TW201815964A - Resin composition and application of same - Google Patents

Abstract

Provided are: a resin composition which has excellent storage stability and is capable of providing a photosensitive resin composition that has high resolving power; a photosensitive resin composition which uses this resin composition; a cured film; a method for producing a cured film; a semiconductor device; and a method for producing a resin composition. A resin composition which contains a heterocyclic ring-containing polymer precursor selected from among polyimide precursors and polybenzoxazole precursors and an acidic compound having a pKa of 4.0 or less. If this resin composition is formed into a cured film having a thickness of 10 [mu]m and is heated at 350 DEG C for 60 minutes, the cured film after the heating has an electrical conductivity of 1.0 * 10<SP>5</SP> [Omega].cm or less.

Description

Resin composition and application

The present invention relates to a resin composition, a photosensitive resin composition, a cured film, a method for producing a cured film, a semiconductor device, and a method for producing a resin composition.

Polyfluorene and polybenzoxazole are excellent in heat resistance and insulation, and are used for insulating films of semiconductor devices. In addition, the following work was also performed, that is, the precursor (polyfluorene imide precursor or polybenzoxazole precursor) before the cyclization reaction with high solvent solubility was replaced with polyimide and polybenzoxazole. After being applied to a substrate or the like, the precursor is heated and cyclized to form a cured film.

As such a polyfluorene imide precursor, for example, Patent Document 1 discloses a negative type containing a polyfluorene imide precursor having a predetermined structure and 100 parts by mass of (B) a photopolymerization initiator in a range of 0.1 to 20 parts by mass. Photosensitive resin composition. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication WO2013 / 168675

Here, it is known that a polyfluorene imide precursor and a polybenzoxazole precursor have poor stability, and when stored for a long time, a ring-closing reaction may occur with the passage of time. For example, the following reactions are caused. [Chemical Formula 1] The upper part shows a partial structure of an example of a polyimide precursor (a repeating unit represented by the formula (1) described later), where A ² represents an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, and R ¹¹⁵ represents 4 Valent organic group, R ¹¹³ represents a hydrogen atom or a monovalent organic group. The lower paragraph shows a partial structure of an example of a polybenzoxazole precursor (repeated unit represented by the formula (2) described later), where R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ Represents a hydrogen atom or a monovalent organic group.

When the photosensitive resin composition containing the polyfluorene imide precursor and the polybenzoxazole precursor is stored for a long period of time, solids are precipitated, and there is a problem that the storage stability of the photosensitive resin composition is insufficient. In addition, even if the storage stability is excellent, as long as the resolution of the photosensitive resin composition is poor, it becomes a problem in the case where a pattern is formed by exposure and development. An object of the present invention is to provide a resin composition that can provide a photosensitive resin composition with excellent storage stability and high resolution, and a photosensitive resin composition, cured film, and cured film using the resin composition. A method for producing a film, a semiconductor device, and a method for producing a resin composition.

Based on the above problems, as a result of intensive studies, the present inventors have found that the above problems can be solved by using an acidic compound having a pKa of 4 or less. Specifically, the above-mentioned problem is solved by the following method <1>, preferably by <2> to <23>. <1> A resin composition comprising a heterocyclic polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor and an acidic compound having a pKa of 4.0 or less, and the resin composition The cured film having a thickness of 10 μm was heated at 350 ° C. for 60 minutes, and the conductivity of the cured film was 1.0 × 10 ⁵ Ω ･ cm or less. <2> The resin composition according to <1>, wherein the heterocyclic-containing polymer precursor includes a repeating unit represented by the following formula (1) or a repeating unit represented by the formula (2): ) [Chemical Formula 2] Formula (2) [Chemical Formula 3] In Formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or Monovalent organic group; In formula (2), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group. <3> The resin composition according to <1> or <2>, wherein the pKa of the acidic compound is 3.5 or less. <4> The resin composition according to any one of <1> to <3>, wherein the molecular weight of the acidic compound is 100 to 300. <5> The resin composition according to any one of <1> to <4>, wherein the acidic compound is selected from a sulfonic acid and a carboxylic acid. <6> The resin composition according to any one of <1> to <4>, wherein the acidic compound is a sulfonic acid. <7> The resin composition according to any one of <1> to <4>, wherein the acidic compound is selected from p-toluenesulfonic acid, camphorsulfonic acid, and methanesulfonic acid. <8> The resin composition according to any one of <1> to <7>, which is a powder. <9> A photosensitive resin composition containing a heterocyclic polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and a resin composition containing an acidic compound having a pKa of 4.0 or less And a photopolymerization initiator. The photosensitive resin composition is a cured film having a thickness of 10 μm, and the cured film has a conductivity of 1.0 × 10 ⁵ Ω ･ cm or less after being heated at 350 ° C. for 60 minutes. <10> The photosensitive resin composition according to <9>, wherein the resin composition is the resin composition according to any one of <2> to <7>. <11> The photosensitive resin composition according to <9> or <10>, which is a photosensitive resin composition for negative development. <12> The photosensitive resin composition according to any one of <9> to <11>, which is used for development using a developer containing an organic solvent. <13> The photosensitive resin composition according to any one of <9> to <12>, which is a photosensitive resin composition for forming an interlayer insulating film for a redistribution layer. <14> A cured film obtained by curing the photosensitive resin composition according to any one of <9> to <13>. <15> The cured film according to <14>, which is an interlayer insulating film for a redistribution layer. <16> A method for producing a cured film, comprising a process of applying the photosensitive resin composition according to any one of <9> to <13> to a substrate; and a photosensitive resin composition corresponding to the substrate Carry out the hardening process. <17> The method for producing a cured film according to <16>, further comprising a process of exposing the cured film and developing the film negatively. <18> The method for producing a cured film according to <17>, wherein the development includes a step of using a developer containing an organic solvent. <19> A semiconductor device having the cured film according to <14> or <15>. <20> A method for producing a resin composition, the resin composition comprising a heterocyclic polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and The manufacturing method includes a process of adding an acidic compound having a pKa of 4.0 or less, and the resin composition is powdered. <21> A method for producing a resin composition, which is the method for producing a resin composition according to any one of <1> to <8>, which includes a heterocyclic polymer precursor synthesis process including A step of adding an acidic compound having a pKa of 4.0 or less. <22> A method for producing a resin composition, which is the method for producing a resin composition according to any one of <1> to <8>, and further comprising: adding a pKa after synthesizing a heterocyclic-containing polymer precursor A step for acidic compounds below 4.0. <23> The method for producing a resin composition according to any one of <20> to <22>, wherein the synthesis process of the heterocyclic-containing polymer precursor includes a step of adding a carbodiimide compound. [Inventive effect]

According to the present invention, it is possible to provide a resin composition which can provide a photosensitive resin composition having excellent storage stability and high resolution, a photosensitive resin composition using the resin composition, a cured film, a method for producing a cured film, and a semiconductor. Device and method for producing resin composition.

The description of the constituent elements in the present invention described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. In the description of the group (atomic group) in the present specification, the unlabeled and unsubstituted labels include those having no substituent and those having a substituent. For example, "alkyl" includes not only alkyl groups (unsubstituted alkyl groups) without substituents, but also alkyl groups (substituted alkyl groups) with substituents. In this specification, "actinic rays" means, for example, a bright line spectrum of a mercury lamp, far ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like represented by an excimer laser. In the present invention, light means actinic rays or radiation. As long as there is no special mention, "exposure" in this specification includes not only exposure based on mercury lamps, far-ultraviolet rays, X-rays, and EUV light typified by excimer lasers, but also drawing based on particle beams such as electron beams and ion beams Also included in the exposure. In this specification, the numerical range indicated by "~" means a range in which numerical values described before and after "~" are included as a lower limit value and an upper limit value. In this specification, "(meth) acrylate" means both or both "acrylate" and "methacrylate", and "(meth) acrylic" means both "acrylic" and "methacrylic" Or, "(meth) acrylfluorenyl" means both or "acrylfluorenyl" and "methacrylfluorenyl". In this specification, the term "manufacturing process" not only includes independent processes, even if it cannot be clearly distinguished from other processes, as long as the intended role of the process is achieved, it is also included in this term. In the present specification, the solid content concentration refers to the mass percentage of the mass of the photoresist component other than the solvent with respect to the total mass of the composition. In addition, unless otherwise stated, solid content concentration means the density | concentration at 25 degreeC. In this specification, unless otherwise stated, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene conversion values based on gel permeation chromatography (GPC measurement). In this specification, HLC-8220GPC (manufactured by Tosoh Corporation) can be used as the weight average molecular weight (Mw) and number average molecular weight (Mn), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, and TSKgel Super can be used as the columns. One of HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) was obtained. The eluent was measured using THF (tetrahydrofuran) unless otherwise specified. In addition, unless otherwise stated, detection was performed using a UV ray (ultraviolet) wavelength 254 nm detector.

[Resin Composition] The resin composition of the present invention includes a heterocyclic-containing polymer precursor (hereinafter, sometimes referred to as "heterocyclic-containing Polymer precursor ") and an acidic compound having a pKa of 4.0 or less, characterized in that the resin composition is a cured film having a thickness of 10 μm and the conductivity of the cured film after heating at 350 ° C for 60 minutes is 1.0 × 10 ⁵ Ω ･ cm or less. With such a structure, a photosensitive resin composition having excellent storage stability and high resolution can be provided. Although this mechanism is inferred, it can be inferred that the addition of an acidic compound having a pKa of 4.0 or less can delay the ring closure reaction of the heterocyclic-containing polymer precursor and improve storage stability. In addition, it is presumed that by reducing the proportion of the closed-loop body in the photosensitive resin composition, it is difficult to increase the viscosity of the photosensitive resin composition, and the resolution can be improved. In addition, by using a compound having a molecular weight of 100 or more as the acidic compound, metal corrosion can be more effectively suppressed.

<Conductivity of cured film of resin composition> The resin composition of the present invention is a cured film having a thickness of 10 μm, and the conductivity of the cured film after heating at 350 ° C. for 60 minutes is 1.0 × 10 ⁵ Ω ･ cm or less. With such a structure, the insulation of the cured film can be maintained. The electrical conductivity was measured according to the method described in Examples described later.

<Heterocyclic-containing polymer precursor> The heterocyclic-containing polymer precursor used in the present invention is at least one selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and a polyimide The precursor is preferred. The polyfluorene imide precursor and the polybenzoxazole precursor may include only one kind, or may include two or more kinds.

<<< Polyimide precursor> The type of polyimide precursor used in the present invention is not particularly limited, but it is preferable to include a repeating unit represented by the following formula (1). Formula (1) [Chemical Formula 4] In Formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or Monovalent organic group. A ¹ and A ² in the formula (1) are preferably an oxygen atom or NH, and more preferably an oxygen atom. R ¹¹¹ in formula (1) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group; a linear aliphatic group having 2 to 20 carbon atoms; and a carbon number of 3 A branched aliphatic group of -20, a cyclic aliphatic group of 3 to 20 carbons, an aromatic group of 6 to 20 carbons, or a group including these combinations are preferred, including 6 to 20 carbons The aromatic group is more preferred.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyfluorene imide precursor include a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine. The diamine may be used alone or in combination of two or more. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group including these combinations A diamine is more preferred, and a diamine containing a group having an aromatic group having 6 to 20 carbon atoms is more preferred. Examples of the aromatic group include the following.

[Chemical Formula 5] In the formula, A is a single bond or selected from the group consisting of an aliphatic hydroxyl group having 1 to 10 carbon atoms, -O-, -C (= O)-, -S-, -S (= O) ₂ -which may be substituted by a fluorine atom. -NHCO- and groups selected from these combinations are preferred, single bond, selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C (= O)- The groups in, -S-, -SO ₂ -are more preferably selected from -CH _2- , -O-, -S-, -SO _2- , -C (CF ₃ ) _2- , and -C (CH ₃ ) The ₂ -valent divalent group is further preferred.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminocyclohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diamino Cyclohexane or 1,4-diaminocyclohexane, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane or 1,4-bis (Aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane and isophorone diamine; methyldiamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl , 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylphosphonium and 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylsulfide and 3,3'-diaminodiphenylsulfide, 4,4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 ' -Dimethyl-4,4 -Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4 -Aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxy Phenyl) fluorene, bis (4-amino-3-hydroxyphenyl) fluorene, 4,4'-diamino-p-terphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, Bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [4- (2-aminophenoxy) benzene Yl] pyrene, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-di Aminodiphenylhydrazone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) ) Benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4 '-Diamino octafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) benzene Group] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3 ', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diamine Diphenylhydrazone, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene Ene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl -Methylphenylenediamine, bis (3-aminopropyl) tetramethyldisilaxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis ( 4-aminophenyl) ethane, diaminophenylanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis (4-amine Phenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis ( 4-aminophenyl) tetradefluorofluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] Fluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-di Methylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4- Amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amine Methyl-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylhydrazone, 4,4'-bis (3- Amino-5-trifluoromethylphenoxy) diphenylhydrazone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3, 3 ', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2 At least one diamine among ', 5,5', 6,6'-hexafluorobenzidine and 4,4'-diaminotetraphenyl.

