TWI875714B - Resin composition, cured film, laminate, method for producing cured film, and semiconductor element - Google Patents

Abstract

The present invention provides a resin composition, a cured film using the resin composition, a laminate, a method for producing the cured film, and a semiconductor device. The resin composition comprises at least one polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, wherein the total content of HNO ₂ , NO ₂ ^- , HNO ₃ , NO ₃ ^- , H ₂ SO ₄ , HSO ₄ ^- , SO ₄ ^2- , H ₂ SO ₃ , HSO ₃ ^- , and SO ₃ ^2- is 1 mass ppb or more and 1000 mass ppm or less relative to the total solid content of the resin composition.

Description

Resin composition, cured film, laminate, method for producing cured film, and semiconductor element

The present invention relates to a resin composition comprising at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors. The present invention also relates to a cured film, a laminate, a method for manufacturing the cured film, and a semiconductor device using the resin composition comprising the polymer precursor.

Resins that are cyclized and cured, such as polyimide resins and polybenzoxazole resins, have excellent heat resistance and insulation properties and are therefore suitable for various uses. The use is not particularly limited, but if the semiconductor element for actual mounting is taken as an example, the use as a material or protective film for an insulating film or sealing material can be cited. (See non-patent documents 1 and 2, etc.). In addition, it is also used as a base film or cover layer of a flexible substrate. Such polyimide resins and the like generally have low solubility in solvents. Therefore, a method is often used in which a polymer precursor before the cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor is dissolved in a solvent. This enables excellent operability, and when manufacturing products such as the above, it can be coated on a substrate and processed in various forms. Then, the polymer precursor is heated and cyclized to form a hardened product. In addition to the high performance of polyimide resins, the excellent adaptability of these resins in manufacturing has led to an increasing expectation for their application in the industry.

Patent document 1 discloses an invention regarding the following contents: a resin composition comprising a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor and a thermal alkali generator. Patent document 1 discloses the following contents: by using a specific thermal alkali generator, the storage stability is good and the cyclization reaction of the polyimide precursor etc. can be carried out at a low temperature. [Prior art document] [Patent document]

[Patent Document 1] International Publication No. 2015/199219 [Non-patent Document]

[Non-patent document 1] Science & technology Co., Ltd. "High-functionalization and application technology of polyimide" April 2008 [Non-patent document 2] Masaaki Kakimoto/supervised, CMC Technology Library "Basics and development of polyimide materials" Published in November 2011

By using the technology of the above-mentioned patent document 1, it is possible to improve the storage stability of a resin composition containing a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor. On the other hand, in order to respond to the diversified properties required of resin compositions containing such polymer precursors in recent years, further research and development is required. For example, it is necessary to further improve the moisture resistance of a cured film obtained from a resin composition containing a polymer precursor.

Therefore, an object of the present invention is to provide a resin composition having good storage stability and capable of forming a cured film having excellent moisture resistance, a cured film, a laminate, a method for producing a cured film, and a semiconductor element.

As a result of in-depth research on a resin composition comprising at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, the inventors found that the above-mentioned purpose can be achieved by the following structure, thereby completing the present invention. The present invention provides the following contents.

<1> A resin composition comprising at least one polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, _wherein ^the total content of HNO2, _{NO2- , HNO3, NO3-, H2SO4, HSO4-, SO42- ,} ^H2SO3 _{, HSO3- and} ^{SO32- is} _{1 ppb} or more ^and 1000 ppm or ^less relative to the total solid content _of the resin composition. <2> The resin composition as described in <1>, further _comprising at least one selected _from a silane coupling agent, a thermal alkali generator, a radical polymerization initiator and a radical polymerizable compound. <3> The resin composition as described in <1> or <2>, wherein the polymer precursor comprises a polyimide precursor. <4> The resin composition as described in <3>, wherein the polyimide precursor has a constituent unit represented by the following formula (1). [Chemical Formula 1] In formula (1), ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group. <5> The resin composition as described in <4>, wherein at least one of ^R113 and ^R114 in formula (1) comprises a radical polymerizable group. <6> The resin composition as described in any one of <1> to <5>, which is used for forming a pattern by developing with a developer containing 90 mass % or more of an organic solvent. <7> The resin composition as described in any one of <1> to <6>, which is used for forming a member in contact with metal. ＜8＞ A resin composition as described in any one of ＜1＞ to ＜7＞, which is used to form an interlayer insulating film for a redistribution layer. ＜9＞ A cured film obtained by curing the resin composition as described in any one of ＜1＞ to ＜8＞. ＜10＞ The cured film as described in ＜9＞ has a film thickness of 1 to 30μm. ＜11＞ A laminate having two or more layers of the cured film as described in ＜9＞ or ＜10＞, and a metal layer between the two layers of the cured film. ＜12＞ A method for manufacturing a cured film, comprising: a film forming step of applying the resin composition as described in any one of ＜1＞ to ＜8＞ to a substrate to form a film. <13> A method for producing a cured film as described in <12>, comprising: an exposure step of exposing the film; and a development step of developing the film. <14> A method for producing a cured film as described in <12> or <13>, comprising a step of heating the film at 80 to 450°C. <15> A semiconductor device having the cured film described in <9> or <10> or the laminated body described in <11>. [Effect of the invention]

According to the present invention, a resin composition having good storage stability and capable of forming a cured film having excellent moisture resistance, a cured film, a laminate, a method for manufacturing a cured film, and a semiconductor element can be provided.

Hereinafter, the content of the present invention will be described. In addition, in this specification, "to" is used to mean that the numerical values described before and after it are included as the lower limit and the upper limit.

The description of the constituent elements of the present invention described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. Regarding the marking of groups (atomic groups) in this specification, the marking without description of substitution and unsubstituted includes both those without substitution and those with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups). In this specification, "exposure" includes exposure using particle beams such as electron beams and ion beams, in addition to exposure using light, unless otherwise specified. In addition, as light used for exposure, active light or radiation such as far ultraviolet light represented by mercury lamp light spectrum, extreme ultraviolet light (EUV light), X-rays, and electron beams can be generally cited. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate", "(meth)acrylic acid" means both or either "acrylic acid" and "methacrylic acid", and "(meth)acryl" means both or either "acryl" and "methacryl". In this specification, the term "step" refers not only to independent steps, but also to steps that can achieve the expected effect even if they cannot be clearly distinguished from other steps. The physical property values in the present invention are set to values at a temperature of 23°C and an air pressure of 101325Pa or less unless otherwise specified. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC measurement) and are defined as styrene-equivalent values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220 (manufactured by TOSOH CORPORATION) and guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as columns. In this measurement, unless otherwise specified, THF (tetrahydrofuran) is used as the eluent. Unless otherwise specified, detection is performed using a UV (ultraviolet) ray detector with a wavelength of 254 nm.

[Resin composition] The resin composition of the present invention comprises at least one polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and the resin composition is characterized in that the total content of HNO ₂ , NO ₂ ^- , HNO ₃ , NO ₃ ^- , H ₂ SO ₄ , HSO ₄ ^- , SO ₄ ^2- , H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- is greater than 1 mass ppb and less than 1000 mass ppm relative to the total solid content of the resin composition. Hereinafter, HNO ₂ , NO ₂ ^- , HNO ₃ , NO ₃ ^- , H ₂ SO ₄ , HSO ₄ ^- , SO ₄ ^2- , H ₂ SO ₃ , HSO ₃ ^- , and SO ₃ ^2- are also collectively referred to as specific components.

The content of the specific component in the resin composition of the present invention is estimated to be 1 ppb or more relative to the total solid content of the resin composition, so that the reaction of the polymer precursor can be suppressed during storage, and as a result, excellent storage stability can be obtained. In addition, the content of the specific component is estimated to be 1000 ppm or less relative to the total solid content of the resin composition, so even if the cured film is exposed to a high humidity environment, it is not easily hydrolyzed, and as a result, a cured film with excellent moisture resistance can be formed.

Furthermore, when the resin composition of the present invention is used to form a component that contacts metal, such as an interlayer insulating film for a redistribution layer, corrosion of the metal can also be suppressed. Therefore, the resin composition of the present invention is preferably used to form a component that contacts metal. As components that contact metal, interlayer insulating films for redistribution layers, insulating tubes, sealing films, substrate materials (base films or cover layers of flexible printed circuit substrates, etc.), etc. can be cited, and interlayer insulating films for redistribution layers are more preferred.

In the resin composition of the present invention, from the viewpoint of moisture resistance and metal corrosion resistance of the obtained cured film, the total content of the above-mentioned specific components is preferably less than 1000 mass ppm, more preferably 900 mass ppm or less, further preferably 800 mass ppm or less, and particularly preferably 500 mass ppm or less relative to the total solid content of the resin composition. The reason for this is unclear, but considering that the storage stability of the resin composition and the moisture resistance of the obtained film can be easily improved by suppressing the reaction of components that promote deterioration, the lower limit is preferably 1.0 ppb by mass or more, more preferably 1.1 ppb by mass or more, further preferably 1.2 ppb by mass or more, and particularly preferably 1.5 ppb by mass or more relative to the total solid content of the resin composition.

In the resin composition of the present invention, the content of each of HNO ₂ , NO ₂ ^- , HNO ₃ , NO ₃ ^- , H ₂ SO ₄ , HSO ₄ ^- , SO ₄ ^2- , H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- is preferably 1000 mass ppm or less, more preferably 900 mass ppm or less, further preferably 800 mass ppm or less, and particularly preferably 500 mass ppm or less, based on the total solid content of the resin composition. Furthermore, the total content of HNO ₂ and NO ₂ ^- is preferably 1000 mass ppm or less, more preferably 900 mass ppm or less, further preferably 800 mass ppm or less, and particularly preferably 500 mass ppm or less, based on the total solid content of the resin composition. Furthermore, the total content of HNO ₃ and NO ₃ ^- is preferably 1000 mass ppm or less, more preferably 900 mass ppm or less, further preferably 800 mass ppm or less, and particularly preferably 500 mass ppm or less, based on the total solid content of the resin composition. Furthermore, the total content of H ₂ SO ₄ , HSO ₄ ^- and SO ₄ ^2- is preferably 1000 mass ppm or less, more preferably 900 mass ppm or less, further preferably 800 mass ppm or less, and particularly preferably 500 mass ppm or less, based on the total solid content of the resin composition. The total content of H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- is preferably 1000 mass ppm or less, more preferably 900 mass ppm or less, further preferably 800 mass ppm or less, and particularly preferably 500 mass ppm or less based on the total solid content of the resin composition.

