TWI779162B - Photosensitive resin composition, cured film, laminated body, manufacturing method of cured film, manufacturing method of laminated body, semiconductor device - Google Patents

Abstract

The present invention provides a photosensitive resin composition comprising a polymer precursor and a compound whose acidity decreases when heated, a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, and a semiconductor device.

Description

Photosensitive resin composition, cured film, laminate, method for producing cured film, method for producing laminate, semiconductor device

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

Cyclized and cured resins such as polyimide resins and polybenzoxazole resins are excellent in heat resistance and insulation, and are therefore suitable for various applications (for example, see Non-Patent Documents 1 and 2). The use is not particularly limited, but if a semiconductor device for actual mounting is taken as an example, it may be used as a material of an insulating film or a sealing material, or the use of the protective film. In addition, it is also used as a base film or a cover layer of a flexible substrate. The aforementioned polyimide resins and the like generally have low solubility in solvents. Therefore, a method in which a polymer precursor before cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor, is dissolved in a solvent is often used. Thereby, excellent workability can be achieved, and when manufacturing each product as mentioned above, it can apply|coat to a board|substrate etc. in various forms, and can be processed. Then, heating and cyclization of the polymer precursor enables the formation of the hardened product. In addition to the high performance possessed by polyimide resins and the like, their industrial application is increasingly expected from the viewpoint of their excellent manufacturing adaptability.

Attempts have been made to apply polyimide as a protective film for an interlayer insulating film (Patent Document 1). In this technique, a resin composition containing a polyimide precursor and 2,4,6-trimethylpyridinium p-toluenesulfonate is used. Accordingly, it is described that a resin composition capable of providing a resin composition with little change in viscosity at room temperature is described. In the technology of Patent Document 2, a resin composition is used, which contains a polyimide precursor, a compound that generates free radicals when irradiated with actinic rays, a specific compound having an oxirane group, and a solvent. Thereby, it is described that it is possible to provide a resin composition which has favorable photosensitive properties, can form a cured film at a low final curing temperature, and has a high weight loss temperature of the cured film. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-108053 [Patent Document 2] Japanese Patent Laid-Open No. 2014-201695 [Non-patent literature]

[Non-Patent Document 1] Science & technology Co., Ltd. "Highly functional polyimide and application technology" April 2008 [Non-Patent Document 2] Masaki Kakimoto/Supervisor, CMC Technical Library "Basics and Development of Polyimide Materials" Published in November 2011

The polymer precursor can be cured by heating as described above. However, due to this characteristic, hardening during storage may easily progress and the stability of the resin may be lacking. On the other hand, if the method of suppressing the cyclization of the precursor is used in the composition in order to prevent curing, the curability may conversely deteriorate and the properties required at the time of film formation may not be satisfied. Therefore, an object of the present invention is to provide a photosensitive resin composition, a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, and a semiconductor device capable of achieving good storage stability while maintaining sufficient curability. .

Based on the above-mentioned problems, the inventors of the present invention have conducted intensive studies. As a result, the storage stability of the polymer precursor has been improved by using a compound that reduces the acidity when heated (hereinafter, sometimes referred to as an "acid disappearing agent"). High, on the other hand, it does not inhibit the curability during the hardening treatment and can maintain sufficient performance. The inventors found that the above-mentioned problems can be solved by this, and completed the present invention. Specifically, the above-mentioned problems are solved by the following means.

式（1）中，A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹¹ 表示2價有機基團，R¹¹⁵ 表示4價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團。 ＜15＞如＜14＞所述之感光性樹脂組成物，其中 上述式（1）中的R¹¹³ 及R¹¹⁴ 中的至少一個包含自由基聚合性基團。 ＜16＞如＜14＞或＜15＞所述之感光性樹脂組成物，其中 上述式（1）中的R¹¹⁵ 係包含芳香環之基團。 ＜17＞如＜14＞～＜16＞中任一項所述之感光性樹脂組成物，其中 上述式（1）中的R¹¹¹ 由-Ar⁰ -L⁰ -Ar⁰ -表示； Ar⁰ 分別獨立地表示芳香族基，L⁰ 表示單鍵、可以經氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-S（=O）₂ -、-NHCO-以及選自上述等的組合之基團。 ＜18＞如＜14＞～＜17＞中任一項所述之感光性樹脂組成物，其中 上述式（1）中的R¹¹¹ 由下述式（51）或式（61）表示； [化學式2]