Diamines (DA-1) to (DA-18) shown below are also preferred.

[Chemical Formula 6]

[Chemical Formula 7]

In addition, as a preferable example, a diamine having at least two alkanediol units in the main chain can be mentioned. A diamine containing one or both of two or more ethylene glycol chains and propylene glycol chains in one molecule is more preferred, and a diamine containing no aromatic ring is more preferred. Specific examples include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148 , JEFFAMINE (registered trademark) EDR-176, JEFFAMINE (registered trademark) D-200, JEFFAMINE (registered trademark) D-400, JEFFAMINE (registered trademark) D-2000, JEFFAMINE (registered trademark) D-4000 (the above are product names , Manufactured by HUNTSMAN CORPORATION), 1- (2- (2- (2-aminopropyloxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-amino Propoxy) propane-2-yl) oxy) propane-2-amine and the like are not limited thereto. JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE ( (Registered trademark) EDR-176 structure.

[Chemical Formula 8]

In the above, x, y, and z are average values.

From the viewpoint of the flexibility of the obtained cured film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. However, Ar is independently an aromatic group, and L is an aliphatic hydroxyl group having 1 to 10 carbon atoms, which can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO _2- , or -NHCO- and optionally A group from the above two or more combinations. Ar is preferably a phenylene group, and L is an aliphatic hydroxyl group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, and -O-, -CO-, -S-, or -SO ₂ -is further preferred. Among them, the aliphatic hydroxyl group is preferably an alkylene group.

From the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability. Formula (51) [Chemical Formula 9] In formula (51), R ¹⁰ to R ¹⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R ¹⁰ to R ¹⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or difluoromethane. Or trifluoromethyl. ^Examples of the monovalent organic group of R ¹⁰ to R ¹⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and 1 to 10 carbon atoms (1 to 6 carbon atoms being Preferred) fluorinated alkyl and the like. Formula (61) [Chemical Formula 10] In formula (61), R ¹⁸ and R ¹⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group. Examples of the diamine compound having a structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4 4,4'-diaminobiphenyl, 2,2'-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. One kind of these may be used or two or more kinds may be used in combination.

R ¹¹⁵ in formula (1) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. Formula (5) [Chemical Formula 11] In formula (5), R ¹¹² is a single bond or is selected from the group consisting of an aliphatic hydroxyl group having 1 to 10 carbon atoms, which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO _2- , -NHCO- And the groups in these combinations are preferred, and the single bond or selected from the group consisting of alkylene having 1 to 3 carbon atoms, -O-, -CO-, -S-, and -SO ₂ -which may be substituted by a fluorine atom. The group is more preferably selected from the group consisting of -CH _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _2- , -O-, -CO-, -S-, and -SO _2- Divalent groups in the group are further preferred.

Formula (6) [Chemical Formula 12]

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in formula (1) include tetracarboxylic acid residues remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. Tetracarboxylic dianhydride may be used alone, or two or more of them may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (O). Formula (O) [Chemical Formula 13] In the formula (O), R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ is the same meaning as in formula (1) is R ^115.

Specific examples of the tetracarboxylic dianhydride include those selected from pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4 '-Diphenyl sulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylhydrazone tetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride , 3,3 ', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ', 4' -Biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2 , 3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4, 4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10- Perylene tetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride Anhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane Anhydride, pyromellitic dianhydride and derivatives of these alkyl having 1 to 6 and / or alkoxy having 1 to 6 derivative of at least one.

Moreover, as a preferable example, tetracarboxylic dianhydride (DAA-1)-(DAA-5) shown below are mentioned. [Chemical Formula 14]

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a radical polymerizable group, and it is more preferable that both of them contain a radical polymerizable group. The radically polymerizable group is a group capable of undergoing a cross-linking reaction by the action of a radical, and a preferable example includes a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) acryl group, and a group represented by the following formula (III).

[Chemical Formula 15]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferred. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH _2- , or a polyoxyalkylene group having 4 to 30 carbon atoms. Examples of preferred R ²⁰¹ include ethylene, propyl, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, and hexamethylene. Methyl, octamethylene, dodecyl methylene, -CH ₂ CH (OH) CH _2- , butyl, propyl, trimethylene, -CH ₂ CH (OH) CH ₂ -are more preferred . It is particularly preferred that R ²⁰⁰ is methyl and R ²⁰¹ is ethyl. As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent capable of improving the solubility of the developing solution is preferably used.

From the viewpoint of solubility in an aqueous developer, R ¹¹³ or R ¹¹⁴ may be a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an aromatic group and an aralkyl group having one, two, or three acidic groups bonded to the carbon constituting the aryl group, and an aromatic group and an aralkyl group having one acidic group. Basis is better. Specific examples include an aromatic group having 6 to 20 carbon atoms having an acidic group, and an aralkyl group having 7 to 25 carbon atoms having an acidic group. More specific examples include a phenyl group having an acidic group and a benzyl group having an acidic group. The acidic group is preferably an OH group. From the viewpoint of solubility with respect to an aqueous developer, R ¹¹³ or R ¹¹⁴ is more preferably a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, and a 4-hydroxybenzyl group.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group are preferred, and an alkyl group substituted with an aromatic group is more preferred. The carbon number of the alkyl group is preferably 1 to 30. The alkyl group may be any of linear, branched, and cyclic. Examples of the linear or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl Alkyl, octadecyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl group, norbornyl group, norbornyl group, pinenyl group, decalinyl group, tricyclodecyl group, tetracyclodecyl group, fluorenylbifluorenyl group, and bicyclic Hexyl and pinenyl. Among them, cyclohexyl is the most preferable from the viewpoint of achieving a balance between high sensitivity. The alkyl group substituted with an aromatic group is preferably a linear alkyl group substituted with an aromatic group, which will be described later. Examples of the aromatic group include a substituted or unsubstituted benzene ring, a naphthalene ring, a cyclopentadiene ring, an inden ring, a fluorene ring, a heptene ring, an indenene ring, a fluorene ring, a fused pentaphenyl ring, Ethane naphthalene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, fluorene ring, extended triphenyl ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring , Pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indazine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring , Naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, morphine ring, acridine ring, morpholine ring, thien ring, chromene ring, fluorene ring, fluorene An oxathiazine ring, an phenothiazine ring, or an morphazine ring. The benzene ring is the best.

In the case where R ¹¹³ is a hydrogen atom in formula (1), R ¹¹⁴ may form a conjugate base with a tertiary amine compound having a hydrogen ethylenic unsaturated bond. Examples of the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropylmethacrylate.

It is also preferable that the polyfluorene imide precursor has a fluorine atom in the structural unit. The fluorine atom content in the polyfluorene imide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

Moreover, in order to improve the adhesiveness with a board | substrate, you may copolymerize with the aliphatic group which has a siloxane structure. Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisilazane and bis (p-aminophenyl) octamethylpentasiloxane.

The repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (1-A). With such a structure, the width of the exposure latitude can be made wider. Formula (1-A) [Chemical Formula 16] In Formula (1-A), A ¹ and A ² represent oxygen atoms, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. At least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and a polymerizable group is preferred.

A ^1, A ^2, the R ^111, R ¹¹³ and R ¹¹⁴ each independently have the formula ^{(1) A 1, A 2} , R 111, R 113 and R ¹¹⁴ have the same meaning, the preferred range is also the same. Same as (5) in the meaning of R ¹¹² and R ¹¹² type, the preferred range is also the same.

The polyimide precursor may be one type of the repeating structural unit represented by the formula (1), but may also be two or more types. Furthermore, it may contain a structural isomer of a repeating unit represented by formula (1). In addition, the polyfluorene imide precursor may include other types of repeating structural units in addition to the repeating units of the formula (1).

As one embodiment of the polyimide precursor in the present invention, 50 mol% or more of the total repeating unit may be exemplified, further 70 mol% or more, and particularly 90 mol% or more may be represented by formula (1). Polyimide precursors of repeat units.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, more preferably 4,000 to 25,000, still more preferably 4,000 to 15,000, and still more preferably 5,000 to 10,000. The degree of dispersion is preferably 1.5 to 4.0, and more preferably 2.0 to 3.5.

The polyfluorene imide precursor is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. A dicarboxylic acid or a dicarboxylic acid derivative is preferably halogenated using a halogenating agent and reacted with a diamine. In the method for producing a polyimide precursor, it is preferable to use an organic solvent during the reaction. The organic solvent may be one kind, or two or more kinds. The organic solvent can be preferably determined depending on the raw materials, but examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

When manufacturing a polyfluorene imide precursor, in order to further improve storage stability, it is preferable to seal the polyfluorene imide precursor with a capping agent such as an acid dianhydride, a monocarboxylic acid, a monofluorinated chlorine compound, and a single active ester compound. Among these, a monoamine is more preferable, and as a preferable compound of a monoamine, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxy group are mentioned. Quinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-amine Naphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-amine Naphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amine Benzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid Acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4 -Aminothiophenol and the like. Two or more of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

When manufacturing polyimide precursors, a process for precipitating solids may also be included. Specifically, a polyfluorene imide precursor in the reaction solution is precipitated in water, and a polyfluorene imide precursor such as tetrahydrofuran is dissolved in a soluble solvent, whereby a solid can be precipitated. Thereafter, the polyfluorene imide precursor is dried to obtain a powdery polyfluorene imide precursor.

<< Polybenzoxazole precursor >> The polybenzoxazole precursor used in the present invention preferably includes a repeating unit represented by the following formula (2). Formula (2) [Chemical Formula 17] In the formula (2), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In the formula (2), R ¹²¹ represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a linear aliphatic group is preferred. In formula (2), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the above formula (1), and a preferable range is also the same.

The polybenzoxazole precursor includes other types of repeating structural units in addition to the repeating units of the above formula (2).

It is preferable that the diamine residue represented by the following formula (SL) is contained as another kind of repeating structural unit from the point which can suppress generation | occurrence | production of the curvature accompanying a closed loop.

[Chemical Formula 18] In formula (SL), Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydroxyl group having 1 to 10 carbon atoms, R ^2s is a hydroxyl group having 1 to 10 carbon atoms, R ^3s , R ^4s , R ^5s , R ^6s At least one of them is an aromatic group, and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be a block polymerization or a random polymerization. Among the mole% of the Z part, the a structure is 5 to 95 mole%, the b structure is 95 to 5 mole%, and a + b is 100 mole%.

In the formula (SL), as preferable Z, there may be mentioned those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by gel permeation chromatography which is generally used. By setting the molecular weight to the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure is reduced, and the effect of suppressing warpage and the effect of improving solubility can be taken into consideration.

When the diamine residue represented by the formula (SL) is included as another kind of repeating structural unit, from the viewpoint of improving alkali solubility, it also includes the remaining four after removing the acid dianhydride group from the tetracarboxylic dianhydride A carboxylic acid residue is preferable as a repeating structural unit. Examples of such a tetracarboxylic acid residue include an example of R ¹¹⁵ in formula (1).

Examples of the polybenzoxazole precursor include 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diamino-2,2 '. -Polybenzoxazole precursors obtained from bis (trifluoromethyl) biphenyl and 4,4'-oxobenzophenone chloride, 2,2'-bis (3-amino-4-hydroxybenzene) Based) Hexafluoropropane and methacrylic acid chloride precursors of polybenzoxazole.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, more preferably 4,000 to 25,000, still more preferably 4,000 to 15,000, and still more preferably 5,000 to 10,000. The degree of dispersion is preferably 1.5 to 4.0, and more preferably 2.0 to 3.5.

<Acidic Compound> The resin composition of the present invention contains an acidic compound having a pKa of 4.0 or less. Here, pKa represents the inverse of the logarithm (-Log ₁₀ Ka) of the dissociation constant (Ka) of the proton of the acidic compound. The pKa value of the acidic compound is measured according to the method described in the examples described later. By including such an acidic compound, a photosensitive resin composition having excellent storage stability and high resolution can be provided. The pKa of the acidic compound used in the present invention is preferably 3.5 or lower, more preferably 3.0 or lower, 2.5 or lower is further preferable, 2.0 or lower is further preferable, 1.0 or lower is further preferable, and 0.0 or lower is further Better. The lower limit of the above pKa is not particularly specified, but is preferably -3.0 or more, more preferably -2.0 or more, and -1.0 or more is more preferable.