The content of the specific component can be adjusted by adjusting the amount of the specific component or the raw material containing the specific component, or the purification conditions of the resin composition or the raw material.

In addition, in this specification, the content of specific components is analyzed by ion chromatography. Specifically, a test sample, a non-aqueous organic solvent and water are mixed, and the amount of the specific component extracted into the aqueous solution by liquid separation operation or centrifugal separation is measured by ion chromatography, thereby calculating the content of the specific component in the test sample. In addition, in the resin composition of the present invention ^, _NO2- ^, _NO3- , ^HSO4- , _SO42- , ^HSO3- and _SO32- among ^the _above - _mentioned specific components ^sometimes exist in the state of salts. In addition, _HNO2 , _HNO3 , _H2SO4 and _H2SO3 among _the above-mentioned specific components sometimes ionize and exist in the state of ions. There is no particular limitation on the atoms or _atomic groups constituting the salts. For example, alkaline metals (lithium, potassium, sodium, etc.), alkaline earth metals (calcium, curium, magnesium, strontium, barium), etc. can be cited.

The resin composition of the present invention is preferably used for developing with a developer containing 90 mass % or more of an organic solvent to form a pattern.

Hereinafter, each component of the resin composition of the present invention will be described in detail.

<Polymer precursor> The resin composition of the present invention includes a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor. From the perspective of more easily and significantly achieving the effect of the present invention, the polymer precursor used in the present invention is preferably a polyimide precursor.

＜＜Polyimide precursor＞＞ The polyimide precursor preferably contains a constituent unit represented by the following formula (1). By setting such a structure, a resin composition with better film strength can be obtained. [Chemical formula 2] ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

^A1 and ^A2 are independently an oxygen atom or NH, preferably an oxygen atom.

＜＜＜R ¹¹¹ ＞＞＞ R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group including a combination thereof. A linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 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 a combination thereof is preferred, and an aromatic group having 6 to 20 carbon atoms is more preferred. R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide 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, the diamine preferably contains a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group containing a combination thereof, and more preferably contains an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following aromatic groups.

[Chemical formula 3]

In the formula, A is preferably a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO-, and combinations thereof; more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, and -SO ₂ -; and even more preferably a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ -.

As the diamine, specifically, there can be mentioned 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane 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'-dimethylcyclohexyl Methane and isophorone diamine; meta-phenylenediamine and para-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'-diaminodiphenyl sulfone and 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminodiphenyl Aminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 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-hydroxyphenyl)sulfonate, bis(4-amino-3-hydroxyphenyl)sulfonate, 4,4'-diaminobiphenyl Benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 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 Aminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]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'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl -4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzyloxy)ethyl methacrylate, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoro Propane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]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- At least one diamine selected from the group consisting of 2,4'-bis(trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 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',5,5',6,6'-hexafluorotoluidine and 4,4'-diaminoquaternaryl.

Furthermore, the following diamines (DA-1) to (DA-18) are also preferred.

[Chemical formula 4]

As a preferred example, a diamine having two or more alkylene glycol units in the main chain can also be cited. Preferably, it is a diamine containing two or more ethylene glycol chains or propylene glycol chains or both in combination in one molecule, and more preferably, it is a diamine containing no aromatic ring. 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, D-200, D-400, D-2000, D-4000 (manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc., but are not limited to these. The following shows the structures of 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, and JEFFAMINE (registered trademark) EDR-176.

[Chemical formula 5]

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 ⁰ -L ⁰ -Ar ⁰ -. Ar ⁰ is independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), preferably a phenylene group. ^{L 0} represents a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO-, and a group selected from a combination thereof. The preferred range has the same meaning as that of A above.

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, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred. [Chemical Formula 6] R ⁵⁰ to R ⁵⁷ are independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group. Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like. [Chemical Formula 7] ^R58 and ^R59 are independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Examples of the diamine compound that gives the structure of formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One of these compounds may be used alone, or two or more thereof may be used in combination.

＜＜＜R ¹¹⁵ ＞＞＞ R ¹¹⁵ in formula (1) represents a tetravalent organic group. As the tetravalent organic group, a group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. [Chemical Formula 8] R ¹¹² has the same meaning as A, and the preferred range is also the same.

Regarding the tetravalent organic group represented by R ¹¹⁵ in formula (1), specifically, there can be mentioned the tetracarboxylic acid residue remaining after removing the acid dianhydride group from tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7). [Chemical Formula 9] R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as R ¹¹⁵ in formula (1).

Specific examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic 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-perylenetetracarboxylic dianhydride, 1,2,4,5 - at least one of naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride and their alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Furthermore, as preferred examples, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below can be cited. [Chemical Formula 10]

＜＜＜R ¹¹³ and R ¹¹⁴ ＞＞＞ In formula (1), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. It is preferred that at least one of ^{R 113} and R ¹¹⁴ contains a free radical polymerizable group, and it is more preferred that both contain a free radical polymerizable group. The free radical polymerizable group is a group that can undergo a crosslinking reaction by the action of a free radical, and a group having an ethylenic unsaturated bond can be cited as a preferred example. As the group having an ethylenic unsaturated bond, a vinyl group, an allyl group, a (meth)acryloyl group, a group represented by the following formula (III), and the like can be cited.

[Chemical formula 11]

In 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 (poly)oxyalkylene group having 4 to 30 carbon atoms (the alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms; and the number of repetitions is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms). In addition, the (poly)oxyalkylene group refers to an oxyalkylene group or a polyoxyalkylene group. Preferred examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, and -CH ₂ CH (OH) CH ₂ -. More preferred are ethylene, propylene, trimethylene, and -CH ₂ CH (OH) CH ₂ -. It is particularly preferred that R ²⁰⁰ is methyl and R ²⁰¹ is ethylene.

As a preferred embodiment of the polyimide precursor in the present invention, the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ includes groups having 1, 2 or 3 acid groups, preferably aliphatic groups, aromatic groups and aralkyl groups having 1 acid group. Specifically, aromatic groups having 6 to 20 carbon atoms and aralkyl groups having 7 to 25 carbon atoms can be mentioned. More specifically, phenyl groups having an acid group and benzyl groups having an acid group can be mentioned. It is more preferred that the acid group is a hydroxyl group. That is, it is preferred that R ¹¹³ or R ¹¹⁴ is a group having a hydroxyl group. As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent that improves the solubility of the developer can be preferably used. From the viewpoint of solubility in aqueous developer, R ¹¹³ or R ¹¹⁴ is more preferably a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group or a 4-hydroxybenzyl group.

From the viewpoint of solubility in organic solvents, 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, an aromatic group is preferred, and an alkyl group substituted by an aromatic group is more preferred. The carbon number of the alkyl group is preferably 1 to 30 (3 or more in the case of a ring). The alkyl group may be any of a linear, branched, and cyclic group. As the linear or branched alkyl group, for example, there can be mentioned methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic alkyl group or a polycyclic alkyl group. Examples of the monocyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of the polycyclic alkyl group include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, bornadiyl, bicyclohexyl and pinenyl. In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferred.

The aromatic group may be specifically a substituted or unsubstituted aromatic alkyl group (as the ring structure constituting the group, there may be mentioned a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indenyl ring, a perylene ring, a condensed pentaphenyl ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a condensed tetraphenyl ring, a chrysene ring, a tris-extended benzene ring, etc.) or a substituted or unsubstituted aromatic heterocyclic group (as the ring structure constituting the group, there may be mentioned a fluorene ring, a biphenyl ring, a pyridine ring, a cyclopentane ... (a) a pyrrolyl ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrrolidine ring, a pyrimidine ring, a pyrimidine ring, an indole ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolyl ring, a quinoline ring, a pyrrolyl ring, a naphthyridine ring, a quinoline ring, a quinazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthracene ring, a chromene ring, a pyrrolidine ring, a phenanthryl ring, a phenanthryl ring, a phenanthryl ring or a phenanthryl ring).

In addition, the polyimide precursor preferably has fluorine atoms in the constituent units. The fluorine atom content in the polyimide precursor is preferably 10 mass % or more, and more preferably 20 mass % or less. The upper limit is not particularly limited, but is practically 50 mass % or less.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the constituent unit represented by formula (1). Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be mentioned.

The constituent unit represented by formula (1) is preferably a constituent unit represented by formula (1-A) or (1-B). [Chemical Formula 12] ^A11 and ^A12 represent an oxygen atom or NH, ^R111 and ^R112 each independently represent a divalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, and at least one of ^R113 and ^R114 is preferably a group containing a free radical polymerizable group, and more preferably a free radical polymerizable group.

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are independently and preferably the same as the preferred ranges of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1). The preferred range of R ¹¹² is the same as R ¹¹² in formula (5), wherein oxygen atom is more preferred. The bonding position of the carbonyl group to the benzene ring in formula (1-A) is preferably 4, 5, 3', 4'. In formula (1-B), 1, 2, 4, 5 are preferred.

In the polyimide precursor, the constituent unit represented by formula (1) may be one type or two or more types. Furthermore, the constituent unit represented by formula (1) may contain structural isomers. Furthermore, in addition to the constituent unit of formula (1), the polyimide precursor may contain other types of constituent units.

As an embodiment of the polyimide precursor of the present invention, 50 mol% or more, further 70 mol% or more, and particularly 90 mol% or more of the total constituent units are polyimide precursors. The upper limit is practically 100 mol% or less.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000 to 500000, more preferably 5000 to 100000, and further preferably 10000 to 50000. Moreover, the number average molecular weight (Mn) is preferably 800 to 250000, more preferably 2000 to 50000, and further preferably 4000 to 25000. The molecular weight dispersion of the polyimide precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. It is preferably obtained by halogenating the dicarboxylic acid or the dicarboxylic acid derivative with a halogenating agent and then reacting it with a diamine. In the method for producing the polyimide precursor, it is preferred to use an organic solvent during the reaction. The organic solvent may be one or more. As the organic solvent, it can be appropriately set according to the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (DEG), N-methylpyrrolidone and N-ethylpyrrolidone.

When preparing the polyimide precursor, it is preferred to include a step of solid precipitation. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, thereby enabling solid precipitation.