式（51）中，R⁵⁰ ～R⁵⁷ 分別獨立地表示氫原子、氟原子或1價有機基團，R⁵⁰ ～R⁵⁷ 中的至少一個表示氟原子、甲基、氟甲基、二氟甲基或三氟甲基； [化學式3]

式（61）中，R⁵⁸ 及R⁵⁹ 分別獨立地表示氟原子、氟甲基、二氟甲基或三氟甲基。 ＜19＞如＜1＞～＜18＞中任一項所述之感光性樹脂組成物，其用於使用了包含90%以上的有機溶劑之顯影液之顯影。 ＜20＞如＜1＞～＜19＞中任一項所述之感光性樹脂組成物，其用於再配線層用層間絕緣膜的形成。 ＜21＞一種硬化膜，其使＜1＞～＜20＞中任一項所述之感光性樹脂組成物硬化而成。 ＜22＞如＜21＞所述之硬化膜，其中 膜厚係1～30μm。 ＜23＞一種積層體，其具有兩層以上的＜21＞或＜22＞所述之硬化膜。 ＜24＞一種積層體，其具有3～7層＜21＞或＜22＞所述之硬化膜。 ＜25＞如＜23＞或＜24＞所述之積層體，其中 於上述硬化膜之間具有金屬層。 ＜26＞一種硬化膜的製造方法，其包括將＜1＞～＜20＞中任一項所述之感光性樹脂組成物適用於基板而形成膜之膜形成步驟。 ＜27＞如＜26＞所述之硬化膜的製造方法，其具有對上述膜進行曝光之曝光步驟及對上述膜進行顯影之顯影步驟。 ＜28＞如＜27＞所述之硬化膜的製造方法，其中 上述顯影中使用之顯影液包含90%以上的有機溶劑。 ＜29＞如＜26＞～＜28＞中任一項所述之硬化膜的製造方法，其包括於80～450℃下對上述膜進行加熱之步驟。 ＜30＞一種積層體的製造方法，其將＜26＞～＜29＞中任一項所述之硬化膜的製造方法進行複數次。 ＜31＞一種半導體器件，其具有＜21＞或＜22＞所述之硬化膜或＜23＞～＜25＞中任一項所述之積層體。 [發明效果]<1> A photosensitive resin composition comprising a polymer precursor selected from polyimide precursors and polybenzoxazole precursors and a compound whose acidity decreases when heated. <2> The photosensitive resin composition as described in <1>, wherein the compound whose acidity decreases upon heating is a compound represented by any one of formulas A1 to A3; (X) _m -L ^A -(Y) _n ････Formula A1 In the formula, X represents -COOH, -SO ₃ H or -PO ₃ H ₂ , L ^A represents m+n valence linking group, Y represents -OH, -COOH or -NH (R ^N ) , R ^N is a hydrogen atom or an organic group, m represents an integer from 1 to 4, and n represents an integer from 1 to 4; (X) _m -L ^A -(Q) _n ････Formula A2 In the formula, X represents -COOH, -SO ₃ H or -PO ₃ H ₂ , L ^A represents the m+n valent linking group, Q represents the group that releases the alkali component by heating; Z-( ^LC -COOH) _nz ････ Formula A3 In the formula, Z represents an nz-valent organic group, L ^C represents * ¹ -(C=O)C(R ^a ) ₂ -* ² , -CH(R ^b )- or -C(R ^b ) ₂ - , R ^a represents a hydrogen atom, alkyl, alkenyl, aryl or aralkyl, R ^b represents an alkyl, alkenyl, aryl or aralkyl, * ¹ represents the bonding position on the Z side, * ² represents COOH Side bonding position, nz is an integer of 1-4. <3> The photosensitive resin composition as described in <2>, wherein in formula A1, X is -SO ₃ H. <4> The photosensitive resin composition according to <2> or <3>, wherein in formula A1, L ^A is a linking group connecting X and Q and having 3 to 6 atoms. <5> The photosensitive resin composition according to any one of <2> to <4>, wherein the relationship between m and n in Formula A1 is m≦n. <6> The photosensitive resin composition according to any one of <1> to <5>, wherein the content of the compound that lowers the acidity upon heating is 0.01% by mass to 10.0% by mass in the photosensitive resin composition %the following. <7> The photosensitive resin composition according to any one of <1> to <6>, wherein the compound whose acidity decreases upon heating is a compound whose acidity decreases by heating at 400°C. <8> The photosensitive resin composition according to any one of <1> to <7>, wherein the pKa of the compound whose acidity decreases upon heating is -5.0 or more and 2.0 or less. <9> The photosensitive resin composition according to any one of <1> to <8>, wherein the pKa difference between before and after heating of the compound whose acidity decreases upon heating is 8.0 or more. <10> The photosensitive resin composition according to any one of <1> to <9>, wherein the compound whose acidity decreases upon heating is a compound whose acid group undergoes intramolecular dehydration condensation by heating. <11> The photosensitive resin composition according to any one of <1> to <10>, wherein the molecular weight of the compound that lowers the acidity upon heating is 80 or more and 1000 or less. <12> The photosensitive resin composition according to any one of <1> to <11>, further comprising a radical polymerization initiator and a radical polymerizable compound. <13> The photosensitive resin composition according to any one of <1> to <12>, wherein the polymer precursor includes a polyimide precursor. <14> The photosensitive resin composition as described in <13>, wherein the polyimide precursor has a structural unit represented by the following formula (1); [Chemical formula 1]