The molecular weight of an acidic compound having a pKa of 4.0 or less is preferably 500 or less, more preferably 400 or less, even more preferably 300 or less, more preferably 250 or less, and even more preferably 200 or less. By using such an acidic compound, the acidic compound is volatilized during hardening, and the corrosion of metals such as when a cured film is used as an insulating film can be more effectively suppressed. The lower limit of the molecular weight is not particularly limited, but 45 or more is preferable, 80 or more is more preferable, and 100 or more is more preferable.

Among acidic compounds with a pKa of 4.0 or less, the type is not particularly limited, but is preferably selected from sulfonic acid, carboxylic acid, imine acid, methylated acid, hydrochloric acid, nitric acid, and sulfuric acid, and is selected from sulfonic acid and carboxylic acid. More preferably, a polyvalent carboxylic acid selected from a sulfonic acid and a divalent or more is more preferred, and a sulfonic acid is further preferred. The acid compound having a pKa of 4.0 or less may be a hydrate or may not be a hydrate.

As the sulfonic acid, a monovalent sulfonic acid having one sulfo group in one molecule is preferred. Specific examples of the sulfonic acid include toluenesulfonic acid (for example, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate), camphorsulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and nonafluoro-1-butanesulfonic acid. Acid, benzenesulfonic acid, poly (p-styrenesulfonic acid), and 2-naphthalenesulfonic acid are preferred, and selected from toluenesulfonic acid, camphorsulfonic acid, and methanesulfonic acid, and at least toluenesulfonic acid is further preferred. .

The carboxylic acid may be a monovalent carboxylic acid having one carboxyl group in one molecule, or a polyvalent carboxylic acid having two carboxyl groups in one molecule, and a polyvalent carboxylic acid is preferred. In the case of a polyvalent carboxylic acid, the number of carboxyl groups in one molecule is preferably 2 to 4, and two is more preferable. Specific examples of the carboxylic acid are selected from formic acid, oxalic acid (for example, oxalic acid dihydrate), maleic acid, malonic acid, pyruvate, DL-lactic acid, trifluoroacetic acid, glyoxylic acid, and maleic acid Methyl esters are preferred, selected from formic acid, oxalic acid, maleic acid, malonic acid, pyruvate, and DL-lactic acid, and selected from oxalic acid, maleic acid, malonic acid, pyruvate, and DL-lactic acid is further preferred, and further selected from oxalic acid, maleic acid, and malonic acid is further preferred, and at least oxalic acid is further preferred.

In the resin composition of the present invention, it is preferable to include an acidic compound having a pKa of 4.0 or less in a proportion of 10 to 0.001 parts by mass with respect to 100 parts by mass of the total amount of the heterocyclic-containing polymer precursor, and 1 to 0.001 parts by mass The ratio is more preferably contained, and the ratio is more preferably 0.1 to 0.005 parts by mass. The resin composition of the present invention may contain one kind of acidic compound having a pKa of 4.0 or less, or may contain two or more kinds of acidic compounds having a pKa of 4.0 or less. When two or more kinds of acid compounds having a pKa of 4.0 or less are included, the total amount is preferably in the above range.

The resin composition of the present invention may contain an acidic compound having a pKa of more than 4.0, but it is preferably not substantially contained. By substantially not included, it means, for example, that the amount of the acidic compound is 1% by mass or less of the total amount of acidic compounds having a pKa of 4.0 or less contained in the resin composition, 0.1% by mass or less is preferable, and 0.01% by mass or less is Better.

<Other Components of Resin Composition> The resin composition of the present invention may contain components other than the heterocyclic-containing polymer precursor and an acidic compound having a pKa of 4.0 or less. Specific examples include solvents and polymerization inhibitors. For details of the solvent and the polymerization inhibitor, refer to the description of the solvent and the polymerization inhibitor in other components of the photosensitive resin composition described later. In addition, it can include impurities derived from raw materials used in the synthesis of the heterocyclic-containing polymer precursor and the like. The resin composition of the present invention preferably does not substantially contain an acid generator. The term “substantially not included” means, for example, that the total amount of the heterocyclic-containing polymer precursor contained in the resin composition is 1% by mass or less, preferably 0.1% by mass or less, and more preferably 0.01% by mass or less.

<Form of Resin Composition> The form of the resin composition of the present invention may be liquid or powder. When the resin composition of the present invention is liquid, it is preferable that 10 to 90% by mass of the resin composition is a solvent. The content of the heterocyclic-containing polymer precursor in the resin composition is preferably 1 to 80% by mass. When the resin composition of the present invention is in a powder form, it is preferable that 80% by mass or more of the resin composition is a heterocyclic-containing polymer precursor. Here, the powdery form means a fine solid material as a main component. The main component refers to the component with the largest content in the resin composition. It means that it is more preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and 98% by mass or more is a further preferred component. . Among the fine solid materials in the present invention, the average of the maximum length is preferably 10 mm or less, and more preferably 5 mm or less. For example, commercially available powdered resins and polymerizable monomers are fine solid substances included in the present invention. The powdery resin composition may contain a solvent, and the content of the solvent is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[Manufacturing method of resin composition] The manufacturing method of the resin composition of the present invention is the production of a resin composition containing a heterocyclic polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor. A method comprising a process of adding an acidic compound having a pKa of 4.0 or less. An acidic compound having a pKa of 4.0 or less may be added during the synthesis process of the heterocyclic-containing polymer precursor, or may be added after synthesizing the heterocyclic-containing polymer precursor. Here, the synthesis process of the heterocyclic-containing polymer precursor refers to a process of starting the reaction of the raw material monomer to the end of the reaction of the raw material monomer. Ending means, for example, filtering the reaction liquid or performing a process based on solvent precipitation. Therefore, the purpose is to continue the reaction without containing trace amounts of ingredients. On the other hand, after the synthesis of a heterocyclic polymer-containing precursor is meant after the synthesis process is completed.

If an acidic compound having a pKa of 4.0 or less is added to the synthesis process of the heterocyclic-containing polymer precursor, the position dependency of the acidic compound present in the polymer can be reduced. An acidic compound having a pKa of 4.0 or less is preferably a compound that does not react with a raw material monomer of a heterocyclic-containing polymer precursor. When an acidic compound having a pKa of 4.0 or less is added to the synthesis process of the heterocyclic-containing polymer precursor, the addition amount of the acidic compound having a pKa of 4.0 or less is relative to the finally obtained heterocyclic-containing polymer precursor 100. It is preferably 50 to 0.1 parts by mass, and more preferably 20 to 1 part by mass.

In the present invention, it is also preferable to add a carbodiimide compound in the synthesis process of the heterocyclic-containing polymer precursor. The carbodiimide compound can function as a condensing agent of a carboxyl group and an amine group when a raw material monomer of a heterocyclic polymer is reacted. As a first embodiment using a carbodiimide compound, the following state can be exemplified. After adding a compound having an acid dianhydride and a polymerizable group and a carbodiimide compound to perform a reaction, a diamine compound is added to further react, thereby A polyimide precursor was obtained. In the case of adding an acidic compound having a pKa of 4.0 or less to the synthesis process of a heterocyclic-containing polymer precursor, in the case of adding a carbodiimide compound, it is added earlier than the acidic compound having a pKa of 4.0 or less A carbodiimide compound is preferred.

Examples of the carbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, diethylcarbodiimide, ethylcyclohexylcarbodiimide, and diphenylcarbodiimide. And at least one of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, dicyclohexylcarbodiimide and diisopropylcarbodiimide is preferred . The molecular weight of the carbodiimide compound is preferably 100 to 400. The addition amount of the carbodiimide compound is preferably 500 to 50 parts by mass, and more preferably 250 to 90 parts by mass, with respect to 100 parts by mass of the heterocyclic ring-containing polymer precursor finally obtained.

[Photosensitive resin composition] The photosensitive resin composition of the present invention includes a resin composition and a photopolymerization initiator. The resin composition includes a heterocyclic ring selected from a polyimide precursor and a polybenzoxazole precursor. Polymer precursor and acidic compound having a pKa of 4.0 or less, characterized in that the photosensitive resin composition is a cured film having a thickness of 10 μm, and the conductivity of the cured film after heating at 350 ° C. for 60 minutes is 1.0 × 10 ⁵ Ω ･ cm or less. Hereinafter, details of the photosensitive resin composition of the present invention will be described.

<Conductivity of the cured film of the photosensitive resin composition> The conductivity of the cured film after the photosensitive resin composition of the present invention is a 10 μm-thick cured film and heated at 350 ° C. for 60 minutes is 1.0 × 10 ⁵ Ω ･ Cm or less. With such a structure, the insulation of the cured film can be maintained. The electrical conductivity was measured according to the method described in Examples described later.

<Resin Composition> The photosensitive resin composition of the present invention includes a resin composition including a heterocyclic polymer precursor and pKa selected from a polyimide precursor and a polybenzoxazole precursor. It is an acidic compound of 4.0 or less. The resin composition contained in the photosensitive resin composition is a cured film having a thickness of 10 μm, and the conductivity of the cured film after heating at 350 ° C. for 60 minutes is preferably 1.0 × 10 ⁵ Ω ･ cm or less. The photosensitive resin composition itself satisfies the above-mentioned conductivity condition, and the resin composition contained in the photosensitive resin composition need not satisfy the above-mentioned conductivity. The details of the heterocyclic-containing polymer precursor and the acidic compound having a pKa of 4.0 or less contained in the photosensitive resin composition are the same as in the case of the resin composition described above, and the preferred ranges are also the same. The resin composition contained in the photosensitive resin composition is preferably a resin composition that satisfies the above-mentioned predetermined conductivity.

The content of the heterocyclic-containing polymer precursor in the photosensitive resin composition of the present invention is preferably 20 to 100% by mass, and more preferably 50 to 99% by mass relative to the total solid content of the photosensitive resin composition. 60 to 98% by mass is more preferred, and 70 to 95% by mass is particularly preferred. The heterocyclic-containing polymer may include one kind, or two or more kinds. In the case where two or more kinds are included, it is preferable that the total measurement falls within the above range. The photosensitive resin composition of the present invention preferably contains an acidic compound having a pKa of 4.0 or less in a ratio of 100 to 0.0001 parts by mass with respect to 100 parts by mass of the total amount of the heterocyclic-containing polymer precursor, and is preferably 10 to 0.001. It is more preferable to include the parts by mass, and it is more preferable to include the parts from 1 to 0.01 parts by mass. The photosensitive resin composition of the present invention may contain one kind of acidic compound having a pKa of 4.0 or less, or may contain two or more kinds. In the case where two or more kinds are included, it is preferable that the total measurement falls within the above range.

<Photopolymerization initiator> There is no restriction | limiting in particular as a photopolymerization initiator which can be used for this invention, It can select from a well-known photopolymerization initiator suitably. For example, a photopolymerization initiator having a sensitivity from the ultraviolet region to the light in the visible region is preferred. Moreover, it may be an active agent which generates an active radical by having an arbitrary action with a photo-excited sensitizer. The photopolymerization initiator preferably contains at least one compound having an absorbance coefficient of about 50 Molar in a range of about 300 to 800 nm (330 to 500 nm is preferred). The molar absorption coefficient of a compound can be measured using a well-known method. For example, a UV-visible spectrometer (Cary-5 spectrophotometer, manufactured by Varian Corporation) is preferably used for measurement at a concentration of 0.01 g / L using an ethyl acetate solvent.

The photosensitive resin composition of the present invention contains a photopolymerization initiator, whereby the photosensitive resin composition of the present invention is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then the light is irradiated to cause a problem. The generated free radicals are hardened and can reduce the solubility in the light-irradiated portion. Therefore, there is an advantage that, for example, by exposing the photosensitive resin composition layer through a photomask having a pattern that covers only the electrode portion, regions having different solubility can be easily manufactured according to the pattern of the electrode.

As the photopolymerization initiator, a known compound can be arbitrarily used. Examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), fluorenylphosphine compounds such as fluorenylphosphine oxide, and hexaarylbisimidazole Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, Metallocene compounds, organoboron compounds, fluorene aromatic hydrocarbon complexes, etc. For the details, refer to the descriptions in paragraphs 0165 to 0182 of Japanese Patent Application Laid-Open No. 2016-027357, and incorporate the contents into this specification.