<<Polybenzoxazole precursor>> The polybenzoxazole precursor preferably includes a constituent unit represented by the following formula (2). [Chemical formula 13] ^R121 represents a divalent organic group, ^R122 represents a tetravalent organic group, and ^R123 and ^R124 each independently represent a hydrogen atom or a monovalent organic group.

R ¹²¹ represents a divalent organic group. As a divalent organic group, a group containing at least one of an aliphatic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 12 carbon atoms) is preferred. As an aromatic group constituting R ¹²¹ , R ¹¹¹ in the above formula (1) can be cited as an example. As the above aliphatic group, a straight-chain aliphatic group is preferred. R ¹²¹ is preferably derived from 4,4'-oxydiphenylformyl chloride. In formula (2), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, the meaning is the same as that of R ¹¹⁵ in the above formula (1), and the preferred range is also the same. ^R122 is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. ^R123 and ^R124 each independently represent a hydrogen atom or a monovalent organic group, and have the same meanings as ^R113 and ^R114 in the above formula (1), and the preferred ranges are also the same.

In addition to the constituent units of the above formula (2), the polybenzoxazole precursor may also contain other types of constituent units. From the perspective of being able to suppress the occurrence of warping of the cured film associated with ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as the other type of constituent unit.

[Chemical formula 14] Z has structure a and structure b, R ^1s is a hydrogen atom or a alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), R ^2s is a alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms), and they may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. In the Z part, it is preferred that the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a+b is 100 mol%.

In formula (SL), as preferred Z, R ^5s and R ^6s in structure b are phenyl groups. In addition, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by a commonly used gel permeation chromatography method. By setting the molecular weight to the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be reduced, and the effects of suppressing warping and improving solubility can be achieved.

When the diamine residue represented by the formula (SL) is included as another type of constituent unit, it is preferred that the precursor further includes a tetracarboxylic acid residue remaining after the acid dianhydride group is removed from tetracarboxylic dianhydride as a constituent unit from the viewpoint of improving the alkali solubility. Examples of such tetracarboxylic acid residues include R ¹¹⁵ in the formula (1).

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 further preferably 10,000 to 50,000. Moreover, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000. The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

The content of the polymer precursor in the resin composition of the present invention is preferably 20% by mass or more relative to the total solid content of the resin composition, 30% by mass or more is more preferred, 40% by mass or more is further preferred, 50% by mass or more is further preferred, 60% by mass or more is further preferred, and 70% by mass or more is further preferred. In addition, the content of the polymer precursor in the resin composition of the present invention is preferably 99.5% by mass or less relative to the total solid content of the resin composition, 99% by mass or less is more preferred, 98% by mass or less is further preferred, and 95% by mass or less is further preferred. The resin composition of the present invention may contain only one polymer precursor, or may contain two or more. When two or more types are included, it is preferred that the total amount be within the above range.

<Thermal alkali generator> The resin composition of the present invention contains a thermal alkali generator. The type of the thermal alkali generator is not particularly limited, but preferably contains at least one selected from an acidic compound that generates a base when heated to 40°C or above and an ammonium salt having an anion and an ammonium cation with a pKa1 of 0 to 4. pKa1 represents the logarithm (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the acid, and the details are described later. By combining these compounds, a cyclization reaction of a polymer precursor, etc. can be carried out at a low temperature. Furthermore, since the thermal alkali generator does not generate alkali unless heated, even when it coexists with a polymer precursor, it can suppress the cyclization of the polymer precursor during storage, and has excellent storage stability.

The thermal alkali generator preferably comprises at least one selected from an acidic compound (A1) that generates a base when heated to 40° C. or higher and an ammonium salt (A2) having an anion with a pKa1 of 0 to 4 and an ammonium cation. The acidic compound (A1) and the ammonium salt (A2) generate a base when heated, and the base generated from these compounds can promote the cyclization reaction of the polymer precursor, and the cyclization of the polymer precursor can be performed at a low temperature. In addition, in this specification, an acidic compound refers to a compound in which 1 g of the compound is collected in a container, 50 mL of a mixed solution of ion-exchange water and tetrahydrofuran (mass ratio of water/tetrahydrofuran = 1/4) is added, and the mixture is stirred at room temperature for 1 hour, and the pH (power of hydrogen) of the solution thus obtained is measured at 20°C with a pH meter of less than 7.

The alkali generation temperature of the thermal alkali generator used in the present invention is preferably 40°C or higher, more preferably 120-200°C. The upper limit of the alkali generation temperature is preferably 190°C or lower, more preferably 180°C or lower, and further 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. The alkali generation temperature can be measured as follows: for example, by using differential scanning calorimetry, the compound is heated to 250°C at 5°C/min in a pressure-resistant capsule, the peak temperature of the lowest temperature heat peak is read, and the peak temperature is taken as the alkali generation temperature.

The base generated by the thermal alkali generator is preferably a diamine or a tertiary amine, and a tertiary amine is more preferred. Tertiary amines are highly alkaline, and therefore can lower the cyclization temperature of the polymer precursor. Furthermore, the boiling point of the base generated by the thermal alkali generator is preferably above 80°C, more preferably above 100°C, and even more preferably above 140°C. Furthermore, the molecular weight of the generated base is preferably 80 to 2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. In addition, the value of the molecular weight is a theoretical value obtained from the structural formula.

In the present embodiment, the acidic compound (A1) preferably contains at least one selected from ammonium salts and compounds represented by the formula (101) or (102) described below.

In this embodiment, the ammonium salt (A2) is preferably an acidic compound. In addition, the ammonium salt (A2) may be a compound including an acidic compound that generates a base when heated to 40°C or higher (preferably 120-200°C), or a compound other than an acidic compound that generates a base when heated to 40°C or higher (preferably 120-200°C).

In this embodiment, the ammonium salt represents 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, or may exist outside the molecule of the ammonium cation, but it is preferred to exist outside the molecule of the ammonium cation. In addition, the anion existing outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the anion outside the molecule of the cation part is also referred to as a counter anion. Formula (101) Formula (102) [Chemical Formula 15] In formula (101) and formula (102), R ¹ to R ⁶ each independently represent a hydrogen atom or a alkyl group, and R ⁷ represents a alkyl group. In formula (101) and formula (102), R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ⁷ may be bonded to form a ring.

The ammonium cation is preferably represented by any one of the following formulas (Y1-1) to (Y1-5). [Chemical Formula 16]

In formula (Y1-1) to (Y1-5), ^R101 represents an n-valent organic group, and ^R1 and ^R7 have the same meanings as in formula (101) or formula (102). In formula (Y1-1) to (Y1-5), ^Ar101 and ^Ar102 each independently represent an aryl group, n represents an integer greater than 1, and m represents an integer from 0 to 5.

In this embodiment, the ammonium salt preferably has an anion and an ammonium cation with a pKa1 of 0 to 4. The upper limit of the pKa1 of the anion is preferably 3.5 or less, and 3.2 or less is further preferred. The lower limit is preferably 0.5 or more, and 1.0 or more is more preferred. If the pKa1 of the anion is within the above range, the polymer precursor can be cyclized at a lower temperature, thereby improving the stability of the resin composition. If the pKa1 is 4 or less, the stability of the thermal alkali generator is good, and the generation of alkali without heating can be suppressed, and the stability of the resin composition is good. If pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the polymer precursor is good. The type of anion is preferably selected from one of carboxylate anions, phenol anions, and phosphate anions. Carboxylate anions are more preferred for the reason of taking into account both the stability and thermal decomposition of the salt. That is, the ammonium salt is preferably a salt of ammonium cation and carboxylate anion. The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and an anion of a divalent carboxylic acid is more preferred. In this manner, a thermal base generator that can further improve the stability, curability, and developability of the resin composition can be provided. In particular, by using anions of divalent carboxylic acids, the stability, curability, and developability of the 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 pKa1 of 3.2 or less is further preferred. In this manner, the stability of the resin composition can be further improved. Here, pKa1 represents the logarithm of the inverse of the dissociation constant of the first proton of an acid, and can be found in Determination of Organic Structures by Physical Methods (author: Brown, H.C., McDaniel, D.H., Hafliger, O., Nachod, F.C.; editor: Braude, E.A., Nachod, F.C.; Academic Press, New York, 1955) or Data for Biochemical Research (author: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959). For compounds not described in these references, values calculated from the structural formula using ACD/pKa software (manufactured by ACD/Labs) were used.

The carboxylate anion is preferably represented by the following formula (X1). [Chemical Formula 17] In formula (X1), EWG represents an electron-withdrawing group.

In the present embodiment, the electron-withdrawing group refers to a group whose Hammett substituent constant σm represents a positive value. σm is described in detail in Yufu Mitsuno's General Commentary, Journal of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965), p. 631-642. In addition, the electron-withdrawing group in the present embodiment is not limited to the substituents described in the above literature. 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), 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 acetyl group, and Ph represents a phenyl group.

EWG is preferably a group represented by the following formula (EWG-1) to (EWG-6). [Chemical Formula 18] In 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 19] In formula (XA), ^L10 represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, ^-NRX- , and a combination thereof, and ^RX represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

As specific examples of the carboxylate anion, there can be cited a maleate anion, a phthalate anion, an N-phenyliminodiacetate anion, and an oxalate anion. These can be preferably used.

As specific examples of the hot alkali generator, the following compounds can be cited. [Chemical Formula 20] [Chemical formula 21]

[Chemical formula 22]

The content of the alkali generator is preferably 0.1 to 50% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. The alkali generator can be used alone or in combination. When two or more types are used, the total amount is preferably within the above range.

<Free radical polymerization initiator> The resin composition of the present invention preferably contains a free radical polymerization initiator. In particular, when a substance containing a free radical polymerizable group is used as a polymer precursor or a free radical polymerizable compound is used, the resin composition of the present invention preferably contains a free radical polymerization initiator. Examples of the free radical polymerization initiator include a photo radical polymerization initiator and a thermal radical polymerization initiator. The free radical polymerization initiator used in the resin composition of the present invention is preferably a photo radical polymerization initiator.

<<Photoradical polymerization initiator>> The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light from the ultraviolet region to the visible region is preferred. In addition, an activator that reacts with a photoexcited sensitizer to generate active free radicals can be used. The photoradical polymerization initiator preferably contains at least one compound having a molar absorbance of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorbance of the compound can be measured using a known method. For example, it is preferably measured at a concentration of 0.01 g/L using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Corporation) and using ethyl acetate as a solvent.

