may be the same or different from each other. R3 in R1 and R2 is an organic group having 1 to 15 carbon atoms. When R1 does not have a hydroxyl group, at least one of R2 is a carboxyl group. When R2 does not have a carboxyl group, at least one of R1 is a hydroxyl group. m is an integer from 0 to 8, and n is an integer from 0 to 8.)

[0175] According to such a configuration, since the NMP concentration is optimized, even when low-molecular compounds such as phenol are by-produced during the production of the polyamide resin, the crystallization of the low-molecular compounds can be suppressed. Thereby, when a varnish is prepared using the photosensitive resin composition containing the polyamide resin, the precipitation of the low-molecular compounds as foreign matters can be suppressed. Further, since the alcohol concentration is optimized, when the varnish containing the polyamide resin is heated after being applied to an object, the smooth decomposition and removal of the low-molecular compounds are promoted. That is, the denseness of the coating film and the dry film before curing is optimized, and the decomposition products generated when the low-molecular compounds are heated are easily released from the coating film and the dry film. As a result, the generation of foreign matters derived from the decomposition products and the like in the resin film can be suppressed. Therefore, a precursor having an amide bond that is used in a photosensitive resin composition capable of suppressing the precipitation of foreign matters and forming a resin film with excellent uniformity is obtained.

[0176] Further, the precursor having an amide bond according to the above embodiment preferably has a weight average molecular weight Mw of 7,000 or more and 50,000 or less, and when the number average molecular weight is Mn, the molecular weight distribution Mw / Mn is 1.00 or more and 2.00 or less.

[0177] According to such a configuration, when forming a coating film on a substrate, a precursor having an amide bond that can produce a photosensitive resin composition having sufficient strength, hardly causing defects such as cracks, and having good sensitivity can be obtained.

[0178] Further, the photosensitive resin composition according to the above embodiment includes the precursor having an amide bond according to the above embodiment and a photosensitizer.

[0179] According to such a configuration, a photosensitive resin composition capable of suppressing the precipitation of foreign matters and forming a resin film with excellent uniformity is obtained.

[0180] The precursor having an amide bond and the photosensitive resin composition according to the present invention have been described based on the above embodiments, but the present invention is not limited to the above embodiments. For example, the precursor having an amide bond and the photosensitive resin composition of the present invention may be those obtained by adding any components to the above embodiments.

Examples

[0181] Next, specific examples of the present invention will be described. 6. Production of Precursor Having Amide Bond 6.1. Example 1 According to the conditions shown in Table 1, a precursor having an amide bond and having a repeating unit represented by the above general formula (1) was prepared by the procedure described below.

[0182] 6.1.1. Mixture Preparation Step 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-methyl-2-pyrrolidone (1500 g), and then 412.7 g (2 mol) of dicyclohexylcarbodiimide dissolved in N-methyl-2-pyrrolidone (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 complete, the precipitated dicyclohexylcarbodiurea was removed by filtration, 4000 g of pure water was added dropwise to the resulting 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.

[0183] 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 a mixed solvent of 3-methyl-2-oxazolidone and γ-butyrolactone (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. Next, 5.58 g (0.034 mol) of 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride dissolved in a mixed solvent of 3-methyl-2-oxazolidone and γ-butyrolactone (13.0 g) was added, and after further stirring for 3 hours, it was cooled to room temperature to terminate the reaction. Then, the stirred product was filtered to obtain a mixture.

[0184] 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 that undergoes dehydration ring closure when heated at 300 to 400 °C to become polybenzoxazole).

[0185]

Chemical formula

[0186] The weight average molecular weight (Mw) of the obtained precursor having an amide bond was 14,600, and the number average molecular weight (Mn) was 9,250.

[0187] 6.2. Examples 2 to 9 and Comparative Examples 1 to 5 A precursor having an amide bond was obtained in the same manner as in Example 1, except that the conditions of the manufacturing process were set so that the NMP concentration and the alcohol concentration of the resulting precursor having an amide bond would be the concentrations shown in Table 1. In Examples 9, Comparative Examples 4 and 5, after the above-mentioned "6.1.1. Mixture preparation step", in the process of obtaining a precursor having an amide bond from the mixture, instead of introducing the reaction mixture into a "water / isopropyl alcohol = 3 / 1 solution", it was introduced into a "water / 2-butanol = 3 / 1 solution".

[0188] 7. Measurement of NMP Concentration and Alcohol Concentration of Precursor For the obtained precursor having an amide bond, the NMP concentration and the alcohol concentration were measured. The measurement results are shown in Table 1.

[0189] 8. Preparation of Photosensitive Resin Composition The precursor having an amide bond obtained in each Example and each Comparative Example, and the raw materials shown below were blended in predetermined blending amounts to prepare a photosensitive resin composition. Specifically, 33% by mass of the above-mentioned precursor having an amide bond was dissolved in the following organic solvent, and further, a photoacid generator, an adhesion aid, and a dissolution accelerator were added and mixed to obtain a varnish-like photosensitive resin composition. The following blending amounts represent mass ratios in the entire photosensitive resin composition.