As the ketone compound, for example, a compound described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611 can be exemplified, and the content is incorporated into the present specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a fluorenylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and a fluorenylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used. As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, commercially available IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 can be used in which the absorption maximum wavelength is matched to a wavelength light source such as 365 nm or 405 nm. Examples of the fluorenylphosphine-based initiator include 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide and the like. In addition, IRGACURE-819 and IRGACURE-TPO (product names: both manufactured by BASF) can be used as commercially available products. Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

As the photopolymerization initiator, an oxime compound is more preferable. By using an oxime compound, exposure latitude can be improved more effectively. It is preferable that the oxime compound has a wide exposure latitude (exposure margin). As specific examples of the oxime compound, a compound described in JP 2001-233842, a compound described in JP 2000-80068, and a compound described in JP 2006-342166 can be used. . Preferred oxime compounds include, for example, compounds having the following structure, 3-benzyloxyiminobutane-2-one, 3-ethoxyiminobutane-2-one, and 3 -Propanyloxyiminobutane-2-one, 2-Ethyloxyiminopentane-3-one, 2-Ethyloxyimino-1-phenylpropane-1-one , 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Imino-1-phenylpropane-1-one and the like. [Chemical Formula 19] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF), ADEKA OPTOMER N-1919 (made by ADEKA CORPORATION, Japanese Patent Application Laid-Open No. 2012-14052) The photopolymerization initiator 2) described in the publication. In addition, TR-PBG-304 (Changzhou Power Electronics New Materials Co., Ltd. Corporation), ADEKA ARCLS NCI-831, and ADEKA ARCLS NCI-930 (manufactured by ADEKA Corporation) can also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used. In addition, an oxime compound having a fluorine atom can also be used. Specific examples of such an oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds 24, 36-40, and Japanese Patent Application No. 2014-500852 described in paragraphs 0345 to 0348, Compound (C-3) and the like described in paragraph 0101 of Japanese Patent Application Laid-Open No. 2013-164471. Examples of the preferred oxime compound include an oxime compound having a specific substituent shown in Japanese Patent Application Laid-Open No. 2007-269779 and an oxime compound having a thioaryl group shown in Japanese Patent Application Laid-Open No. 2009-191061. Wait.

From the viewpoint of exposure sensitivity, the photopolymerization initiator is selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a fluorenylphosphine compound, Phosphine oxide compound, metallocene compound, oxime compound, triarylimidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-pyrene Compounds and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred. Further preferred photopolymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, fluorenylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, and diamines. At least one compound selected from the group of benzophenone compounds and acetophenone compounds selected from the group of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is It is further preferable to use a metallocene compound or an oxime compound, and an oxime compound is particularly preferable. In addition, as the photopolymerization initiator, N, N'-tetraalkyl-, such as benzophenone and N, N'-tetramethyl-4,4'-diaminobenzophenone (myrone), can be used. 4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 2-methyl-1- Aromatic ketones such as [4- (methylthio) phenyl] -2-morpholinyl-acetone-1, quinones formed by condensing with aromatic rings such as alkyl anthraquinone, and benzoin such as benzoin alkyl ether Ether compounds, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyldimethylketal, and the like. In addition, a compound represented by the following formula (I) can also be used. [Chemical Formula 20] In formula (I), R ⁵⁰ is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, At least at least one of a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms. A substituted phenyl or biphenyl group, R ⁵¹ is a group represented by formula (II) or the same group as R ⁵⁰ , and R ⁵² to R ⁵⁴ are each independently an alkyl group having 1 to 12 carbons and carbon Alkoxy or halogen of 1-12. [Chemical Formula 21] In the formula, R ⁵⁵ to R ⁵⁷ are the same as R ⁵² to R ^{54 in} the formula (I).

As the photopolymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. WO2015 / 125469 can also be used.

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 5 to 15% by mass based on the total solid content of the photosensitive resin composition of the present invention. The photopolymerization initiator may contain one kind or two or more kinds. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably in the above range.

<Other Components of Photosensitive Resin Composition> The photosensitive resin composition of the present invention may include components other than the heterocyclic-containing polymer precursor, an acidic compound having a pKa of 4.0 or less, and a photopolymerization initiator. Specific examples include solvents and polymerization inhibitors. In addition, it can include impurities derived from raw materials used in the synthesis of the heterocyclic-containing polymer precursor and the like. It is preferable that the resin composition of the present invention does not substantially contain an acid generator. Here, “substantially not included” means, for example, that the content of the acid generator contained in the resin composition is 1% by mass or less, preferably 0.1% by mass or less, and 0.01% by mass of the total amount of the heterocyclic polymer precursor. % Is better.

<< Thermal alkali generator >> The photosensitive resin composition of this invention may contain a thermal alkali generator. By using a hot alkali generator, during the heating process of the ring-closing reaction of a heterocyclic-containing polymer precursor, an alkali species that promotes the ring-closing reaction can be generated. Therefore, the ring-closing rate tends to be increased. There is no particular limitation on the type of the hot alkali generator, but it is preferable to include a hot alkali generator. The hot alkali generator contains an acidic compound selected from the group consisting of an acidic compound (where pKa is greater than 4) Compound) and at least one of an anion and an ammonium cation having a pKa1 of 0 to 4. Here, pKa1 represents the logarithm (-Log ₁₀ Ka) of the inverse of the dissociation constant (Ka) of the first proton of the acid.

The acidic compound (A1) and the ammonium salt (A2) generate a base upon heating. Therefore, the base generated from these compounds can promote the cyclization reaction of the heterocyclic polymer precursor, and can be used at low temperatures. Cyclization of heterocyclic polymer precursors is performed. In addition, even if these compounds coexist with a heterocyclic-containing polymer precursor that is hardened by cyclization with a base, the cyclization of the heterocyclic-containing polymer precursor is hardly performed unless heating is performed. A photosensitive resin composition excellent in storage stability. In addition, in the present specification, an acidic compound refers to a compound that collects 1 g of a compound in a container, adds 50 ml of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4), and uses pH (power of hydrogen (pH) meter, the measured value of the solution obtained by stirring at room temperature for 1 hour at 20 ° C is less than 7.

In this embodiment, the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C or higher, and more preferably 120 to 200 ° C. The upper limit of the alkali generation temperature is preferably 190 ° C or lower, more preferably 180 ° C or lower, and even more preferably 165 ° C or lower. The lower limit of the alkali generation temperature is preferably 130 ° C or higher, and more preferably 135 ° C or higher. If the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C or higher, it is difficult to generate an alkali during storage, so that a photosensitive resin composition having excellent storage stability can be prepared. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C or lower, the cyclization temperature of the heterocyclic-containing polymer precursor can be reduced. The alkali generation temperature can be measured by, for example, using differential scanning calorimetry, heating the compound to 250 ° C at 5 ° C / min in a pressure-resistant capsule, and reading the peak temperature of the lowest temperature exothermic peak. The peak temperature is taken as the alkali generation temperature.

In this embodiment, it is preferable that the base generated by the hot alkali generator is a secondary amine or a tertiary amine, and a tertiary amine is more preferable. The tertiary amine is highly basic, so it is possible to lower the cyclization temperature of polyimide precursors and polybenzoxazole precursors. The boiling point of the alkali generated by the hot alkali generator is preferably 80 ° C or higher, more preferably 100 ° C or higher, and even more preferably 140 ° C or higher. The molecular weight of the generated base is preferably 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is preferably 500 or less. The molecular weight value is a theoretical value obtained from a structural formula.

In this embodiment, the acidic compound (A1) preferably contains one or more compounds selected from an ammonium salt and a compound having an ammonium structure represented by the formula (101) or (102) described later.

In this embodiment, it is preferable that the said ammonium salt (A2) is an acidic compound. In addition, the ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C or higher (preferably 120 to 200 ° C), or it may be a compound other than heated to 40 ° C or higher (120 to 200 ° C is (Preferably) compounds other than acidic compounds which generate a base.

In this embodiment, the ammonium salt refers to a salt of an ammonium cation and an anion represented by the following formula (101) or formula (102). The anion may be bonded to any part of the ammonium cation via a covalent bond, and may be provided outside the molecule of the ammonium cation, but it is preferable to have an anion outside the molecule of the ammonium cation. In addition, having an anion outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded by a covalent bond. Hereinafter, the anion outside the molecule to the cation part is also called a counter anion. Formula (101) Formula (102) [Chemical Formula 22] In the formulae (101) and (102), R ¹ to R ⁶ each independently represent a hydrogen atom or a hydroxyl group, and R ⁷ represents a hydroxyl group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁵ and R ^{7 in} formulas (101) and (102) may be bonded to form a ring, respectively.

The ammonium cation is preferably represented by any one of the following formulae (Y1-1) to (Y1-5). [Chemical Formula 23]

Formula (Y1-1) (Y1-5) in ~, R ¹⁰¹ represents a n-valent organic group, the same meanings as R ¹ and R ⁷ of formula (101) or (102) R ¹ and R ^7. In the formulae (Y1-1) to (Y1-4), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5.

In this embodiment, the ammonium salt preferably has an anion and an ammonium cation having a pKa1 of 0 to 4. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the heterocyclic-containing polymer precursor can be cyclized at a lower temperature, and the stability of the photosensitive resin composition can be improved. When the pKa1 is 4 or less, the stability of the hot alkali generator is good, the generation of alkali without heating can be suppressed, and the stability of the photosensitive resin composition is good. When pKa1 is 0 or more, it is difficult to neutralize the generated base, and the cyclization efficiency of a heterocyclic-containing polymer precursor and the like is good. The type of the anion is preferably one selected from the group consisting of a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferred for reasons of considering the stability of the salt and the thermal decomposability. That is, a salt in which an ammonium salt is an ammonium cation and a carboxylate anion is more preferable. The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. In this state, it is possible to use a hot alkali generator that further improves the stability, curability, and developability of the photosensitive resin composition. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the photosensitive resin composition can be further improved. In this embodiment, the carboxylate anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. A pKa1 of 3.5 or less is more preferred, and a 3.2 or less is even more preferred. In this state, the stability of the photosensitive resin composition can be further improved. Here, as for pKa1, the value calculated by the structural formula using software of ACD / pKa (made by ACD / Labs CORPORATION) was used.

The carboxylate anion is preferably represented by the following formula (X1). [Chemical Formula 24] In the formula (X1), EWG represents an electron withdrawing group.

The electron-withdrawing group in this embodiment refers to a case where the Hammett substituent constant σm represents a positive value. Here, σm is described in detail by Tono Takeo, General Society of Organic Synthetic Chemistry, No. 23, No. 8 (1965) p. 631-642. The electron-withdrawing group in this embodiment is not limited to the substituent described in the above-mentioned document. Examples of substituents in which σm represents a positive value include CF ₃ group (σm = 0.43), CF ₃ CO group (σm = 0.63), HC≡C group (σm = 0.21), and CH ₂ = CH group ( σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH = CH group (σm = 0.21), PhCO group (σm = 0.34), H ₂ NCOCH ₂ group (σm = 0.06), etc. . In addition, Me represents a methyl group, Ac represents an ethenyl group, and Ph represents a phenyl group (hereinafter, the same).

EWG is preferably a group represented by the following formulae (EWG-1) to (EWG-6). [Chemical Formula 25] In the formulae (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group, and Ar represents an aromatic group.

In this embodiment, the carboxylate anion is preferably represented by the following formula (XA). Formula (XA) [Chemical Formula 26] In formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from the group consisting of an alkylene group, an alkenyl group, an aromatic group, -NR ^X- , and these combinations, and R ^X represents a hydrogen atom, an alkyl group, Alkenyl or aryl.

Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenylimide diacetate anion, and an oxalate anion.

Specific examples of the hot alkali generator include the following compounds. [Chemical Formula 27] [Chemical Formula 28]

[Chemical Formula 29] [Chemical Formula 30]

When the photosensitive resin composition of the present invention contains a thermal alkali generator, the content of the thermal alkali generator is preferably 0.1 to 50% by mass based on the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, more preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and 4% by mass or less. As the hot alkali generator, one kind or two or more kinds can be used. In the case of using two or more kinds, it is preferable that the total measurement falls within the above range.