As the photoradical polymerization initiator, any known compound can be used. For example, alkyl halides derivatives (e.g., compounds having a trioxane skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. can be cited. For the details thereof, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, the contents of which are incorporated into this specification.

Examples of the ketone compound include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can also be preferably used. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators 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, IRGACURE 127 (manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (manufactured by BASF) can be used. As the aminoacetophenone-based initiator, compounds described in Japanese Patent Publication No. 2009-191179, which have a maximum absorption wavelength that matches a wavelength light source such as 365 nm or 405 nm, can also be used. As the acylphosphine-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide can be cited. In addition, commercially available products IRGACURE-819 or IRGACURE-TPO (manufactured by BASF) can be used. As the metallocene compound, IRGACURE-784 (manufactured by BASF) and the like are exemplified.

As the photo-radical polymerization initiator, an oxime compound is more preferred. By using an oxime compound, the exposure tolerance can be further effectively improved. Among oxime compounds, the exposure tolerance (exposure margin) is relatively wide, and it also functions as a photohardening accelerator, so it is particularly preferred. As specific examples of oxime compounds, the compounds described in Japanese Patent Publication No. 2001-233842, the compounds described in Japanese Patent Publication No. 2000-080068, and the compounds described in Japanese Patent Publication No. 2006-342166 can be used. Preferred oxime compounds include, for example, compounds having the following structures: 3-benzoyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetyloxyiminopentane-3-one, 2-acetyloxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. Oxime-based photopolymerization initiators have a linking group of >C=NOC(=O)- in the molecule. [Chemical formula 23] Among the commercial products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKAARKLS NCI-831 and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used. Furthermore, oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Unexamined Patent Publication No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Unexamined Patent Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Unexamined Patent Publication No. 2013-164471. Optimum oxime compounds include oxime compounds having specific substituents described in Japanese Unexamined Patent Publication No. 2007-269779, and oxime compounds having thioaryl groups described in Japanese Unexamined Patent Publication No. 2009-191061.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is a compound selected from the group consisting of trihalomethyl trioxane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halogenated methyl oxadiazole compounds, and 3-aryl substituted coumarin compounds. More preferred photoradical polymerization initiators are trihalogenomethyl trioxane compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. It is further preferred to select at least one compound from the group consisting of trihalogenomethyl trioxane compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds. It is further preferred to use metallocene compounds or oxime compounds, and oxime compounds are further preferred. In addition, the photoradical polymerization initiator may include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-aminophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-aminopropanone-1, quinones formed by condensation of an aromatic ring with an alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin, benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, a compound represented by the following formula (I) may be used. [Chemical Formula 24] In formula (I), R ^I00 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, a phenyl group substituted by at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, or a biphenyl group, R ^I01 is a group represented by formula (II), or is the same group as R ^I00 , and R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen. [Chemical Formula 25] In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 in the above formula (I).

Furthermore, the photoradical polymerization initiator may include compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

When a photo radical polymerization initiator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass %, and further preferably 1.0 to 10 mass % relative to the total solid content of the resin composition of the present invention. The photo radical polymerization initiator may contain only one kind or two or more kinds. When two or more photo radical polymerization initiators are included, the total amount thereof is preferably within the above range.

＜＜Thermal radical polymerization initiator＞＞ Thermal radical polymerization initiator is a compound that generates radicals by heat energy and starts or promotes the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymer precursor can be cyclized and the polymerization reaction of the polymer precursor can be carried out, so that a higher degree of heat resistance can be achieved. As a thermal radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Publication No. 2008-063554 can be cited.

When a thermal free radical polymerization initiator is contained, its content is preferably 0.1 to 30 mass % relative to the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass %, and further preferably 5 to 15 mass %. The thermal free radical polymerization initiator may contain only one kind or two or more kinds. When two or more thermal free radical polymerization initiators are contained, the total amount thereof is preferably within the above range.

<Polymerizable compound> <<Free radical polymerizable compound>> The resin composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, a free radical polymerizable compound can be used. A free radical polymerizable compound is a compound having a free radical polymerizable group. As the free radical polymerizable group, groups having ethylenic unsaturated bonds such as vinyl, allyl, vinylphenyl, (meth)acryloyl, etc. can be cited. The free radical polymerizable group is preferably (meth)acryloyl.

The number of radical polymerizable groups possessed by the radical polymerizable compound may be 1 or 2 or more. The radical polymerizable compound preferably has 2 or more radical polymerizable groups, and more preferably has 3 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 radical polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more.

From the viewpoint of developing properties, the resin composition of the present invention preferably contains at least one free radical polymerizable compound having two or more functional groups, and more preferably contains at least one free radical polymerizable compound having three or more functional groups. In addition, it may be a mixture of a free radical polymerizable compound having two or more functional groups and a free radical polymerizable compound having three or more functional groups. In addition, the number of functional groups of a free radical polymerizable compound refers to the number of free radical polymerizable groups in one molecule.

Specific examples of free radical polymerizable compounds include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl groups, amino groups, and thiohydrides with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. Furthermore, addition reaction products of unsaturated carboxylates or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylates or amides with dissociative substituents such as halogen groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Furthermore, as another example, instead of the above-mentioned unsaturated carboxylic acids, a compound group substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. can be used. As a specific example, the description of paragraphs 0113 to 0122 of Japanese Patent Publication No. 2016-027357 can be referred to, and the contents are incorporated into this specification.

In addition, the radical polymerizable compound is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyletrol tri(meth)acrylate, neopentyletrol tetra(meth)acrylate, dipentyletrol penta(meth)acrylate, dipentyletrol hexa(meth)acrylate, hexylene glycol (meth)acrylate, trihydroxymethylpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, etc., which are (meth)acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol. The present invention is preferably a compound of 2,4-dimethacrylate, ... In addition, polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds having cyclic ether groups and ethylenically unsaturated bonds such as (meth)acrylate glycidyl can also be cited. In addition, as preferred free radical polymerizable compounds other than the above, compounds having a fluorene ring and having two or more groups containing ethylenically unsaturated bonds described in Japanese Patent Publication No. 2010-160418, Japanese Patent Publication No. 2010-129825, Japanese Patent Publication No. 4364216, etc. or cardo resins can also be used. Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and vinylphosphonic acid compounds described in Japanese Patent Publication No. 02-025493 can be cited. In addition, compounds containing a perfluoroalkyl group described in Japanese Patent Publication No. 61-022048 can also be used. Furthermore, those introduced as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of WO-2015/199219 can also be preferably used, and the contents thereof are incorporated into the present specification.

In addition, the following compounds described as formula (1) and formula (2) together with specific examples in Japanese Patent Application Laid-Open No. 10-062986 can also be used as radical polymerizable compounds. These compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resulting compound.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as other radical polymerizable compounds, and these contents are incorporated into this specification.

As the radical polymerizable compound, dipentatriol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentatriol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) and the structure in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue is preferred. The oligomer type of the above can also be used.

As commercially available products of the radical polymerizable compound, for example, there can be cited SR-494 manufactured by Sartomer Company, Inc. as a tetrafunctional acrylate having four ethoxy chains, SR-209, 231, 239 manufactured by Sartomer Company, Inc. as a bifunctional methyl acrylate having four vinyloxy chains, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having six pentoxy chains, TPA-330 as a trifunctional acrylate having three isobutyloxy chains, urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), 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 (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (NOF CORPORATION.), etc.

As free radical polymerizable compounds, urethane acrylates such as those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. Furthermore, as the radical polymerizable compound, a compound having an amino structure or a sulfide structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 01-105238 can also be used.

The free radical polymerizable compound may be a free radical polymerizable compound having an acid group such as a carboxyl group or a phosphoric acid group. Among the free radical polymerizable compounds having an acid group, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, and free radical polymerizable compounds having acid groups by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides are more preferred. Particularly preferred is a free radical polymerizable compound having an acid group by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides, wherein the aliphatic polyhydroxy compound is a compound of neopentyl triol and/or dipentyl triol. As commercially available products, for example, as polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd., M-510, M-520, etc. can be cited. The preferred acid value of the radical polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. When the acid value of the radical polymerizable compound is within the above range, the production or handling properties are excellent, and further the developing properties are excellent. In addition, the polymerizability is also good.

From the viewpoint of suppressing warping accompanying the control of the elastic modulus of the cured film, the resin composition of the present invention can preferably use a monofunctional radically polymerizable compound as the radically polymerizable compound. As the monofunctional free radical polymerizable compound, (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, N-vinyl compounds such as N-vinyl pyrrolidone and N-vinyl caprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate can be preferably used. As the monofunctional free radical polymerizable compound, a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatility before exposure.

＜＜Polymerizable compounds other than the above-mentioned free radical polymerizable compounds＞＞ The resin composition of the present invention may also contain polymerizable compounds other than the above-mentioned free radical polymerizable compounds. Examples of polymerizable compounds other than the above-mentioned free radical polymerizable compounds include compounds having hydroxymethyl, alkoxymethyl or acyloxymethyl groups; epoxy compounds; cyclohexane compounds; and benzophenone compounds.

<<<Compounds having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group>>> As the compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4), or (AM5) is preferred.

[Chemical formula 26] (In the formula, t represents an integer of 1 to 20, R ¹⁰⁴ represents a t-valent organic group having 1 to 200 carbon atoms, R ¹⁰⁵ represents a group represented by -OR ¹⁰⁶ or -OCO-R ¹⁰⁷ , R ¹⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ¹⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

[Chemical formula 27] (In the formula, R ⁴⁰⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , R ⁴⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁴⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

[Chemical formula 28] (In the formula, u represents an integer of 3 to 8, R ⁵⁰⁴ represents a u-valent organic group having 1 to 200 carbon atoms, R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ , R ⁵⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁵⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (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 (manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc.

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, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, and NIKALAC MW-100LM (manufactured by Sanwa Chemical Co., Ltd.).