[0190] 8.1. Organic Solvent ·GBL (γ-butyrolactone): 54.8% by mass ·DMSO (dimethyl sulfoxide): 4% by mass

[0191] 8.2. Photoacid Generator (Photosensitizer) ·Compound represented by the following formula (B-2): 4.5% by mass

[0192]

Chemical formula

[0193] 8.3. Adhesion Aid · 3-Methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.): 0.4% by mass · Cyclohexyldimethoxymethylsilane (manufactured by Shin-Etsu Silicone Co., Ltd.): 0.8% by mass · Phenyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.): 0.2% by mass

[0194] 8.4. Dissolution Promoter · 2,2'-Dihydroxydiphenylmethane: 1.7% by mass · Biphenyl-2,3',4,5',6-pentol: 0.6% by mass

[0195] 9. Evaluation of Photosensitive Resin Composition The following evaluations were performed on the prepared varnish-like photosensitive resin composition.

[0196] 9.1. Evaluation of the Influence of Quenching First, the container containing the photosensitive resin composition was brought into contact with dry ice for 10 minutes to quench it. Next, the quenched photosensitive resin composition was coated on a Si substrate using a coater-developer. Next, it was prebaked at a temperature of 120°C for 4 minutes using a hot plate. Thereby, a resin dry film was obtained. The obtained resin dry film was placed in an oven and postbaked at a temperature of 220°C for 1 hour under a nitrogen atmosphere. Thereby, a resin cured film with a film thickness of 7 μm was obtained. Next, the obtained resin cured film was observed with an optical microscope. And the observation results were evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.

[0197] A: No foreign matter is observed B: Slight foreign matter is observed C: A large number of (more than B) foreign matters are observed

[0198] 9.2. Evaluation of the Influence of Short-Time Prebaking First, a photosensitive resin composition was coated on a Si substrate by a coater-developer. Next, using a hot plate, it was pre-baked at a temperature of 120°C for 1 minute. As a result, a resin dry film with a film thickness of 10 μm was obtained. Next, the obtained resin dry film was visually observed. Then, the observation results were evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.

[0199] A: No unevenness or foreign matter is observed B: Slight unevenness or foreign matter is observed C: A large number (more than B) of unevenness or foreign matter is observed

[0200]

Table 1

[0201] As shown in Table 1, the photosensitive resin composition containing the precursor having an amide bond in each example suppressed the generation of foreign matter in the resin cured film even after rapid cooling. Considering that low molecular compounds are likely to precipitate when rapidly cooled, the photosensitive resin composition of each example has the advantage of being storable regardless of the environment, for example. In addition, the photosensitive resin composition containing the precursor having an amide bond in each example suppressed the generation of unevenness and foreign matter even after a short pre-bake. A short pre-bake is considered to cause non-uniformity in the temperature of the coating film and to create an environment prone to the generation of thickness unevenness and foreign matter. In contrast, by using the photosensitive resin composition of each example, the generation of unevenness and foreign matter could be suppressed even in such an environment.

[0202] Therefore, it was confirmed that according to the precursor having an amide bond according to the present invention, it is possible to realize a photosensitive resin composition capable of suppressing the precipitation of foreign matter and forming a resin film with excellent uniformity.

Claims

1. A precursor having an amide bond with a repeating unit represented by the general formula (1), wherein the mass concentration of N-methyl-2-pyrrolidone (NMP) is 0.1 ppm or more and 30 ppm or less, and the mass concentration of an alcohol having 2 to 6 carbon atoms is 0.01% or more and 7.0% or less, characterized in that it is a precursor having an amide bond. 【Chemical Formula 1】 (In the general formula (1), X and Y are organic groups. R １ is a hydroxyl group, -O-R ３ , an alkyl group, an acyloxy group, or a cycloalkyl group, and when there are a plurality of them, they may be the same or different from each other. R ２ is a hydroxyl group, a carboxyl group, -O-R ３ , or -COO-R ３ , and when there are a plurality of them, they may be the same or different from each other. R １ and R ２ in R ３ is an organic group having 1 to 15 carbon atoms. When there is no hydroxyl group as R １ , at least one of R ２ is a carboxyl group. When there is no carboxyl group as R ２ , at least one of R １ is a hydroxyl group. m is an integer of 0 to 8, and n is an integer of 0 to 8.)

2. The precursor having an amide bond according to claim 1, wherein the weight average molecular weight Mw is 7,000 or more and 50,000 or less, and when the number average molecular weight is Mn, the molecular weight distribution Mw / Mn is 1.00 or more and 2.00 or less.

3. A photosensitive resin composition comprising the precursor having an amide bond according to claim 1 or 2, and a photosensitizer. ​

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