<< Solvent> It is preferable that the photosensitive resin composition of this invention contains a solvent. The solvent can be any known solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, fluorenes, and amidines. Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. , Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (such as methyl alkoxyacetate, alkoxy Ethyl acetate, butyl ethoxyacetate (such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkoxypropanoic acid alkyl esters (such as methyl 3-alkoxypropanoate, ethyl 3-alkoxypropanoate, etc. (such as methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g. methyl 2-alkoxypropionate , Ethyl 2-alkoxypropionate, 2-alkoxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl ester, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy-2-methylpropane Methyl ester and ethyl 2-alkoxy-2-methylpropionate (eg methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.) ), Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like. Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve B. Acid esters, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Ether acetate and the like. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include toluene, xylene, anisole, and limonene. As the fluorene, for example, dimethyl fluorene is preferred. Preferred examples of the amidines include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamidine. Amine, etc.

From the viewpoint of improving the properties of the coating surface, it is also preferable that the solvent is a mixture of two or more kinds. Among them, selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethylsulfinium, ethylcarbitol acetate, butylcarbitol ethyl A mixed solution composed of two or more of an acid ester, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. It is particularly preferred to use dimethyl sulfene and γ-butyrolactone.

From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the photosensitive resin composition of the present invention becomes 5 to 80% by mass, and more preferably 5 to 70% by mass. 10 60% by mass is particularly preferred. The solvent content may be adjusted by the desired thickness and coating method. For example, if the coating method is a spin coating method or a slit coating method, the content of the solvent having the solid content concentration in the above range is preferred. In the case of the spray coating method, an amount of 0.1 to 50% by mass is preferable, and an amount of 1.0 to 25% by mass is more preferable. By adjusting the amount of the solvent according to the coating method, a photosensitive resin composition layer having a desired thickness can be uniformly formed. The solvent may contain only one kind or two or more kinds. When two or more kinds of solvents are contained, the total amount is preferably in the above range.

<< Polymerizable Compound> The photosensitive resin composition of the present invention preferably contains a polymerizable compound (hereinafter, also referred to as a "polymerizable monomer"). With such a structure, a cured film having excellent heat resistance can be formed.

As the polymerizable monomer, a compound (radical polymerizable compound) having a radical polymerizable group can be used. Examples of the radical polymerizable group include a group having an ethylenically unsaturated bond such as a styryl group, a vinyl group, a (meth) propenyl group, and an allyl group. The radical polymerizable group is preferably a (meth) propenyl group.

The polymerizable monomer may have one radical polymerizable group, or may have two or more, but it is preferable to have two or more radical polymerizable groups, and it is more preferable to have three or more radical polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

The molecular weight of the polymerizable monomer is preferably 2,000 or less, more preferably 1500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more.

From the viewpoint of developability, the photosensitive resin composition of the present invention preferably contains at least one bifunctional or more polymerizable monomer containing two or more polymerizable groups, and contains at least one trifunctional or more polymerizable monomer. Body is better. Moreover, it may be a mixture of a bifunctional polymerizable monomer and a trifunctional or more polymerizable monomer. The number of functional groups of the polymerizable monomer means the number of radical polymerizable groups in one molecule.

Specific examples of the polymerizable monomer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amidines. Ester of unsaturated carboxylic acid and polyhydric alcohol compound and ammonium of unsaturated carboxylic acid and polyamine compound are preferable. In addition, it is also preferable to use an addition reaction product of an unsaturated carboxylic acid ester or amidoamine having a nucleophilic substituent such as a hydroxyl group, an amine group, and a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and Dehydration condensation reactants of functional or polyfunctional carboxylic acids. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amidoamine having an electrophilic substituent such as an isocyanate group and an epoxy group with a monofunctional or polyfunctional alcohol, an amidine, or a thiol is also preferable. Further preferred are substitution reactions of unsaturated carboxylic acid esters or amidoamines, monofunctional or polyfunctional alcohols, amidoamines, and thiols with detachable substituents such as halo and tosylsulfonyloxy. . As another example, instead of the unsaturated carboxylic acid described above, a group of compounds substituted with vinyl phenol derivatives such as unsaturated phosphonic acid and styrene, vinyl ethers, and allyl ethers may be used. As a specific example, reference can be made to the descriptions in paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357, which are incorporated into this specification.

As for the polymerizable monomer, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples of this include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, and pentaerythritol tri (methyl) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri ( After the addition of ethylene oxide or propylene oxide to polyfunctional alcohols, such as propylene glycoloxypropyl) ether, tris (propylene glycoloxyethyl) isocyanurate, glycerol, and trimethylolethane ( (Meth) acrylic compounds such as those described in JP 48-41708, JP 50-6034, and JP 51-37193 Esters, polyester acrylates described in JP 48-64183, JP 49-43191, and JP 52-30490, as epoxy resins and (meth) acrylic acid Polyfunctional acrylics such as epoxy acrylates of reaction products Ester or methacrylate and a mixture of these. The compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also preferred. In addition, polyfunctional (meth) acrylates obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated group such as glycidyl (meth) acrylate in a polyfunctional carboxylic acid can also be mentioned. In addition, as other preferable polymerizable monomers, those having a fluorene ring and having ethylenic properties described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, and Japanese Patent No. 4364216 can also be used. Two or more compounds of unsaturated bond groups or cardo resin. In addition, as other examples, Japanese Unexamined Patent Publication No. 46-43946, Japanese Unexamined Patent Publication No. 1-40337, and Japanese Unexamined Patent Publication No. 1-40336 may include specific unsaturated compounds and Japanese Unexamined Patent Publication No. Hei 2 Vinylphosphonic acid-based compounds and the like described in JP-25493. In addition, a compound containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. 61-22048 can also be used. It can also be used as a photopolymerizable monomer and oligomer introduced in the Journal of the Adhesion Society of Japan vol. 20, No. 7, pages 300 to 308 (1984). .

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Laid-Open No. 2015-034964 are also preferably used, and these contents are incorporated in this specification.

In addition, as described in Japanese Patent Application Laid-Open No. 10-62986 as formula (1) and formula (2) together with specific examples thereof, after adding ethylene oxide or propylene oxide to a polyfunctional alcohol, (meth) acrylic acid Esterified compounds can also be used as polymerizable monomers.

In addition, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as polymerizable monomers, and these contents are incorporated herein.

The polymerizable monomers are dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; Nippon Kayaku Co., Ltd., A-TMMT; Shin-Nakamura Chemical Co., Ltd.); dipentaerythritol penta (meth) acrylate (KAYARAD D-310 as a commercial product; Nippon Kayaku Co., Ltd. .), Dipentaerythritol hexa (meth) acrylate (available commercially as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) and these ( A structure in which a (meth) acrylfluorenyl group is bonded via an ethylene glycol residue and a propylene glycol residue is preferred. These oligomer types can also be used.

Examples of commercially available polymerizable monomers include SR-494, a four-functional acrylate having four ethoxy chains, and bifunctional methyl having four ethoxy chains, which are manufactured by Sartomer Company Inc. Acrylate is SR-209 made by Sartomer Company Inc., 6-functional acrylate with 6 penteneoxy chains, made by Nippon Kayaku Co., Ltd., is DPCA-60, and 3 methacryloxy chains Trifunctional acrylates are TPA-330, NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA- 40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by KYOEISHA CHEMICAL Co., Ltd), Blemmer PME400 (NOF CORPORATION制) and so on.

The polymerizable monomer is also preferably acrylic acid as described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Urethanes or ethylene oxides described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. It is a carbamate compound of the skeleton. In addition, as the polymerizable monomer, Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 1-105238 can be used as having a amine structure in the molecule. Or thioether structure compounds.

The polymerizable monomer may be a polymerizable monomer having an acid group such as a carboxyl group, a sulfo group, or a phosphate group. The polymerizable monomer having an acidic radical is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. An unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic dianhydride to form an acidic radical. A polymerizable monomer is more preferred. Among polymerizable monomers having an acidic radical reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic dianhydride, a compound in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol is particularly preferred. As a commercial item, M-510, M-520, etc. are mentioned as a polybasic acid modified acrylic oligomer by TOAGOSEI CO., LTD., For example. The polymerizable monomer having an acid group may be used singly or in combination of two or more kinds. If necessary, a polymerizable monomer having no acid group and a polymerizable monomer having an acid group may be used in combination. The preferred acid value of the polymerizable monomer having an acid radical is 0.1 to 40 mgKOH / g, and 5 to 30 mgKOH / g is particularly preferred. When the acid value of a polymerizable monomer is the said range, it will be excellent in manufacture and handleability, and will also be excellent in developability. In addition, the polymerizability was good.

From the viewpoint of good polymerizability and heat resistance, the content of the polymerizable monomer is preferably 1 to 50% by mass based on the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 30% by mass or less. The polymerizable monomers may be used singly or in combination of two or more kinds. The mass ratio of the heterocyclic-containing polymer precursor to the polymerizable monomer (the heterocyclic-containing polymer precursor / polymerizable monomer) is preferably 98/2 to 10/90, and 95/5 to 30 / 70 is more preferable, and 90/10 to 50/50 is the best. When the mass ratio of the heterocyclic-containing polymer precursor to the polymerizable monomer is within the above range, a cured film having more excellent polymerizability and heat resistance can be formed.

From the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the cured film, the photosensitive resin composition of the present invention can preferably use a monofunctional polymerizable monomer. As the monofunctional polymerizable monomer, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxy Ethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N -(Meth) acrylic acid derivatives such as methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. , N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate Class, etc. As the monofunctional polymerizable monomer, in order to suppress volatilization before exposure, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.

The photosensitive resin composition of the present invention can contain other polymerizable compounds in addition to the heterocyclic-containing polymer precursor and the radical polymerizable compound described above. Examples of other polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group, or a fluorenylmethyl group; epoxy compounds; oxetane compounds; and benzoxazine compounds.

(A compound having a hydroxymethyl group, an alkoxymethyl group, or a fluorenylmethyl group) As a compound having a hydroxymethyl group, an alkoxymethyl group, or a fluorenylmethyl group, a compound represented by the following formula (AM1) Is better.

[Chemical Formula 31] (In the formula, t represents an integer of 1 to 20, R ⁴ represents a t-valent organic group having 1 to 200 carbon atoms, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , and R ⁶ represents a hydrogen atom. Or an organic group having 1 to 10 carbons, and R ⁷ represents an organic group having 1 to 10 carbons.)

The content of the compound represented by the formula (AM1) is preferably 5 to 40 parts by mass based on 100 parts by mass of the heterocyclic-containing polymer precursor. 10 to 35 parts by mass is more preferred. In addition, the total amount of other polymerizable compounds is preferably 10 to 90% by mass of the compound represented by the following formula (AM4), and 10 to 90% by mass of the compound represented by the following formula (AM5) is also preferred.

[Chemical Formula 32] (In the formula, R ⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , and R ⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms. Group, R ⁷ represents an organic group having 1 to 10 carbon atoms.)

[Chemical Formula 33] (In the formula, u represents an integer of 3 to 8, R ⁴ represents a u-valent organic group having 1 to 200 carbon atoms, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , and R ⁶ represents a hydrogen atom or An organic group having 1 to 10 carbon atoms, and R ⁷ represents an organic group having 1 to 10 carbon atoms.)

By using a compound having the above-mentioned hydroxymethyl group or the like, when the photosensitive resin composition of the present invention is applied to an arbitrary substrate having unevenness, it is possible to more effectively suppress the occurrence of depressions. In addition, it has excellent pattern processability, and can form a cured film having a 5% mass reduction temperature of 350 ° C. or higher, and more preferably 380 ° C. or higher. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC , DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (the above are the product names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (product name, manufactured by SanWa Chemical co, .LTD.), 2,6-dimethoxymethyl-4-t-buthylphenol (2,6-dimethoxymethyl-4-tert-butylphenol), 2 2,6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacethoxymethyl-p-cresol (2,6-diethoxymethyl-p-cresol) )Wait.

Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, and HML- TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the product name above, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (product name, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are product names, manufactured by SanWa Chemical co, .LTD.).

(Epoxy compound (compound having an epoxy group)) As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a cross-linking reaction at a temperature of 200 ° C or lower, and a dehydration reaction due to cross-linking does not occur, and thus film shrinkage is difficult to occur. Therefore, containing an epoxy compound can effectively suppress low-temperature curing and warping of the photosensitive resin composition.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further reduced, and warpage can be suppressed. In addition, a cured film having high flexibility and excellent elongation and the like can be obtained. The polyethylene oxide group is one in which the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of the epoxy compound include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkanediol type epoxy resins such as propylene glycol diglycidyl ether; and polyalkylene dipropylene glycols such as polypropylene glycol diglycidyl ether. Alcohol-type epoxy resins; epoxy-containing silicones, such as polymethyl (glycidyloxypropyl) siloxane; but are not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) Trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (above are product names, manufactured by DIC Corporation), RIKARESIN (registered trademark) Trademark) BEO-60E (product name, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the product name above, made by ADEKA CORPORATION), etc. Among these, a polyethylene oxide-based epoxy resin is preferable in terms of suppression of warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E are preferred because they contain polyethylene oxide groups.