＜＜＜Epoxy compound (compound having epoxy group)＞＞＞ As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. Epoxy groups undergo crosslinking reaction below 200°C, and since dehydration reaction from crosslinking does not occur, it is difficult to cause film shrinkage. Therefore, by containing epoxy compounds, low-temperature curing and warping of the composition can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the modulus of elasticity and can suppress warping. The polyethylene oxide group means that the number of ethylene oxide constituent units is 2 or more, preferably 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy-containing silicones such as polymethyl (glycidyloxypropyl) siloxane, etc., but are not limited to these. Specifically, we can cite 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) EXA-4850-150, EPICLON (Registered trademark) EXA-4850-1000, EPICLON (Registered trademark) EXA-4816, EPICLON (Registered trademark) EXA-4822 (manufactured by DIC Corporation), RIKARESIN (Registered trademark) BEO-60E (manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (manufactured by ADEKA CORPORATION), etc. Among them, epoxy resins containing polyethylene oxide groups are preferred from the viewpoint of suppressing warping and having excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups and are therefore preferred.

＜＜＜Oxycyclobutane compounds (compounds having an oxycyclobutyl group)＞＞＞ As oxycyclobutane compounds, there can be cited compounds having two or more oxycyclobutane rings in one molecule, 3-ethyl-3-hydroxymethoxycyclobutane, 1,4-bis{[(3-ethyl-3-oxycyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxycyclobutyl)methyl]ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these may be used alone or in combination of two or more.

＜＜＜Benzotriazole compounds (compounds with polybenzotriazole groups)＞＞＞ Benzotriazole compounds are preferred because they do not produce degassing during curing due to the cross-linking reaction derived from the ring-opening addition reaction, thereby reducing thermal shrinkage and inhibiting the occurrence of warping.

Preferred examples of benzophenone compounds include B-a type benzophenone, B-m type benzophenone (manufactured by Shikoku Chemicals Corporation), benzophenone adducts of polyhydroxystyrene resins, and novolac type dihydrobenzophenone compounds. These may be used alone or in combination of two or more.

When a polymerizable compound is contained, its content is preferably greater than 0 mass % and less than 60 mass % relative to the total solid content of the resin composition of the present invention. It is more preferred that the lower limit is 5 mass % or more. It is more preferred that the upper limit is 50 mass % or less, and it is further preferred that it is 30 mass % or less. In addition, when a free radical polymerizable compound is contained, its content is preferably greater than 0 mass % and less than 60 mass % relative to the total solid content of the resin composition of the present invention. It is more preferred that the lower limit is 5 mass % or more. It is more preferred that the upper limit is 50 mass % or less, and it is further preferred that it is 30 mass % or less. Other polymerizable compounds may be used alone or in combination of two or more. When two or more are used simultaneously, it is preferred that their total amount be within the above range.

<Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfones, and amides. As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, butyl 3-methoxypropionate, etc.) methyl 2-alkoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionates (e.g. methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, 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 acetate, etc. can be cited as preferred. As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. can be cited as preferred. As aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. can be cited as preferred. As the sulfoxides, for example, dimethyl sulfoxide is preferred. As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, etc. are preferred.

Regarding the solvent, from the viewpoint of improving the properties of the coating surface, a mixture of two or more is also preferred. In the present invention, a solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl solvent acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, or a mixed solvent consisting of two or more is preferred. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone simultaneously.

Regarding the content of the solvent, from the perspective of coating properties, it is preferred that the total solid content concentration of the resin composition of the present invention is 5 to 80 mass %, 5 to 75 mass %, 10 to 70 mass %, and 40 to 70 mass %. The content of the solvent can be adjusted according to the desired thickness and coating method. The solvent may contain only one or more. When containing two or more solvents, it is preferred that the total is within the above range.

<Migration inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, it is possible to effectively inhibit the migration of metal ions from the metal layer (metal wiring) into the resin composition layer. The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxadiazole ring, thiazole ring, pyrazole ring, isoxadiazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, phenazine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having thiourea and thiohydrin, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Furthermore, an ion scavenger that captures anions such as halogen ions may also be used.

As other migration inhibitors, the rustproofing agent described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219, etc. can be used.

As a specific example of the migration inhibitor, the following compound can be cited. [Chemical Formula 29]

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

<Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butyl-pyrogallol, 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, phenothiocyanate, N-nitrosodiphenylamine, N-phenyl Naphthylamine, 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-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used. In addition, the following compound (Me is methyl) can also be used. [Chemical Formula 30]

When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass %, more preferably 0.02 to 3 mass %, and even more preferably 0.05 to 2.5 mass % relative to the total solid content of the 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 thereof is preferably within the above range.

<Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes or wiring. Examples of the metal adhesion improver include silane coupling agents.

Examples of silane coupling agents include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. 2014/097594. Furthermore, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358. Furthermore, it is also preferable to use the following compound as the silane coupling agent. In the following formula, Et represents an ethyl group. [Chemical Formula 31]

Furthermore, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymer precursor. By setting it to be above the above lower limit, the adhesion between the cured film and the metal layer after the curing step becomes good, and by setting it to be below the above upper limit, the heat resistance and mechanical properties of the cured film after the curing step become good. The metal adhesion improver may be only one kind or may be two or more kinds. When two or more kinds are used, it is preferred that the total is within the above range.

<Other additives> The resin composition of the present invention can be compounded with various additives as needed, such as thermal acid generators, sensitizing pigments, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, and aggregation inhibitors, within the scope of not impairing the effects of the present invention. When compounding such additives, it is preferred that the total compounding amount is set to 3% by weight or less of the solid content of the composition.

＜＜Thermal acid generator＞＞ The resin composition of the present invention may contain a thermal acid generator. When the specific thermal base generator has a protective group, the thermal acid generator is used to remove the protective group.

The content of the thermal acid generator is preferably 0.01 parts by mass or more relative to 100 parts by mass of the polymer precursor, and 0.1 parts by mass or more is more preferred. The inclusion of 0.01 parts by mass or more of the thermal acid generator promotes the crosslinking reaction and the cyclization of the polymer precursor, thereby further improving the mechanical properties and chemical resistance of the cured film. In addition, from the perspective of the electrical insulation of the cured film, the content of the thermal acid generator is preferably 20 parts by mass or less, 15 parts by mass or less is more preferred, and 10 parts by mass or less is further preferred. The thermal acid generator may be used alone or in combination of two or more. When two or more types are used, it is preferred that the total amount be within the above range.

<<Sensitizing dye>> The resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and produces electron transfer, energy transfer, heat, etc. Thereby, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo chemical changes and decompose, and generate free radicals, acids, or bases. For details about the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Publication No. 2016-027357, and the contents are incorporated into this specification.

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

＜＜Chain transfer agent＞＞ The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As chain transfer agents, for example, a compound group having SH, PH, SiH and GeH in the molecule is used. These generate free radicals by donating hydrogen to low-activity free radicals, or by deprotonation after oxidation. In particular, thiol compounds can be preferably used. In addition, the chain transfer agent can also use compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219.

When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass relative to 100 parts by mass of the total solid content of the resin composition of the present invention. 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 range thereof is preferably within the above range.

＜＜Surfactant＞＞ From the viewpoint of further improving the coating properties, various surfactants can be added to the resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, non-ionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants, etc. can be used. In addition, the following surfactants are also preferred. [Chemical formula 32]

Furthermore, the surfactant may include compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219.

When the resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass % relative to the total solid content of the resin composition of the present invention, and more preferably 0.005 to 1.0 mass %. The surfactant may be only one kind or two or more kinds. When there are two or more kinds of surfactants, the total range thereof is preferably within the above range.

＜＜Higher fatty acid derivative＞＞ In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention and localized on the surface of the composition during the drying process after coating. In addition, the higher fatty acid derivative may also be the compound described in paragraph 0155 of International Publication No. 2015/199219. When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more kinds of higher fatty acid derivatives, it is preferably that the total range thereof is within the above range.

<Restrictions on other contained substances> From the perspective of coating surface properties, the water content of the resin composition of the present invention is preferably less than 5 mass %, more preferably less than 1 mass %, and even more preferably less than 0.6 mass %.

From the perspective of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When multiple metals are included, the total of the metals is preferably within the above range. Furthermore, as a method for reducing the metal impurities accidentally contained in the resin composition of the present invention, there can be cited methods such as selecting a raw material with a lower metal content as a raw material constituting the resin composition of the present invention, filtering the raw material constituting the resin composition of the present invention through a filter, lining the inside of a device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

Considering the use as a semiconductor material and from the viewpoint of wiring corrosion, the content of halogen atoms in the resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm. Among them, the content of halogen atoms in the form of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. It is preferred that the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is respectively within the above range.

As a container for the resin composition of the present invention, a conventionally known container can be used. In addition, as a container, in order to suppress the mixing of impurities into the raw materials or the composition, it is also preferable to use a multi-layer bottle having an inner wall of the container composed of six types of six layers of resin or a bottle having a seven-layer structure formed of six types of resin. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

[Preparation of resin composition] The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be carried out by a conventionally known method. In addition, for the purpose of removing foreign matter such as garbage or particles in the composition, filtering using a filter is preferably performed. The pore size of the filter is preferably 1 μm or less, 0.5 μm or less is more preferably, and 0.1 μm or less is further preferably. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be used after being cleaned with an organic solvent in advance. In the filtering step of the filter, multiple filters can be used in parallel or in series. When using multiple filters, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cycle filtering. In addition, filtering can be performed after pressurization. When filtering after pressurization, the pressurization pressure is preferably above 0.05MPa and below 0.3MPa. In addition to filtering using filters, impurity removal treatment using adsorbents can also be performed. Filtering and impurity removal treatment using adsorbents can also be combined. As adsorbents, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

[Cured film, laminate, semiconductor element and method for manufacturing the same] Next, the cured film, laminate, semiconductor element and method for manufacturing the same are described. The cured film of the present invention is obtained by curing the resin composition of the present invention. The film thickness of the cured film of the present invention can be set to 0.5 μm or more, and can be set to 1 μm or more. In addition, as an upper limit, it can be set to 100 μm or less, and can also be set to 30 μm or less. The film thickness of the cured film of the present invention is preferably 1 to 30 μm.

The cured film of the present invention may be laminated in two or more layers, and further in three to seven layers, to form a laminate. The laminate having two or more layers of the cured film of the present invention preferably has a metal layer between the cured films. Such a metal layer can be preferably used as a metal wiring such as a redistribution layer.