In formula (1), A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or 1-valent organic group. <15> The photosensitive resin composition according to <14>, wherein at least one of R ¹¹³ and R ¹¹⁴ in the formula (1) includes a radical polymerizable group. <16> The photosensitive resin composition as described in <14> or <15>, wherein R ¹¹⁵ in the formula (1) is a group containing an aromatic ring. <17> The photosensitive resin composition according to any one of <14> to <16>, wherein R ¹¹¹ in the above formula (1) is represented by -Ar ⁰ -L ⁰ -Ar ⁰ -; Ar ⁰ respectively Independently represents an aromatic group, L ⁰ represents a single bond, an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O ) ₂ -, -NHCO-, and a group selected from combinations of the above and the like. <18> The photosensitive resin composition according to any one of <14> to <17>, wherein R ¹¹¹ in the above formula (1) is represented by the following formula (51) or formula (61); 2]

In formula (51), R ⁵⁰ to R ⁵⁷ independently represent a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ represents a fluorine atom, methyl, fluoromethyl, difluoromethyl base or trifluoromethyl; [chemical formula 3]

In formula (61), R ⁵⁸ and R ⁵⁹ each independently represent a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group. <19> The photosensitive resin composition according to any one of <1> to <18>, which is used for image development using a developer containing 90% or more of an organic solvent. <20> The photosensitive resin composition as described in any one of <1>-<19> used for formation of the interlayer insulating film for rewiring layers. <21> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <20>. <22> The cured film according to <21>, wherein the film thickness is 1 to 30 μm. <23> A laminate having two or more layers of the cured film described in <21> or <22>. <24> A laminate having 3 to 7 layers of the cured film described in <21> or <22>. <25> The laminate according to <23> or <24>, which has a metal layer between the cured films. <26> A method for producing a cured film, including a film forming step of applying the photosensitive resin composition according to any one of <1> to <20> to a substrate to form a film. <27> The manufacturing method of the cured film as described in <26> which has the exposure process of exposing the said film, and the image development process of developing the said film. <28> The method for producing a cured film according to <27>, wherein the developer used for the image development contains 90% or more of an organic solvent. <29> The manufacturing method of the cured film any one of <26>-<28> which includes the process of heating the said film at 80-450 degreeC. <30> A method for producing a laminate comprising performing the method for producing a cured film according to any one of <26> to <29> a plurality of times. <31> A semiconductor device comprising the cured film described in <21> or <22> or the laminate described in any one of <23> to <25>. [Invention effect]

According to the present invention, it is possible to provide a photosensitive resin composition, a photosensitive resin, a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, and Semiconductor device.

Hereinafter, the contents of the present invention will be described. In addition, in this specification, "-" is used for the meaning of the range which uses the numerical value described before and after that as a lower limit and an upper limit.