The content of the epoxy compound is preferably 5 to 50 parts by mass relative to 100 parts by mass of the heterocyclic-containing polymer precursor, more preferably 10 to 50 parts by mass, and even more preferably 10 to 40 parts by mass. When the content of the epoxy compound is 5 parts by mass or more, warping of the obtained cured film can be more suppressed, and when it is 50 parts by mass or less, pattern burying due to reflow during curing can be more suppressed.

(Oxetane compound (compound having oxetanyl group)) Examples of the oxetane compound include a compound having two or more oxetane rings in one molecule, and 3-ethyl 3-hydroxymethyloxetane, 1,4-bis {[((3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- ( 2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like. As a specific example, Aron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) made by TOAGOSEI CO., LTD. Can be preferably used, and these can be used alone or in combination of two or more kinds. .

The content of the oxetane compound is preferably 5 to 50 parts by mass relative to 100 parts by mass of the heterocyclic-containing polymer precursor, more preferably 10 to 50 parts by mass, and even more preferably 10 to 40 parts by mass.

(Benzoxazine compounds (compounds having a benzoxazolyl group)) The benzoxazine compounds are cross-linked by the ring-opening addition reaction, which does not generate outgassing during hardening, further reduces heat shrinkage and suppresses warping. It is better to consider the generation of the song.

Preferred examples of the benzoxazine compound include Ba-type benzoxazine, Bm-type benzoxazine (the above is the product name, manufactured by SHIKOKU CHEMICALS CORPORATION), and benzoxazine of polyhydroxystyrene resin. Product, phenol novolak type dihydroxybenzoxazine compound. These may be used alone or in combination of two or more.

The content of the benzoxazine compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the heterocyclic-containing polymer precursor.

<< Migration inhibitor> It is preferable that the photosensitive resin composition further contains a migration inhibitor. By including a migration inhibitor, the migration of metal ions originating from the metal layer (metal wiring) into the photosensitive resin composition layer can be effectively suppressed. The migration inhibitor is not particularly limited, and examples thereof include a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, Azole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having sulfur Urea and mercapto compounds, hindered phenol compounds, salicylic acid derivative compounds, hydrazine derivative compounds. In particular, triazole (for example, 1,2,4-triazole), triazole compounds such as benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole can be preferably used.

In addition, an ion trapping agent that captures anions such as a halide ion can also be used.

As other migration inhibitors, rust inhibitors described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-15701, compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, and Japanese Patent Laid-Open No. 2011 -59656, the compounds described in paragraph 0052, Japanese Patent Laid-Open No. 2012-194520, the compounds described in paragraphs 0114, 0116, and 0118, and the like.

Specific examples of the migration inhibitor include 1H-1,2,3-triazole and 1H-tetrazole.

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the photosensitive resin composition is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0% by mass is more preferable. The migration inhibitor may be only one type, or may be two or more types. When there are two or more kinds of migration inhibitors, the total amount is preferably in the above range.

<<< polymerization inhibitor> It is preferable that the photosensitive resin composition of the present invention contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol (1,4-methoxyphenol), di-tertiary butyl-p-cresol, gallophenol, and p-tertiary butyl- Catechol, p-benzoquinone (1,4-benzoquinone), diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2, 2'-Methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitroso diphenylamine, N -Phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol , 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N -Sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4-hydroxy-3,5-tert-butyl) phenylmethane and the like. In addition, the polymerization inhibitors described in paragraph 0060 of Japanese Patent Laid-Open No. 2015-127817 and the compounds described in paragraphs 031 to 0046 of International Publication No. WO2015 / 125469 can also be used. The following compounds (Me is methyl) can be used. [Chemical Formula 34] When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass based on the total solid content of the photosensitive resin composition of the present invention. The polymerization inhibitor may be only one kind, or two or more kinds. When there are two or more kinds of polymerization inhibitors, the total amount is preferably in the above range.

<<< Metal Adhesion Improver> The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion with a metal material used in an electrode, wiring, or the like. Examples of the metal adhesion improving agent include a silane coupling agent and the like.

Examples of the silane coupling agent include compounds described in paragraphs 0061 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication WO2011 / 080992A1, and Japanese Patent Laid-Open No. 2014 The compounds described in paragraphs 0060 to 0061 of Japanese Patent Publication No. -191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-41264, and the compounds described in paragraph 0055 of International Publication No. WO2014 / 097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group. [Chemical Formula 35]

In addition, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186, and thioethers described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 Compound.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the heterocyclic-containing polymer precursor, and the range of 0.5 to 15 parts by mass is more preferable. When it is set to 0.1 parts by mass or more, the adhesion between the cured film and the metal layer after the hardening process becomes good. When it is set to 30 parts by mass or less, the heat resistance and mechanical properties of the hardened film after the hardening process are changed Well. The metal adhesion improving agent may be only one type, or may be two or more types. In the case of using two or more kinds, it is preferable that the total amount is within the above range.

<< Other additives >> The photosensitive resin composition of the present invention can be blended with various additives, such as a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, etc., as needed, as long as the effect of the present invention is not impaired. Higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. When these additives are blended, the total blended amount is preferably 3% by mass or less of the solid content of the photosensitive resin composition.

(Thermal acid generator) The photosensitive resin composition of this invention may contain a thermal acid generator. Thermal acid generators generate acid by heating, promote the cyclization of heterocyclic polymer precursors, and further improve the mechanical properties of the cured film. Examples of the thermal acid generator include compounds described in paragraph 0059 of Japanese Patent Application Laid-Open No. 2013-167742.

The content of the thermal acid generator is preferably 0.01 part by mass or more with respect to 100 parts by mass of the heterocyclic-containing polymer precursor, and more preferably 0.1 part by mass or more. By containing 0.01 mass parts or more of a thermal acid generator, the crosslinking reaction and the cyclization of the heterocyclic polymer-containing precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. From the viewpoint of the electrical insulation of the cured film, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less. One type of thermal acid generator may be used, or two or more types may be used. In the case of using two or more kinds, it is preferable that the total measurement falls within the above range.

(Sensitizing dye) The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electronically excited state. The sensitizing dye in an electronically excited state is brought into contact with a thermal alkali generator, a thermal radical polymerization initiator, a radical polymerization initiator, and the like to generate electron transfer, energy transfer, and heat generation effects. As a result, the thermal base generator, thermal radical polymerization initiator, and radical polymerization initiator cause chemical changes to decompose, and generate radicals, acids, or bases. For details of the sensitizing dye, reference can be made to the description in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, which is incorporated into this specification.

When the photosensitive resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, and 0.1 to 15% by mass relative to the total solid content of the photosensitive resin composition of the present invention. More preferably, 0.5 to 10% by mass is more preferable. The sensitizing dye may be used singly or in combination of two or more kinds.

(Chain Transfer Agent) The photosensitive resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined in, for example, the third edition of the polymer dictionary (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in a molecule can be used. These can generate free radicals by supplying hydrogen to low-active free radicals, or can generate free radicals by deprotonation after oxidation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles) can be preferably used. Wait).

When the photosensitive resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention, and 1 to 10 parts by mass is more preferred, and 1 to 5 parts by mass is even more preferred. The chain transfer agent may be only one kind, or two or more kinds. When there are two or more kinds of chain transfer agents, the total amount is preferably in the above range.

(Surfactant) Various surfactants can be added to the photosensitive resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferred. [Chemical Formula 36]

When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, and 0.005 to 1.0% by mass relative to the total solid content of the photosensitive resin composition of the present invention. For the better. The surfactant may be only one kind, or two or more kinds. When there are two or more kinds of surfactants, it is preferable that the total amount is within the above range.

(Higher fatty acid derivative) In order to prevent polymerization inhibition caused by oxygen, the photosensitive resin composition of the present invention may be added with a higher fatty acid derivative such as behenic acid and ammonium behenate. It exists locally on the surface of the photosensitive resin composition during drying. When the photosensitive resin composition of this invention has a higher fatty acid derivative, it is preferable that content of a higher fatty acid derivative is 0.1-10 mass% with respect to the total solid content of the photosensitive resin composition of this invention. The higher fatty acid derivative may be only one type, or may be two or more types. When there are two or more types of higher fatty acid derivatives, the total amount is preferably in the above range.

<<< Restrictions on Containing Other Substances> From the viewpoint of the properties of the coated surface, the moisture content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and less than 0.6 The mass% is particularly good.

From the viewpoint of insulation, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million, parts per million), more preferably less than 1 mass ppm, and more preferably less than 0.5 mass ppm. Especially good. Examples of the metal include sodium, potassium, magnesium, calcium, rhenium, chromium, and nickel. When a plurality of metals are included, it is preferable that the total of these metals is within the above range. In addition, as a method for reducing metal impurities inadvertently contained in the photosensitive resin composition of the present invention, as a raw material constituting the photosensitive resin composition of the present invention, a material having a small metal content is selected, and The raw materials of the photosensitive resin composition of the present invention are filtered by a filter, the inside of the device is lined with polytetrachlorovinyl or the like, and distillation is performed under conditions that minimize contamination.

From the viewpoint of wiring corrosion, the photosensitive resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and particularly preferably less than 200 mass ppm. Among them, those in the state of a halogen ion are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of the chlorine atom and the bromine atom, or the total of the chloride ion and the bromine ion are in the above ranges.

<Preparation of photosensitive resin composition> The photosensitive resin composition of this invention can be prepared by mixing each said component. The mixing method is not particularly limited, and can be performed by a conventionally known method. Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign materials such as waste materials and fine particles in the photosensitive resin composition. The pore diameter of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrachloroethylene, polyethylene or nylon. The filter can also be used in advance by organic solvents. In the filtration process of the filter, a plurality of filters may be connected and used in series or in parallel. When using multiple types of filters, filters with different pore sizes and / or materials can be used in combination. In addition, various materials may be filtered several times. In the case of a plurality of filtrations, the filtration may be circular. In addition, filtration may be performed under pressure. When filtering is performed under pressure, the pressure is preferably 0.05 MPa to 0.3 MPa. In addition to filtration using a filter, removal of impurities using an adsorbent can also be performed. It is also possible to combine filter filtration and impurity removal treatment using adsorption materials. As the adsorbent, a known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolites, and organic adsorbents such as activated carbon.

[Curing film, method for producing cured film, and application of cured film] The photosensitive resin composition of the present invention can be cured and used as a cured film. In the field to which the manufacturing method of the cured film of this invention can be applied, the insulating film of a semiconductor device, especially an interlayer insulating film for redistribution layers etc. are mentioned. The photosensitive resin composition of the present invention is used for negative development. It is also used for development using a developer containing an organic solvent. Examples of the organic solvent used in the developing solution include organic solvents that can be blended with the photosensitive resin composition, and cyclopentanone is preferred. That is, the present invention also includes a cured film obtained by curing the photosensitive resin composition of the present invention, and a semiconductor device including the cured film. The present invention also discloses a method for producing a cured film including a process of applying the photosensitive resin composition of the present invention to a substrate and a process of curing the photosensitive resin composition applied to the substrate. In addition, the method for producing the cured film includes a process of exposing the cured film and performing negative development, and it is more preferable to perform the development using a developer containing an organic solvent. The cured film in the present invention can also be used for photoresists (galvanic resists, galvanic resists, etching resists, solder top resists) and the like for electronics. In addition, the cured film in the present invention can also be used for the production of a layout such as an offset plate or a screen plate, the use of a molded component for etching, the production of a protective varnish and a dielectric layer in electronics, especially microelectronics, and the like.

Next, an embodiment of a semiconductor device using the photosensitive resin composition for an interlayer insulating film for a redistribution layer will be described. The semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a multilayer body 101 in which a plurality of semiconductor elements (semiconductor wafers) 101 a to 101 d are stacked is arranged on a wiring substrate 120. In addition, in this embodiment, a case where the number of stacked layers of a semiconductor element (semiconductor wafer) is four is described. However, the number of stacked layers of a semiconductor element (semiconductor wafer) is not particularly limited, and may be two layers, eight, for example. Floor, 16 floor, 32 floor, etc. It may be one floor.

Each of the plurality of semiconductor elements 101a to 101d includes a semiconductor wafer such as a silicon substrate. The uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof. The semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) provided integrally with the through electrodes are provided on both surfaces of each semiconductor element.