Examples of fields to which the cured film of the present invention can be applied include insulating films for semiconductor elements, interlayer insulating films for redistribution layers, and stress buffer films. In addition, examples include sealing films, substrate materials (base films or cover layers of flexible printed circuit boards, interlayer insulating films), and insulating films for actual mounting purposes such as those patterned by etching. For such applications, for example, see Science & Technology Co., Ltd., "Advanced Functionality and Application Technology of Polyimide," April 2008, Kakimoto Masaaki, CMC Technical Library, "Fundamentals and Development of Polyimide Materials," November 2011, and Japan Polyimide and Aromatic Polymer Research Society, "Latest Polyimide: Fundamentals and Applications," NTS, August 2010.

Furthermore, the cured film of the present invention can also be used in the production of offset printing plates or screen printing plates, the use of molded parts, the production of protective varnishes and dielectric layers in electronics, especially microelectronics, and the like.

The method for producing a cured film of the present invention includes using the resin composition of the present invention. Specifically, it is preferred to include the following steps (a) to (d). (a) A film forming step of applying the resin composition to a substrate to form a film (b) An exposure step of exposing the film after the film forming step (c) A developing step of developing the exposed resin composition layer (d) A heating step of heating the developed resin composition at 80 to 450°C In this embodiment, the exposed resin layer can be further cured by heating after development.

The method for manufacturing a laminated body of a preferred embodiment of the present invention includes the method for manufacturing a cured film of the present invention. The method for manufacturing a laminated body of the present embodiment forms a cured film according to the above-mentioned method for manufacturing a cured film, and then, after forming the cured film, further, performs step (a) again or steps (a) to (c), or steps (a) to (d). In particular, it is preferred to perform the above-mentioned steps in sequence a plurality of times, for example 2 to 5 times (that is, a total of 3 to 6 times). By laminating the cured film in this way, a laminated body can be formed. In the present invention, it is particularly preferred to provide a metal layer on a portion where a cured film is provided, between cured films, or in both. Furthermore, in the manufacture of the laminate, it is not necessary to repeat all of steps (a) to (d). As described above, a laminate of a cured film can be obtained by performing at least (a), preferably (a) to (c) or (a) to (d) a plurality of times.

<Film formation step (layer formation step)> The manufacturing method of the preferred embodiment of the present invention includes a film formation step (layer formation step) of applying a resin composition to a substrate to form a film (layer). The type of substrate can be appropriately set according to the application, but there is no particular limitation. Examples include semiconductor manufacturing substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, evaporated films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, and electrode plates of plasma display panels (PDP). In the present invention, semiconductor manufacturing substrates are particularly preferred, and silicon substrates are more preferred. In addition, when a resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes a substrate. As a method of applying the resin composition to the substrate, coating is preferred. Specifically, as an applicable method, there can be exemplified dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the perspective of the uniformity of the thickness of the resin composition layer, spin coating, slit coating, spray coating, and inkjet coating are more preferred. By adjusting the appropriate solid component concentration or coating conditions according to the method, a resin layer of desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, spin coating, spray coating, inkjet coating, etc. are preferred, and as long as it is a rectangular substrate, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of the spin coating method, for example, the rotation speed can be 500 to 2000 rpm for about 10 seconds to 1 minute.

<Drying step> The manufacturing method of the present invention may further include a drying step for removing the solvent after forming the resin composition layer and after the film forming step (layer forming step). The preferred drying temperature is 50 to 150°C, 70 to 130°C is more preferred, and 90 to 110°C is further preferred. The drying time is exemplified as 30 seconds to 20 minutes, 1 minute to 10 minutes is preferred, and 3 minutes to 7 minutes is more preferred.

<Exposure step> The manufacturing method of the present invention may include an exposure step of exposing the resin composition layer. The exposure amount is not particularly limited as long as it can cure the resin composition. For example, it is preferably 100 to 10000 mJ/ ^cm2 , and more preferably 200 to 8000 mJ/ ^cm2 , calculated as the exposure energy at a wavelength of 365 nm. The exposure wavelength can be appropriately set within the range of 190 to 1000 nm, and preferably 240 to 550 nm. Regarding the exposure wavelength, if described in terms of its relationship with the light source, the following examples can be cited: (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), wide (3 wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6nm), (6) electron beams, etc. The resin composition of the present invention is preferably exposed by a high-pressure mercury lamp, and preferably by i-rays. This can achieve high exposure sensitivity.

<Development treatment step> The manufacturing method of the present invention may include a development treatment step of developing the exposed resin composition layer. By developing, the unexposed portion (non-exposed portion) is removed. There is no particular limitation on the development method as long as the desired pattern can be formed. For example, a development method such as swirling immersion, spraying, immersion, and ultrasonic waves can be used. Development is performed using a developer. Regarding the developer, as long as the unexposed portion (non-exposed portion) can be removed, it can be used without particular limitation. It is preferred that the developer contains an organic solvent, and it is more preferred that the developer contains more than 90% of the organic solvent. In the present invention, it is preferred that the developer contains an organic solvent having a ClogP value of -1 to 5, and it is more preferred that the developer contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained by inputting the structural formula into ChemBioDraw as a calculated value. As for the organic solvent, esters include, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.) ), 3-alkoxy alkyl propionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxy alkyl propionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.) ethyl propionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl Solvent acetate, 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 acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., and as sulfoxides, dimethyl sulfoxide can be suitably mentioned. In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. Preferably, 50% by mass or more of the developer is an organic solvent, more preferably 70% by mass or more of the developer is an organic solvent, and even more preferably 90% by mass or more of the developer is an organic solvent. In addition, 100% by mass of the developer may be an organic solvent.

The developing time is preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, and it can usually be carried out at 20 to 40°C. After the treatment with the developer, rinsing can be performed. It is preferred that the rinsing be performed with a solvent different from the developer. For example, the solvent contained in the resin composition can be used for rinsing. The rinsing time is preferably 5 seconds to 1 minute.

<Heating step> The manufacturing method of the present invention preferably includes a heating step after the film forming step (layer forming step), the drying step or the developing step. In the heating step, a cyclization reaction of the polymer precursor is performed. As the heating temperature (maximum heating temperature) of the layer in the heating step, 50°C or more is preferred, 80°C or more is more preferred, 140°C or more is further preferred, 150°C or more is further preferred, 160°C or more is further preferred, and 170°C or more is further preferred. As the upper limit, 500°C or less is preferred, 450°C or less is more preferred, 350°C or less is further preferred, 250°C or less is further preferred, and 220°C or less is still further preferred. Regarding heating, it is preferred that the heating rate be 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, 2 to 10°C/min is more preferred, and 3 to 10°C/min is further preferred. By setting the heating rate to 1°C/min or more, it is possible to ensure productivity while preventing excessive volatilization of amines, and by setting the heating rate to 12°C/min or less, it is possible to alleviate the residual stress of the cured film. The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and further preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when a resin composition is applied to a substrate and then dried, it is the temperature of the dried film (layer), for example, it is preferably gradually increased from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition. The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes. In particular, when forming a multi-layer laminate, from the viewpoint of the adhesion between the layers of the cured film, heating is preferably performed at a heating temperature of 180°C to 320°C, and more preferably at 180°C to 260°C. The reason for this is uncertain, but it is believed that the acetylene groups of the polymer precursor between the layers undergo crosslinking reactions at this temperature.

Heating can be performed in stages. For example, the pre-treatment step can be performed by heating from 25°C to 180°C at 3°C/min and maintaining at 180°C for 60 minutes, and then heating from 180°C to 200°C at 2°C/min and maintaining at 200°C for 120 minutes. The heating temperature of the pre-treatment step is preferably 100-200°C, more preferably 110-190°C, and even more preferably 120-185°C. In the pre-treatment step, it is also preferred to perform the treatment while irradiating with ultraviolet rays as described in the gazette of U.S. Patent No. 9159547. The properties of the membrane can be improved by such pre-treatment steps. The pretreatment step can be performed in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pretreatment can be a two-stage step or more, for example, pretreatment step 1 can be performed in the range of 100 to 150°C, and then pretreatment step 2 can be performed in the range of 150 to 200°C. Furthermore, cooling can be performed after heating, and the cooling speed in this case is preferably 1 to 5°C/minute.

Regarding the heating step, it is preferred to conduct the heating step in a low oxygen concentration environment by flowing an inert gas such as nitrogen, helium, or argon to prevent decomposition of the polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

<Metal layer forming step> The manufacturing method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the resin composition layer after the development process. As the metal layer, there is no particular limitation, and existing metal types can be used, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten, copper and aluminum are more preferred, and copper is further preferred. The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Table No. 2001-521288, Japanese Patent Publication No. 2004-214501, and Japanese Patent Publication No. 2004-101850 can be used. For example, photolithography, stripping, electrolytic plating, electroless plating, etching, printing, and methods combining these methods can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be cited. As for the thickness of the metal layer, 0.1 to 50 μm is preferred in the thickest wall portion, and 1 to 10 μm is more preferred.

<Lamination step> The manufacturing method of the present invention preferably also includes a lamination step. The lamination step includes a series of steps of (a) film formation step (layer formation step), (b) exposure step, (c) development step, and (d) heating step, which are performed again in sequence on the surface of the hardened film (resin layer) or the metal layer. Among them, it can be a state in which only the film formation step (a) is repeated. In addition, it can also be a state in which the heating step (d) is performed at the end or in the middle of the lamination. That is, it can also be set as follows: repeat the steps (a) to (c) for a specified number of times, and then perform heating (d) to harden the resin composition layer to be layered. In addition, the (c) development step can include the (e) metal layer formation step, and at this time, the heating (d) can be performed each time, or the heating (d) can be performed collectively after the predetermined number of layering. It is beyond doubt that the above-mentioned drying step and heating step can also be appropriately included in the layering step. When the lamination step is further performed after the lamination step, a surface activation treatment step may be further performed after the above-mentioned heating step, after the above-mentioned exposure step, or after the above-mentioned metal layer forming step. Plasma treatment is exemplified as the surface activation treatment. The above-mentioned lamination step is preferably performed 2 to 5 times, and 3 to 5 times is more preferably performed. For example, a structure of the resin layer such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer having more than 3 layers and less than 7 layers is preferably, and more than 3 layers and less than 5 layers is further preferably. In the present invention, after the metal layer is provided, it is preferred to further form a hardened film (resin layer) of the resin composition in a manner covering the metal layer. Specifically, it is possible to cite an embodiment in which (a) a film forming step, (b) an exposure step, (c) a developing step, (e) a metal layer forming step, and (d) a heating step are sequentially repeated, or (a) a film forming step, (b) an exposure step, (c) a developing step, and (e) a metal layer forming step are sequentially repeated, and (d) a heating step is provided at the end or in the middle. By alternately performing the step of laminating the resin composition layer (resin) and the step of forming the metal layer, the resin composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses a semiconductor device having a cured film or laminate of the present invention. As a specific example of a semiconductor device using the resin composition of the present invention in the formation of an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Publication No. 2016-027357, and such contents are incorporated into this specification. [Example]

The present invention is further described in detail below by way of examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

<Method for determining the content of specific components (HNO ₂ , NO ₂ ^- , HNO ₃ , NO ₃ ^- , H ₂ SO ₄ , HSO ₄ ^- , SO ₄ ^2- , H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- )> 20 g of the test sample, 50 g of tetrahydrofuran as a non-aqueous organic solvent, and 50 g of ultrapure water were mixed. When solids were precipitated by adding water, the solids were removed by centrifugal separation. When solids were not precipitated, the organic layer and the aqueous layer were separated (liquid separation operation), and the content of the specific components extracted into the aqueous solution was determined by ion chromatography. As a measuring device, Shimadzu HIC-20A (manufactured by Shimadzu Corporation) was used.