The description of the constituent requirements in the present invention described below may be based on representative embodiments of the present invention, but the present invention is not limited to these embodiments. Regarding the notation of a group (atomic group) in this specification, the notation of substitution and non-substitution includes both those without a substituent and those with a substituent. For example, "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Unless otherwise specified, "exposure" in this specification includes not only exposure by light but also drawing by particle beams such as electron beams and ion beams. In addition, as the light used for exposure, active rays or radiation such as extreme ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, and electron beams represented by bright line spectra of mercury lamps and excimer lasers are generally mentioned. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid". Both or any of them, "(meth)acryl" means both or either of "acryl" and "methacryl". In this specification, the term "step" is not only an independent step, but also includes in this term as long as the expected action of the step can be achieved even when it cannot be clearly distinguished from other steps. In the present specification, the solid content refers to the mass percentage of components other than the solvent relative to the total mass of the composition. In addition, unless otherwise specified, the solid content concentration refers to the concentration at 25°C. In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as styrene-equivalent values based on gel permeation chromatography (GPC measurement). In this specification, for weight average molecular weight (Mw) and number average molecular weight (Mn), for example, HLC ^- 8220 (manufactured by TOSOH CORPORATION) can be used, and guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super ^HZ2000 (manufactured by TOSOH CORPORATION) were used to obtain them. Unless otherwise specified, the eluent was measured with THF (tetrahydrofuran). In addition, unless otherwise specified, detection was performed using a detector with a wavelength of 254 nm of UV rays (ultraviolet rays).

The photosensitive resin composition of the present invention (hereinafter, sometimes simply referred to as "the composition of the present invention" or "resin composition of the present invention") includes a polymer precursor and a compound that reduces acidity when heated (hereinafter, sometimes known as "acid vanishers"). Thereby, as described above, good storage stability can be realized while maintaining sufficient curability. Although the reason for obtaining such a special effect is not clear, it can be inferred as follows. That is, it is considered that the acid disappearing agent behaves as an acidic compound at room temperature, and may hinder the cyclization reaction of the polymer precursor. On the other hand, when the acid disappearing agent is heated to a predetermined temperature, a reaction occurs in the molecule, whereby the acid group disappears without hindering the ring closure reaction. Therefore, sufficient curability of the resin can be maintained without hindering cyclization during heat curing. By such a mechanism, it is presumed that good stability during storage can be achieved while sufficiently maintaining the curability during curing. Hereinafter, regarding the photosensitive resin composition of the present invention, preferred embodiments will be described centering on its component composition.

＜Polymer precursor＞ The photosensitive resin composition of the present invention comprises a polymer precursor selected from polyimide precursors and polybenzoxazole precursors. As a polymer precursor, a polyimide precursor is more preferable, and the polyimide precursor containing the structural unit represented by following formula (1) is still more preferable.

式（1）中，A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹¹ 表示2價有機基團，R¹¹⁵ 表示4價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團。<<Polyimide Precursor>> It is preferable that the polyimide precursor contains a structural unit represented by the following formula (1). By setting it as such a structure, the composition more excellent in film strength can be obtained. [chemical formula 4]

In formula (1), A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or 1-valent organic group.

A ¹ and A ² are each independently an oxygen atom or NH, preferably an oxygen atom.

<<<R ¹¹¹ >>> R ¹¹¹ represents a divalent organic group. Examples of divalent organic groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or combinations thereof, straight-chain aliphatic groups having 2 to 20 carbon atoms An aliphatic group, a branched aliphatic group with 3 to 20 carbons, a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons, or a combination of these groups are preferred. The number of aromatic groups of 6-20 is more preferable. R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. One kind of diamine may be used, or two or more kinds may be used. Specifically, the diamine contains a straight-chain aliphatic group with 2 to 20 carbons, a branched or cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons, or a combination thereof Groups are preferred, and diamines containing aromatic groups with 6 to 20 carbon atoms are more preferred. Examples of the aromatic group include the following aromatic groups.

[chemical formula 5]

In the formula, A is a single bond or selected from aliphatic hydrocarbon groups with 1 to 10 carbons that may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -S(=O) ₂ - , -NHCO- and the groups in the combination of these are preferred, single bond or selected from the group of alkylene with 1 to 3 carbons that may be substituted by fluorine atoms, -O-, -C(=O)-, The groups in -S- and -SO ₂ - are more preferably selected from the group including -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - and -C(CH ₃ ) The divalent group in the ₂ - group is further preferred.

Specific examples of diamines include those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminocyclohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclopentane Cyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane and isophorone diamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4 ,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4 ,4'-diaminodiphenylsulfide and 3,3-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide and 3,3'-diaminodiphenylsulfide, 4,4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2' -Dimethyl-4,4'-diaminobiphenyl (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)pyridine, bis(4-amino-3-hydroxyphenyl)pyridine, 4 ,4'-diamino-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]pyridine, bis[4 -(3-aminophenoxy)phenyl]pyridine, bis[4-(2-aminophenoxy)phenyl]pyridine, 1,4-bis(4-aminophenoxy)benzene, 9 ,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl anthracene, 1,3-bis(4-aminophenoxy) Benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diamino Diphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 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) terpene, 4,4'-dimethyl-3,3'-diaminodiphenylphenone, 3,3 ',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzoyloxy)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-diamino terpene, 2,5-bis Aminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluoro Toluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl) Decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 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-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl] Trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-tri Fluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylene, 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 , at least one diamine selected from 5',6,6'-hexafluorobenzidine and 4,4'-diaminoquaterphenyl.