The laminated body 101 has a structure in which a semiconductor element 101a not having a through electrode and semiconductor elements 101b to 101d having a through electrode 102b to 102d are flip-chip bonded. That is, the electrode pad of the semiconductor element 101a without a through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b with a through electrode 102b adjacent thereto are connected by a metal bump 103a such as a solder bump, and The connection pad on the other side of the semiconductor element 101b having the through electrode 102b and the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the through electrode 102c adjacent thereto are connected by a metal bump 103b such as a solder bump. Similarly, the connection pads on the other side of the semiconductor element 101c having the through electrode 102c and the connection pads on the semiconductor element 101c side of the semiconductor element 101d having the through electrode 102d adjacent thereto are connected by metal bumps such as solder bumps. 103c connection.

An underfill layer 110 is formed in the gap between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are laminated via the underfill layer 110.

The laminated body 101 is laminated on the wiring substrate 120. As the wiring substrate 120, for example, a multilayer wiring substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material can be used. Examples of the wiring substrate 120 using a resin substrate include a multilayer copper-clad laminated board (multilayer printed wiring board) and the like.

A surface electrode 120 a is provided on one surface of the wiring substrate 120. An insulating film 115 is formed between the wiring substrate 120 and the multilayer body 101, and a redistribution layer 105 is formed. The wiring substrate 120 and the multilayer body 101 are electrically connected to each other via the redistribution layer 105. The insulating film 115 is formed using the photosensitive resin composition in the present invention. That is, one end of the redistribution layer 105 is connected to an electrode pad formed on the surface of the redistribution layer 105 side of the semiconductor element 101d via a metal bump 103d such as a solder bump. The other end of the redistribution layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump. An underfill layer 110 a is formed between the insulating film 115 and the laminated body 101. An underfill layer 110b is formed between the insulating film 115 and the wiring substrate 120.

In addition to the above, the cured film in the present invention can be widely used in various applications using polyimide or polybenzoxazole. In addition, polyimide or polybenzoxazole has strong heat resistance. Therefore, the cured film and the like in the present invention are also preferably used in transparent plastic substrates for display devices such as liquid crystal displays and electronic paper, automotive components, heat-resistant coatings, Coating agent, film application. [Example]

The following examples further illustrate the present invention. The materials, usage amounts, proportions, processing contents, processing steps, etc. shown in the following examples can be changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Acidic compound> The following acidic compounds were used. <<< Measurement of pKa of Acidic Compound> For the measurement of pKa, the value calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs CORPORATION) was used.

[Table 1]

<Synthesis of heterocyclic-containing polymer precursor composition (resin composition)> (Synthesis Example 1) [Derived from 4,4'-oxo diphthalic dianhydride, 2-hydroxyethyl methacrylic acid Synthesis of Polyester and Polyimide Precursor Composition A-1 of Diamine (a) shown below] 42.4 g of 4,4'-oxodiphthalic dianhydride and 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were stirred at a temperature of 60 ° C for 4 hours. Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 76.0 g of the diamine (a) shown below was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at -10 ± 5 ° C, and the mixture was stirred for 1 hour. Then, 20 mL of ethanol and 200 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution to precipitate a polyimide precursor, and the mixture was filtered and dried at 45 ° C. under reduced pressure for 2 days. The weight average molecular weight of the obtained powdery polyfluorene imide precursor was 26,500, and the number average molecular weight was 9,300. Diamine (a) [Chemical Formula 37]

(Synthesis Example 2) [Polyimide precursor composition A-2 derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and diamine (a) Synthesis] 42.4 g of 4,4'-oxo diphthalic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, 100 mL of tetrahydrofuran, and a temperature of 60 ° C Stired for 4 hours. Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 76.0 g of diamine (a) was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes, and the mixture was stirred for 1 hour, and 3.0 g was added. Oxalic acid, 20 mL of ethanol and 200 mL of gamma-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution to precipitate a polyimide precursor, and the mixture was filtered and dried at 45 ° C. under reduced pressure for 2 days. The weight average molecular weight of the obtained powdery polyimide precursor was 25,100, and the number average molecular weight was 8,500.

(Synthesis Example 3) [Polyimide precursor composition A-3 derived from 4,4'-oxo diphthalic dianhydride, 2-hydroxyethyl methacrylate, and diamine (a) Synthesis] 42.4 g of 4,4'-oxo diphthalic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, 100 mL of tetrahydrofuran, and a temperature of 60 ° C Stired for 4 hours. Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of diisopropylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 76.0 g of diamine (a) was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes, and the mixture was stirred for 1 hour, followed by 3.0 g of methanesulfonic acid, 20 mL of ethanol, and 200 mL of gamma-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution to precipitate a polyimide precursor, and the mixture was filtered and dried at 45 ° C. under reduced pressure for 2 days. The weight-average molecular weight of the obtained powdery polyimide precursor was 26,800, and the number-average molecular weight was 9,400.

(Synthesis Example 4) [Polymer derived from pyromellitic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl Synthesis of hydrazone imide precursor composition A-4] 29.8 g of pyromellitic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed at 60 ° C. It was stirred at the temperature for 4 hours. Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, 40.2 g of 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl was dissolved in 200 mL of γ-butyrolactone over 60 minutes at -10 ± 5 ° C. The solution was added dropwise to the reaction mixture, and after stirring the mixture for 1 hour, 20 mL of ethanol and 200 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution to precipitate a polyimide precursor, and the mixture was filtered and dried at 45 ° C. under reduced pressure for 2 days. The weight average molecular weight of the obtained powdery polyfluorene imide precursor was 24,900, and the number average molecular weight was 8,400.

(Synthesis Example 5) [Polymer derived from pyromellitic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl Synthesis of hydrazone imide precursor composition A-5] 29.8 g of pyromellitic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed at 60 ° C. It was stirred at the temperature for 4 hours. Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, 40.2 g of 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl was dissolved in 200 mL of γ-butyrolactone over 60 minutes at -10 ± 5 ° C. The solution was added dropwise to the reaction mixture, and after stirring the mixture for 1 hour, 3.0 g of formic acid, 20 mL of ethanol, and 200 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution to precipitate a polyimide precursor, and the mixture was filtered and dried at 45 ° C. under reduced pressure for 2 days. The weight average molecular weight of the obtained powdery polyimide precursor was 25,200, and the number average molecular weight was 8,800.

(Synthesis Example 6) [Polymer derived from pyromellitic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl Synthesis of hydrazone imide precursor composition A-6] 14.9 g of pyromellitic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, 250 mL of diglyme (Diethylene glycol dimethyl ether), and stirred at a temperature of 60 ° C for 4 hours. Next, the reaction mixture was cooled to -10 ° C, and while maintaining the temperature at -10 ± 5 ° C, 17.0 g of SOCl _{2 was} added over 60 minutes. After diluting with 50 mL of N-methylpyrrolidone, 20.1 g of 4,4'-diamino-2,2 'was dissolved in 100 mL of N-methylpyrrolidone over 60 minutes at -10 ± 5 ° C. -A solution of bis (trifluoromethyl) biphenyl was added dropwise to the reaction mixture, and after stirring the mixture for 1 hour, 3.0 g of 10-camphorsulfonic acid and 20 mL of ethanol were added. 6 L of water was added to the obtained reaction solution to precipitate a polyimide precursor, and the solid was filtered and dissolved in 380 g of tetrahydrofuran. 6 L of water was added to the obtained solution to precipitate the polyimide precursor, and the solid was filtered again and dried under reduced pressure at 45 ° C for 2 days. The weight average molecular weight of the powdery polyfluorene imide precursor obtained was 23,900, and the number average molecular weight was 8,000.

(Synthesis Example 7) [Polyimide precursor derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diaminodiphenyl ether [Synthesis of composition A-7] 42.4 g of 4,4'-oxodiphthalic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, 100 mL of tetrahydrofuran, It was stirred at a temperature of 60 ° C for 4 hours. Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of diisopropylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction at -10 ± 5 ° C over 60 minutes. In the mixture, the mixture was stirred for 30 minutes. Next, a solution in which 25.1 g of 4,4'-diaminodiphenyl ether was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C for 60 minutes, and the mixture 1 was stirred. After hours, 20 mL of ethanol and 200 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution to precipitate a polyimide precursor, and the mixture was filtered and dried at 45 ° C. under reduced pressure for 2 days. The weight average molecular weight of the obtained powdery polyfluorene imide precursor was 25,400, and the number average molecular weight was 8,500.

(Synthesis Example 8) [Polyimide precursor derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diaminodiphenyl ether [Synthesis of composition A-8] 42.4 g of 4,4'-oxodiphthalic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, 100 mL of tetrahydrofuran, It was stirred at a temperature of 60 ° C for 4 hours. Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of diisopropylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction at -10 ± 5 ° C over 60 minutes. In the mixture, the mixture was stirred for 30 minutes. Next, a solution in which 25.1 g of 4,4'-diaminodiphenyl ether was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C for 60 minutes, and the mixture 1 was stirred. After hours, 3.0 g of p-toluenesulfonic acid monohydrate, 20 mL of ethanol, and 200 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution to precipitate a polyimide precursor, and the mixture was filtered and dried at 45 ° C. under reduced pressure for 2 days. The weight average molecular weight of the obtained powdery polyfluorene imide precursor was 24,800, and the number average molecular weight was 8,800.

(Synthesis Example 9) [Derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diamino-2,2'-bis (tri Synthesis of Fluoromethyl) Biphenylimide Precursor Composition A-9] 21.2 g of 4,4'-oxo diphthalic dianhydride and 18.0 g of 2-hydroxyethyl methyl The acrylate, 23.9 g of pyridine, and 250 mL of diglyme were stirred at a temperature of 60 ° C for 4 hours. Next, the reaction mixture was cooled to -10 ° C, and while maintaining the temperature at -10 ± 5 ° C, 17.0 g of SOCl _{2 was} added over 60 minutes. After diluting with 50 mL of N-methylpyrrolidone, 20.1 g of 4,4'-diamino-2,2 'was dissolved in 100 mL of N-methylpyrrolidone over 60 minutes at -10 ± 5 ° C. -A solution of bis (trifluoromethyl) biphenyl was added dropwise to the reaction mixture, and after stirring the mixture for 1 hour, 20 mL of ethanol was added. 6 L of water was added to the obtained reaction solution to precipitate a polyimide precursor, and the solid was filtered and dissolved in 380 g of tetrahydrofuran. 6 L of water was added to the obtained solution to precipitate the polyimide precursor, and the solid was filtered again and dried under reduced pressure at 45 ° C for 2 days. The weight average molecular weight of the obtained powdery polyimide precursor was 24,400, and the number average molecular weight was 8,400.

(Synthesis Example 10) [Derived from 4,4'-oxo diphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diamino-2,2'-bis (tri [Synthesis of fluoromethyl) biphenylimide precursor composition A-10] 21.2 g of 4,4'-oxo diphthalic dianhydride and 18.0 g of 2-hydroxyethyl methyl The acrylate, 23.9 g of pyridine, and 250 mL of diglyme were stirred at a temperature of 60 ° C for 4 hours. Next, the reaction mixture was cooled to -10 ° C, and while maintaining the temperature at -10 ± 5 ° C, 17.0 g of SOCl _{2 was} added over 60 minutes. After diluting with 50 mL of N-methylpyrrolidone, 20.1 g of 4,4'-diamino-2,2 'was dissolved in 100 mL of N-methylpyrrolidone over 60 minutes at -10 ± 5 ° C. -A solution of bis (trifluoromethyl) biphenyl was added dropwise to the reaction mixture, and after stirring the mixture for 1 hour, 3.0 g of p-toluenesulfonic acid monohydrate and 20 mL of ethanol were added. 6 L of water was added to the obtained reaction solution to precipitate a polyimide precursor, and the solid was filtered and dissolved in 380 g of tetrahydrofuran. 6 L of water was added to the obtained solution to precipitate the polyimide precursor, and the solid was filtered again and dried under reduced pressure at 45 ° C for 2 days. The weight average molecular weight of the obtained powdery polyimide precursor was 24,400, and the number average molecular weight was 8,400.

(Synthesis Example 11) [Polybenzoxazole precursor derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-oxobenzophenone chloride Synthesis of Composition A-11] 28.0 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 200 mL of N-methylpyrrolidone with stirring. Next, while maintaining the temperature at 0 to 5 ° C, 25.0 g of 4,4'-oxodibenzoyl chloride was added dropwise over 10 minutes, and the stirring was continued for 60 minutes. 6 L of water was added to the obtained reaction solution to precipitate a polybenzoxazole precursor, and the solid was filtered and dried under reduced pressure at 45 ° C for 2 days. The weight-average molecular weight of the obtained powdery polybenzoxazole precursor was 28,500, and the number-average molecular weight was 9,800.