<Synthesis Example 1> [Synthesis of a polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and benzyl alcohol (A-1: a polyimide precursor having no free radical polymerizable group)] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N-methylpyrrolidone and dried using a molecular sieve. The suspension was heated at 100°C for 3 hours. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while the temperature was maintained at -10±4°C. During the addition of SOCl ₂ , the viscosity increased. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution prepared by dissolving 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at -5 to 0°C over 20 minutes. Next, after the reaction mixture was reacted at 0°C for 1 hour, 70 g of ethanol was added, and stirred at room temperature overnight. Next, the polyimide precursor was precipitated in 5L of water, and the water-polyimide precursor mixture was stirred at 5000rpm for 15 minutes. The obtained wet solid was dissolved in 300mL of tetrahydrofuran (THF), and then 300mL of water was added and the separation operation was repeated 3 times. The obtained THF/polyimide precursor solution was reprecipitated with 5L of water. The polyimide precursor was removed by filtration, stirred again in 4L of water for 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried at 45°C for 3 days under reduced pressure. The weight average molecular weight of the polyimide precursor was 18,000. Furthermore, when the contents of specific components (HNO ₂ , NO ₂ ^- , HNO ₃ , NO ₃ ^- , H ₂ SO ₄ , HSO ₄ ^- , SO ₄ ^2- , H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- ) in the polyimide precursor were measured by ion chromatography, no specific components were detected.

A-1 [Chemical formula 33]

<Synthesis Example 2> [Synthesis of a polyimide precursor derived from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-2: a polyimide precursor having a free radical polymerizable group)] 14.06 g (64.5 mmol) of pyromellitic acid dianhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol) and 100 g of diethylene glycol dimethyl ether (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ , and then converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and a polyimide precursor was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor was 19,000. In addition, the content of specific components (HNO ₂ , NO ₂ ^- , HNO ₃ , NO ₃ ^- , H ₂ SO ₄ , HSO ₄ ^- , SO ₄ ^2- , H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- ) in the polyimide precursor was measured by ion chromatography, and as a result, no specific components were detected.

A-2 [Chemical formula 34]

<Synthesis Example 3> [Synthesis of a polyimide precursor (A-3: a polyimide precursor having a radical polymerizable group) derived from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol) and 100 g of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 18 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and a polyimide precursor was obtained in the same manner as in Synthesis Example 1. Furthermore, the content of specific components (HNO ₂ , NO ₂ ^- , HNO ₃ , NO ₃ ^- , H ₂ SO ₄ , HSO ₄ ^- , SO ₄ ^2- , H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- ) in the polyimide precursor was measured by ion chromatography, and as a result, no specific components were detected.

A-3 [Chemical formula 35]

<Synthesis Example 4> [Synthesis of a polyimide precursor (A-4: a polyimide precursor having a radical polymerizable group) derived from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (o-toluene) and 2-hydroxyethyl methacrylate] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol) and 100 g of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 18 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor using 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 1, and a polyimide precursor was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor was 19,000. Furthermore, the content of specific components (HNO ₂ , NO ₂ ^- , HNO ₃ , NO ₃ ^- , H ₂ SO ₄ , HSO ₄ ^- , SO ₄ ^2- , H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- ) in the polyimide precursor was measured by ion chromatography, and as a result, no specific components were detected.

A-4 [Chemical formula 36]

<Synthesis Example 5> [Synthesis of polybenzoxazole precursor (A-5) derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydiphenylformyl chloride] 13.92 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to 100 mL of N-methyl-2-pyrrolidone and stirred to dissolve. Then, 11.21 g of 4,4'-oxydiphenylformyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5°C, and stirring was continued for 60 minutes. Next, the polybenzoxazole precursor was precipitated in 6 liters of water, and the water-polybenzoxazole precursor mixture was stirred at 5000 rpm for 15 minutes. The polybenzoxazole precursor was removed by filtration, stirred again in 6 liters of water for 30 minutes, and filtered again. Then, the obtained polybenzoxazole precursor was dried at 45° C. for 3 days under reduced pressure. The weight average molecular weight of the polybenzoxazole precursor was 15,000. In addition, no specific components (HNO ₂ , NO ₂ ^- , HNO ₃ , NO ₃ - , H ₂ SO 4 , HSO 4 ^- , SO _{4 2-} , H ₂ SO ³ , HSO ₃ ^{- ,} and SO _{3 2-} ) were detected _in ^the polybenzoxazole precursor.

A-5 [Chemical formula 37]

<Example and Comparative Example> The components listed in the following table were mixed to obtain each resin composition. Regarding the components other than the polymer precursor, the components listed in the following table were also subjected to repeated purification methods such as distillation and crystallization. The content of a specific component in these components was confirmed by ion chromatography, and it was confirmed that these components did not contain the specific component. The obtained resin composition was filtered under pressure through a filter with a pore width of 0.8μm. Next, sodium nitrite, nitric acid, sodium nitrate, sulfuric acid, potassium bisulfate, sodium sulfate, sulfurous acid water, sodium bisulfite and sodium sulfite were added to adjust the contents of HNO ₂ , NO ₂ ^- , HNO ₃ , NO ₃ ^- , H ₂ SO ₄ , HSO ₄ ^- , SO ₄ ^2- , H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- to the contents shown in the following table, thereby preparing the resin compositions of the Examples and Comparative Examples. The contents of the above components added to the resin composition and subjected to water extraction were measured by ion chromatography.

[Table 1] Polymer precursor Thermoalkali generator Free Radical Polymerization Initiator Free radical polymerizable compounds Polymerization inhibitor Migration inhibitors Metal Adhesion Improver Solvent The sum of HNO ² and NO ^2- The sum of HNO ³ and NO ^3- The sum of H ₂ SO ₄ , HSO ₄ ^- and SO ₄ ^2- The sum of H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- Total content of specific ingredients Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Mass ppm Mass ppm Mass ppm Mass ppm Mass ppm Composition 1 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 5 5 2 2 14 Composition 2 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0.1 10 3 7 20.1 Composition 3 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0 3 50 1 54 Composition 4 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0.05 2 0 0.05 2.1 Composition 5 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 230 250 185 275 940 Composition 6 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0 0 0.002 0 0.002 Composition 7 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0.01 0 0 0 0.01 Composition 8 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0 0.003 0.01 0 0.013 Composition 9 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0 0 0 0.01 0.01 Composition 10 A-2 33.6 B-2 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-2 0.126 G-1 0.63 I-1 45 I-2 15 2 3 0.5 1.5 7 Composition 11 A-3 33.6 B-3 0.3 C-1 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 3.5 5 1.3 0.7 10.5 Composition 12 A-4 33.6 B-3 0.75 C-1 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 10 0 0.5 1.5 12 Composition 13 A-5 33.6 B-4 0.3 C-1 1.26 D-2 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 15 1.5 0 1 17.5 Composition 14 A-3 33.6 B-5 0.75 C-2 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-3 0.63 I-1 45 I-2 15 2 2 2.5 1 7.5 Composition 15 A-3 33.6 B-4 0.75 C-1 1.26 D-3 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 0.5 1 0.5 2 4 Composition 16 A-3 33.6 B-4 0.75 C-3 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-3 15 0.5 0.5 0.5 10 11.5 Composition 17 A-3 33.6 B-4 0.75 C-1 1.26 D-1 5.88 E-3 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0 5 0 1.5 6.5 Composition 18 A-5 33.6 B-5 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-3 0.126 G-1 0.63 I-1 45 I-2 15 1 0.5 0.3 0.1 1.9 Composition 19 A-3 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-4 0.126 G-1 0.63 I-1 45 I-3 15 0.01 0.5 1 0.1 1.61 Composition 20 A-3 33.6 B-2 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-3 0.63 I-1 45 I-2 15 0.5 1.5 0 15 17 Composition 21 A-3 33.6 B-5 0.75 C-3 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-3 15 9 3 2.5 10 24.5

[Table 2] Polymer precursor Thermoalkali generator Free Radical Polymerization Initiator Free radical polymerizable compounds Polymerization inhibitor Migration inhibitors Metal Adhesion Improver Solvent The sum of HNO ² and NO ^2- The sum of HNO ³ and NO ^3- The sum of H ₂ SO ₄ , HSO ₄ ^- and SO ₄ ^2- The sum of H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- Total content of specific ingredients Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Mass ppm Mass ppm Mass ppm Mass ppm Mass ppm Composition 22 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0 0 0 0 0 Composition 23 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 500 330 260 100 1190 Composition 24 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0 0 1100 20 1120 Composition 25 A-2 33.6 B-2 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-2 0.126 G-1 0.63 I-1 45 I-2 15 160 220 280 380 1040 Composition 26 A-3 33.6 B-3 0.3 C-1 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 430 185 230 210 1055 Composition 27 A-4 33.6 B-3 0.75 C-1 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 100 190 335 415 1040 Composition 28 A-5 33.6 B-4 0.3 C-1 1.26 D-2 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 255 325 200 250 1030 Composition 29 A-3 33.6 B-5 0.75 C-2 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-3 0.63 I-1 45 I-2 15 330 320 190 220 1060 Composition 30 A-3 33.6 B-4 0.75 C-1 1.26 D-3 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 550 300 285 100 1235 Composition 31 A-3 33.6 B-4 0.75 C-3 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-3 15 80 170 450 305 1005 Composition 32 A-3 33.6 B-4 0.75 C-1 1.26 D-1 5.88 E-3 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 250 280 310 170 1010 Composition 33 A-5 33.6 B-5 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-3 0.126 G-1 0.63 I-1 45 I-2 15 600 55 215 155 1025 Composition 34 A-3 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-4 0.126 G-1 0.63 I-1 45 I-3 15 110 115 360 520 1105 Composition 35 A-3 33.6 B-2 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-3 0.63 I-1 45 I-2 15 500 100 150 290 1040 Composition 36 A-3 33.6 B-5 0.75 C-3 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-3 15 300 330 280 170 1080

The raw materials listed in the above table are as follows.