Moreover, diamine (DA-1)-(DA-18) shown below is also preferable.

[chemical formula 6]

Moreover, the diamine which has at least 2 or more alkylene glycol units in a main chain can also be mentioned as a preferable example. It is preferable to combine diamine containing any one or both of two or more ethylene glycol chains and propylene glycol chains in one molecule, more preferably a diamine not containing an 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 (the above are product names, manufactured by HUNTSMAN), 1-(2-(2-(2-amino Propoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc. , but not limited to these. 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) structure of EDR-176.

[chemical formula 7]

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 -. Among them, Ar ⁰ are each independently an aromatic hydrocarbon group (preferably having 6-22 carbon atoms, more preferably having 6-18 carbon atoms, and particularly preferably having 6-10 carbon atoms), and preferably a phenylene group. L ⁰ represents a single bond, an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO- and groups selected from combinations thereof. The definition of the preferable range is the same as that of A above.

R⁵⁰ ～R⁵⁷ 分別獨立地為氫原子、氟原子或1價有機基團，R⁵⁰ ～R⁵⁷ 中的至少一個為氟原子、甲基、氟甲基、二氟甲基或三氟甲基。 作為R⁵⁰ ～R⁵⁷ 的1價有機基團時，可舉出碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式9]

R⁵⁸ 及R⁵⁹ 分別獨立地為氟原子、氟甲基、二氟甲基或三氟甲基。 作為賦予式（51）或（61）的結構之二胺化合物，可舉出二甲基-4,4’-二胺基聯苯、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。可以使用該等中的一種，亦可以組合使用兩種以上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, a divalent organic group represented by formula (61) is more preferable from the viewpoint of i-ray transmittance and availability. [chemical formula 8]

R ⁵⁰ to R ⁵⁷ are each 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, methyl, fluoromethyl, difluoromethyl or trifluoromethyl . As the monovalent organic group of R ⁵⁰ to R ⁵⁷ , unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), unsubstituted alkyl groups having 1 to 10 carbons (preferably carbon 1 to 6) fluorinated alkyl groups, etc. [chemical formula 9]

R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group. Examples of the diamine compound giving 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, 4,4'-diaminooctafluorobiphenyl, etc. One of these can be used, or two or more can be used in combination

R¹¹² 的定義與A相同，較佳範圍亦相同。<<<R ¹¹⁵ >>> R ¹¹⁵ in the formula (1) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group including an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. [chemical formula 10]

The definition of ^R112 is the same as that of A, and the preferred range is also the same.

R¹¹⁵ 表示4價有機基團。R¹¹⁵ 的定義與式（1）的R¹¹⁵ 相同。Specific examples of the tetravalent organic group represented by R ¹¹⁵ in the formula (1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. Tetracarboxylic dianhydride may be used only by 1 type, and may use 2 or more types. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7). [chemical formula 11]

R ¹¹⁵ represents a tetravalent organic group. The definition of R ¹¹⁵ is the same as that of R ¹¹⁵ in the formula (1).

Specific examples of tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3 ',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethylbenzene Ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3 ,3',4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic 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-naphthalene tetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3, 4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10 -Phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1, At least one of 2,3,4-benzenetetracarboxylic dianhydride and these alkyl derivatives having 1 to 6 carbons and alkoxy derivatives having 1 to 6 carbons.

Moreover, tetracarboxylic dianhydride (DAA-1) - (DAA-5) shown below can also be mentioned as a preferable example. [chemical formula 12]

<<< 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 preferable that at least one of R ¹¹³ and R ¹¹⁴ is a repeating unit containing a radical polymerizable group, and it is more preferable that both of them contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example includes a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth)acryl group, a group represented by the following formula (III), and the like.