(Synthesis Example 12) [Polybenzoxazole precursor derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-oxobenzophenone chloride Synthesis of Composition A-12] 28.0 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 200 mL of N-methylpyrrolidone with stirring. Next, while maintaining the temperature at 0 to 5 ° C., 25.0 g of 4,4′-oxobenzophenazine chloride was added dropwise over 10 minutes, and the stirring was continued for 60 minutes, and 3.0 g of maleic acid was added. acid. 6 L of water was added to the obtained reaction solution to precipitate a polybenzoxazole precursor, and the solid was filtered and dried under reduced pressure at 45 ° C for 2 days. The weight average molecular weight of the obtained powdery polybenzoxazole precursor was 26,900, and the number average molecular weight was 9,700.

(Synthesis Example 13) [Polybenzoxazole precursor derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-oxodibenzophene chloride Synthesis of Composition A-13] 28.0 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 200 mL of N-methylpyrrolidone with stirring. Next, while maintaining the temperature at 0 to 5 ° C., 25.0 g of 4,4′-oxodibenzoic acid chloride was added dropwise over 10 minutes, and the stirring was continued for 60 minutes, and 3.0 g of p-toluenesulfonic acid was added. Monohydrate. 6 L of water was added to the obtained reaction solution to precipitate a polybenzoxazole precursor, and the solid was filtered and dried under reduced pressure at 45 ° C for 2 days. The weight average molecular weight of the obtained powdery polybenzoxazole precursor was 26,900, and the number average molecular weight was 9,700.

<Conductivity of Resin Composition> Each resin composition prepared in Synthesis Examples 1 to 13 was a cured film having a thickness of 10 μm, and the conductivity of the cured film after being heated at 350 ° C. for 60 minutes was measured. Using an insulation resistivity meter (manufactured by ADVANTEST CORPORATION, product name R8340), the electrical conductivity was measured by the double ring electrode method. The coating film was placed on a circular electrode, and the resistance was measured by an insulation resistance meter, and the volume resistivity was obtained from the electrode shape. As the insulation resistivity meter, a product named R8340 manufactured by ADVANTEST CORPORATION was used. When the resin composition is in a liquid state, the resin composition is applied to a substrate, and the solvent is dried to make the cured film having the thickness described above, and the conductivity after the heating is measured. When the viscosity is high, the resin composition is dissolved in a solvent dissolved at 25 ° C., and the resin composition is applied to a substrate, and the solvent is dried to make the cured film having the thickness described above. In addition, the conductivity after the heating is measured rate. In the case where the resin composition is in a powder form, the resin composition is dissolved in a solvent dissolved at 25 ° C., and then the resin composition is applied to a substrate, and the solvent is dried to obtain a cured film having the thickness described above. Electrical conductivity after heating. When an arbitrary resin composition is used, the obtained cured film is fully cyclized with a heterocyclic-containing polymer precursor, and its conductivity is 1.0 × 10 ⁵ Ω ･ cm or less.

<Preparation of photosensitive resin composition> The photosensitive resin composition was prepared by mixing each component described in the following Table 2 or Table 3 and making it a uniform solution. The photosensitive resin composition obtained as described above was passed through a filter having a pore width of 0.8 μm and subjected to pressure filtration.

<< Conductivity of photosensitive resin composition >> The conductivity of the photosensitive resin composition was measured in the same manner as the conductivity of the resin composition. When an arbitrary photosensitive resin composition is used, the obtained cured film is also fully cyclized with a heterocyclic-containing polymer precursor, and has a conductivity of 1.0 × 10 ⁵ Ω ･ cm or less.

<<Resolution> The above-mentioned photosensitive resin composition is spin-formed on a silicon wafer having a thickness of 250 μm and a diameter of 100 mm (1200 rpm, 30 seconds) for application. The silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a film having a thickness of 10 μm on the silicon wafer. Next, the film coated on the silicon wafer was pattern-exposed using an aligner (Karl-Suss MA150) and an exposure mask (line / space = 1/1). Exposure was performed under a high-pressure mercury lamp, and 500 mJ / cm ^{2 was} irradiated in terms of exposure energy at a wavelength of 365 nm. After the irradiation, the image was developed with cyclopentanone for 75 seconds. Observe the obtained pattern, and set the minimum line width where the line and space are separated and resolved as the resolution.

<< Storage stability >> 10 g of the above-mentioned photosensitive resin composition was sealed in a container (material of the container: light-shielding glass, capacity: 100 mL), and allowed to stand in an environment of 25 ° C and a relative humidity of 65%. The stability was evaluated in the time until solids precipitated from the photosensitive resin composition. The longer the time, the higher the stability of the photosensitive resin composition, which is a better result. Precipitation of the solid was carried out by pressure filtration with a mesh having a pore diameter of 0.8 μm, and the presence or absence of foreign matter on the mesh was visually observed. A: Even after 120 days, no precipitation of solids was observed. B: Solids precipitated over 60 days and within 120 days. C: Solids precipitated over 30 days and within 60 days. D: A solid precipitated within 30 days.

<<< Corrosive Metal> The above-mentioned photosensitive resin composition is spin-formed on a copper substrate having a thickness of 250 μm (1200 rpm, 30 seconds) and applied. The silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a 10 μm-thick film on a copper substrate. Next, the temperature was raised at a temperature increase rate of 10 ° C / min in a nitrogen atmosphere, and after reaching 230 ° C, it was maintained for 3 hours. After cooling, the film on the copper substrate was physically peeled. The copper substrate was visually observed, and the area ratio colored to rust was calculated to evaluate the metal corrosivity. The smaller the area ratio, the less corrosive the metal. A: 1% or less. B: More than 1% and less than 5%. C: More than 5% and less than 10%. D: More than 10%.

[Table 2] [table 3]

(A) Resin (heterocyclic-containing polymer precursor composition) A-1 to A-13: heterocyclic-containing polymer precursor composition produced by Synthesis Examples 1 to 13

(B) Polymerizable compound B-1: NK ester M-40G (manufactured by Shin-Nakamura Chemical Co., Ltd.) B-2: SR-209 (manufactured by Sartomer Company Inc.) B-3: NK ester A-9300 (Manufactured by Shin-Nakamura Chemical Co., Ltd.) B-4: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)

(C) Photopolymerization initiator C-1: IRGACURE OXE 01 (manufactured by BASF) C-2: IRGACURE OXE 02 (manufactured by BASF) C-3: IRGACURE OXE 04 (manufactured by BASF) C-4: IRGACURE-784 (Manufactured by BASF) C-5: NCI-831 (manufactured by ADEKA CORPORATION)

(D) Hot alkali generator D-1: the following compound D-2: the following compound D-3: the following compound [Chemical Formula 38]

(E) Polymerization inhibitor E-1: 1,4-benzoquinone E-2: 1,4-methoxyphenol

(F) Additive F-1: 1,2,4-triazole F-2: 1H-tetrazole

(G) Silane coupling agent G-1: the following compound G-2: the following compound G-3: the following compound [Chemical Formula 39] (H) Solvent H-1: γ-butyrolactone H-2: Dimethyl sulfene H-3: N-methyl-2-pyrrolidone H-4: Ethyl lactate For example, when the type column is "H-1 / H-2" and the mass% column is "48 + 12", it means that 48% by mass of H-1 is contained and 12% by mass of H-1 is contained. H-2.

(I) Acidic compound I-1: formic acid I-2: oxalic acid I-3: maleic acid I-4: malonic acid I-5: pyruvate I-6: DL-lactic acid I-7: p-toluene Sulfonic acid monohydrate I-8: 10-Camphorsulfonic acid I-9: Methanesulfonic acid I-10: Acetic acid

As is clear from the results of the above-mentioned Table 2 or Table 3, the photosensitive resin composition using the resin composition of the present invention has high resolution and excellent storage stability. In particular, as the acidic compound, those having a pKa of 3.5 or less, further 3.0 or less, and particularly 2.0 or less are used to further enhance the effect of the present invention. In addition, as the acidic compound, one having a molecular weight of 100 or more is used to more effectively increase the inhibitory effect of metal corrosion.

100‧‧‧ semiconductor device

101a ～ 101d‧‧‧Semiconductor element

101‧‧‧Laminated body

102b ～ 102d‧‧‧through electrode

103a ～ 103e‧‧‧ metal bump

105‧‧‧ redistribution layer

110, 110a, 110b‧‧‧ Underfill

115‧‧‧ insulating film

120‧‧‧ wiring board

120a‧‧‧ surface electrode

FIG. 1 is a schematic diagram showing a configuration of an embodiment of a semiconductor device.

Claims (23)

A resin composition comprising a heterocyclic polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and an acidic compound having a pKa of 4.0 or less, and the resin composition is set to 10 μm. The thickness of the cured film having a thickness of 60 ° C. after heating at 350 ° C. for 60 minutes is 1.0 × 10 ⁵ Ω ･ cm or less. The resin composition according to item 1 of the scope of the patent application, wherein the aforementioned heterocyclic polymer-containing precursor contains a repeating unit represented by the following formula (1) or a repeating unit represented by the formula (2): ) Equation (2) In Formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or Monovalent organic group; In formula (2), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group. The resin composition according to claim 1 or claim 2, wherein the pKa of the acidic compound is 3.5 or less. The resin composition according to claim 1 or claim 2, wherein the molecular weight of the acidic compound is 100 to 300. The resin composition according to claim 1 or claim 2, wherein the acidic compound is selected from a sulfonic acid and a carboxylic acid. The resin composition according to claim 1 or claim 2, wherein the acidic compound is a sulfonic acid. The resin composition according to item 1 or item 2 of the patent application range, wherein the acidic compound is selected from p-toluenesulfonic acid, camphorsulfonic acid, and methanesulfonic acid. The resin composition according to item 1 or item 2 of the patent application scope is powder. A photosensitive resin composition comprising a heterocyclic polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, a resin composition including an acidic compound having a pKa of 4.0 or less, and The photopolymerization initiator used the photosensitive resin composition as a cured film having a thickness of 10 μm, and the cured film had a conductivity of 1.0 × 10 ⁵ Ω ･ cm or less after being heated at 350 ° C. for 60 minutes. The photosensitive resin composition according to item 9 of the patent application scope, wherein the resin composition is the resin composition according to item 2 of the patent application scope. The photosensitive resin composition according to claim 9 or claim 10, which is a photosensitive resin composition for negative development. The photosensitive resin composition according to claim 9 or claim 10, which is used for development using a developing solution containing an organic solvent. The photosensitive resin composition according to claim 9 or claim 10, which is a photosensitive resin composition for forming an interlayer insulating film for a redistribution layer. A cured film obtained by curing the photosensitive resin composition according to any one of claims 9 to 13 of the scope of patent application. The cured film according to item 14 of the scope of patent application, which is an interlayer insulating film for a redistribution layer. A method for manufacturing a cured film, comprising a process of applying the photosensitive resin composition according to any one of claims 9 to 13 to a substrate and applying the photosensitive resin to the substrate The composition undergoes a hardening process. The method for manufacturing a cured film according to item 16 of the scope of patent application, further comprising a process of exposing the aforementioned cured film and developing the film negatively. The method for producing a cured film according to item 17 of the scope of patent application, wherein the development includes a step of using a developer containing an organic solvent. A semiconductor device having a hardened film as described in claim 14 or 15. A method for producing a resin composition, wherein the resin composition includes a heterocyclic polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and the method for producing the resin composition includes adding A process in which an acid compound having a pKa of 4.0 or less is used, and the resin composition is powdered. A method for manufacturing a resin composition, which is the method for manufacturing a resin composition according to any one of claims 1 to 8 of the scope of application for a patent, in the aforementioned synthetic process of the heterocyclic-containing polymer precursor, The method includes the step of adding an acidic compound having a pKa of 4.0 or less. A method for manufacturing a resin composition, which is the method for manufacturing a resin composition according to any one of claims 1 to 8 of the scope of application for a patent, and includes: synthesizing the aforementioned heterocyclic-containing polymer precursor and adding the same Step of acidic compound with pKa of 4.0 or less. The method for manufacturing a resin composition according to item 20 of the scope of application, wherein the synthetic process of the heterocyclic-containing polymer precursor includes a step of adding a carbodiimide compound.