(Polymer precursor) A-1 to A-5: the above-mentioned polymer precursors A-1 to A-5

(Thermoalkali generator) B-1 to B-5: Compounds having the following structure [Chemical Formula 38]

(Free radical polymerization initiator) C-1: IRGACURE OXE 01 (manufactured by BASF) C-2: IRGACURE OXE 02 (manufactured by BASF) C-3: IRGACURE 369 (manufactured by BASF)

(Free radical polymerizable compound) D-1: A-DPH (manufactured by Shin Nakamura Chemical Co., Ltd.) D-2: SR-209 (manufactured by Sartomer Company inc., compound having the following structure) [Chemical formula 39] D-3: A-TMMT (manufactured by Shin Nakamura Chemical Co., Ltd.)

(Polymerization inhibitor) E-1: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) E-2: p-Benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) E-3: p-Methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Migration inhibitor) F-1 to F-4: Compounds having the following structures [Chemical Formula 40]

(Metal Adhesion Improver) G-1 to G-3: Compounds having the following structures. In the following structural formula, Et represents an ethyl group. [Chemical Formula 41]

(Solvent) I-1: γ-Butyrolactone (manufactured by SANWAYUKA INDUSTRY CORPORATION) I-2: Dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.) I-3: N-methyl-2-pyrrolidone (manufactured by Ashland Corporation)

<Evaluation of storage stability> The viscosity of the resin compositions of compositions 1 to 36 was measured using an E-type viscometer (0 day). After the resin compositions were left to stand at 25°C for 14 days in a sealed container, the viscosity was measured again using an E-type viscometer (14 days). The viscosity variation rate was calculated according to the following formula. The lower the viscosity variation rate, the higher the storage stability. Viscosity variation rate = |100×{1-(viscosity (14 days)/viscosity (0 day))}| The viscosity measurement was performed at 25°C, and other procedures were in accordance with JIS Z 8803:2011. A: Viscosity change rate is less than 5% B: Viscosity change rate is more than 5% and less than 10% C: Viscosity change rate is more than 10% and less than 15% D: Viscosity change rate is more than 15% and less than 20%

<Evaluation of moisture resistance> The resin compositions of compositions 1 to 36 were applied to a silicon wafer using a spin coating method and dried at 100°C for 5 minutes using a hot plate to form a resin composition layer with a thickness of about 15μm. The resin composition layer was heated at a rate of 10°C/min in a nitrogen atmosphere until it reached 250°C, and then heated for 3 hours to form a cured film. The silicon wafer with the cured film was placed in a constant temperature and humidity layer at a temperature of 85°C and a humidity of 85% for 24 hours, and the percentage of the area where the modification (whitening, cracks) occurred relative to the area of the cured film was observed to evaluate the moisture resistance. A: The modified area is less than 2% of the area of the hardened film B: The modified area is more than 2% and less than 5% of the area of the hardened film C: The modified area is more than 5% and less than 10% of the area of the hardened film D: The modified area is more than 10% of the area of the hardened film

<Copper Corrosion> The resin compositions of compositions 1 to 36 were applied to a copper wafer using a spin coating method and dried on a hot plate at 100°C for 5 minutes to form a resin composition layer with a thickness of about 15μm. The resin composition layer was heated at a rate of 10°C/min in a nitrogen atmosphere until it reached 250°C, and then heated for 3 hours to form a cured film. The copper wafer with the cured film was placed in a constant temperature and humidity layer at a temperature of 85°C and a humidity of 85% for 24 hours, and the corrosion sites on the copper wafer were observed using an optical microscope. The copper corrosion was evaluated by observing the percentage of the area of the corrosion site relative to the area of the side of the copper wafer with the cured film. A: The area of the corrosion site is less than 5% relative to the area of the side of the copper wafer with the cured film B: The area of the corrosion site is 5% or more and less than 10% relative to the area of the side of the copper wafer with the cured film C: The area of the corrosion site is 10% or more and less than 20% relative to the area of the side of the copper wafer with the cured film D: The area of the corrosion site is 20% or more relative to the area of the side of the copper wafer with the cured film

[Table 3] Resin composition used Preserve stability Moisture resistance Copper Corrosion Embodiment 1 Composition 1 A A A Embodiment 2 Composition 2 A A A Embodiment 3 Composition 3 A A A Embodiment 4 Composition 4 A A A Embodiment 5 Composition 5 A A B Embodiment 6 Composition 6 A B A Embodiment 7 Composition 7 A A A Embodiment 8 Composition 8 A A A Embodiment 9 Composition 9 A A A Embodiment 10 Composition 10 A A A Embodiment 11 Composition 11 A A A Embodiment 12 Composition 12 A A A Embodiment 13 Composition 13 A A A Embodiment 14 Composition 14 A A A Embodiment 15 Composition 15 A A A Embodiment 16 Composition 16 A A A Embodiment 17 Composition 17 A A A Embodiment 18 Composition 18 A A A Embodiment 19 Composition 19 A A A Embodiment 20 Composition 20 A A A Embodiment 21 Composition 21 A A A Comparison Example 1 Composition 22 B B A Comparison Example 2 Composition 23 C D C Comparison Example 3 Composition 24 C D C Comparison Example 4 Composition 25 B C C Comparison Example 5 Composition 26 B C C Comparative Example 6 Composition 27 B C C Comparison Example 7 Composition 28 B C C Comparative Example 8 Composition 29 B C C Comparative Example 9 Composition 30 D D D Comparative Example 10 Composition 31 B C C Comparative Example 11 Composition 32 B C C Comparative Example 12 Composition 33 B C C Comparative Example 13 Composition 34 B C C Comparative Example 14 Composition 35 B C C Comparative Example 15 Composition 36 B C C

According to the above results, the resin composition of the embodiment has good storage stability and can form a cured film with excellent moisture resistance. Furthermore, the evaluation of copper corrosion resistance is also good. In addition, although Examples 1 to 9 and Comparative Examples 1 to 3 are test examples using resin compositions that differ only in the content of a specific component, Examples 1 to 9 using compositions 1 to 9 having a content of a specific component of 1 mass ppb or more and 1000 mass ppm or less relative to the total solid content of the resin composition show an evaluation of storage stability that is superior by 1 grade or more compared to Comparative Examples 1 to 3 using resin compositions 22 to 24 having a content of a specific component outside the above range. In addition, regarding moisture resistance and copper corrosion resistance, they are also equal to or superior by one grade or more. In addition, the results of Example 10 and Comparative Example 4, Example 11 and Comparative Example 5, Example 12 and Comparative Example 6, Example 13 and Comparative Example 7, Example 14 and Comparative Example 8, Example 15 and Comparative Example 9, Example 16 and Comparative Example 10, Example 17 and Comparative Example 11, Example 18 and Comparative Example 12, Example 19 and Comparative Example 13, Example 20 and Comparative Example 14, and Example 21 and Comparative Example 15 also show the same tendency.

without

without

without.

Claims (17)

A resin composition comprising a pre-driver selected from polyimide and polybenzo

In at least one polymer precursor of the azole precursor, _the ^{total content of} HNO2 ^, _NO2- , _HNO3 , _NO3- , _H2SO4 , ^HSO4- _{, SO42-} , _H2SO3 , _HSO3- and _SO32- is 1 ppb or more _and 1000 ppm or less based on the total solid content of the _resin composition ^. The resin composition as described in Item 1 of the patent application scope also contains at least one selected from silane coupling agent, thermal salt generator, free radical polymerization initiator and free radical polymerizable compound. A resin composition as described in item 1 or 2 of the patent application, wherein the polymer precursor comprises a polyimide precursor. The resin composition as described in claim 3, wherein the polyimide precursor has a constituent unit represented by the following formula (1):

In formula (1), ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group. The resin composition as described in claim 4, wherein at least one of R ¹¹³ and R ¹¹⁴ in formula (1) contains a free radical polymerizable group. The resin composition described in item 1 or 2 of the patent application scope is used to form a pattern by developing with a developer containing 90% by mass or more of an organic solvent. A resin composition as described in item 1 or 2 of the patent application scope, which is used to form a component in contact with metal. A resin composition as described in item 1 or 2 of the patent application scope, which is used to form an interlayer insulating film for a redistribution layer. The resin composition as described in item 1 or 2 of the patent application, wherein the total content of HNO ₂ , NO ₂ ^- , HNO ₃ , NO ₃ ^- , H ₂ SO ₄ , HSO ₄ ^- , SO ₄ ^2- , H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- is 6.5 mass ppm or more and 1000 mass ppm or less relative to the total solid content of the resin composition. A resin composition as described in item 1 or 2 of the patent application, wherein the total content of HNO ₂ and NO ₂ ^- is 1.0 mass ppb or more and 1000 mass ppm or less relative to the total solid content of the resin composition, or the total content of H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- is 1.0 mass ppb or more and 1000 mass ppm or less relative to the total solid content of the resin composition. A cured film obtained by curing the resin composition described in any one of items 1 to 10 of the patent application scope. The cured film described in Item 11 of the patent application has a film thickness of 1μm~30μm. A laminate having two or more layers of the hardened film described in Item 11 of the patent application, wherein a metal layer is provided between the two layers of hardened film. A method for manufacturing a hardened film, comprising: a film forming step, applying the resin composition described in any one of items 1 to 10 of the patent application scope to a substrate to form a film. The method for manufacturing a hardened film as described in Item 14 of the patent application scope comprises: an exposure step of exposing the film; and a development step of developing the film. The method for manufacturing a hardened film as described in Item 14 of the patent application scope includes the step of heating the film at 80°C to 450°C. A semiconductor component having a hardened film as described in item 11 of the patent application scope.