[chemical formula 13]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, more preferably a methyl group. In formula (III), R ²⁰¹ represents an alkylene group with 2 to 12 carbons, -CH ₂ CH(OH)CH ₂ - or a (poly)oxyalkylene group with 4 to 30 carbons (as an alkylene group, carbon The number 1 to 12 is preferred, 1 to 6 is more preferred, and 1 to 3 is particularly preferred; the repeated number is 1 to 12 is preferred, 1 to 6 is more preferred, and 1 to 3 is especially preferred). In addition, (poly)oxyalkylene refers to oxyalkylene or polyoxyalkylene. Among preferred ^R201 examples, ethylidene, propylidene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, Hexamethylene, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, ethylidene, propylidene, trimethylene, -CH ₂ CH(OH)CH ₂ - are better. Especially preferably, R ²⁰⁰ is a methyl group, and R ²⁰¹ is an ethylenyl group.

As a preferred embodiment of the polyimide precursor in the present invention, as the monovalent organic group of R ¹¹³ or R ¹¹⁴ , there are 1, 2 or 3 acid groups, preferably 1 acid group. Aliphatic, aromatic and aralkyl groups. Specifically, an aromatic group having 6 to 20 carbon atoms having an acid group, and an aralkyl group having 7 to 25 carbon atoms having an acid group are mentioned. More specifically, there may be mentioned a phenyl group having an acidic group and a benzyl group having an acidic group. An acid group is more preferably a hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ is preferably 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 an aqueous developer, R ¹¹³ or R ¹¹⁴ is more preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, and 4-hydroxybenzyl.

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and an alkyl group substituted with an aromatic group is more preferable. The carbon number of the alkyl group is preferably 1 to 30 (3 or more when cyclic). The alkyl group may be any of linear, branched and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, Alkyl, octadecyl, isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, camphenyl, camphenyl (camphenyl), decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, camphenyl Diacyl, dicyclohexyl and pinenyl. Among them, cyclohexyl group is most preferable from the viewpoint of balance and high sensitivity. Also, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable. Examples of the aromatic group include substituted or unsubstituted benzene rings, naphthalene rings, pentadene rings, indene rings, azulene rings, heptadene rings, indenene rings, perylene rings, condensed pentaphenyl rings, acenaphthene rings, etc. Alkene ring, phenanthrene ring, anthracene ring, condensed tetraphenyl ring, fenene ring, three phenylene ring, oxene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring , Pyridine ring, pyrimidine ring, dat ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinol ring, quinoline ring, phthalein ring, naphthalene ring Pyridine ring, quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthracene ring, thianthrene ring, chromene ring, mouth mountain mouth star ring, phenanthrene ring ring, brown thiol 𠯤 ring or brown 𠯤 ring. The benzene ring is the best. (Hereafter, the aromatic group is referred to as Aro)

Moreover, it is also preferable that a polyimide precursor has a fluorine atom in a structural unit. The content of fluorine atoms in the polyimide precursor is preferably at least 10% by mass, and more preferably at most 20% by mass. The upper limit is not particularly limited, but is actually 50% by mass or less.

Also, for the purpose of improving the adhesiveness with the substrate, an aliphatic group having a siloxane structure may be copolymerized with a structural unit represented by formula (1). Specifically, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are mentioned as a diamine component.

A¹¹ 及A¹² 表示氧原子或NH，R¹¹¹ 及R¹¹² 分別獨立地表示2價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團，R¹¹³ 及R¹¹⁴ 中的至少一者為包含自由基聚合性基團之基團，自由基聚合性基團為較佳。The structural unit represented by formula (1) is preferably a structural unit represented by formula (1-A). [chemical formula 14]

A ¹¹ and A ¹² represent an oxygen atom or NH, R ¹¹¹ and R ¹¹² independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or a monovalent organic group, R ¹¹³ and R ¹¹⁴ At least one of them is a group containing a radical polymerizable group, preferably a radical polymerizable group.

The definitions of A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are independently the same as those of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1), and the preferred ranges are also the same. The definition of R ¹¹² is the same as that of R ¹¹² in formula (5), and the preferred range is also the same.

In the polyimide precursor, the structural unit represented by the formula (1) may be one kind, or two or more kinds. Moreover, structural isomers of the structural unit represented by formula (1) may be contained. In addition, the polyimide precursor may contain other types of repeating structural units in addition to the structural units of the above-mentioned formula (1).

As an embodiment of the polyimide precursor in the present invention, 50 mol% or more of the total constituent units, further 70 mol% or more, especially 90 mol% or more are represented by the formula (1). The polyimide precursor of the constituent unit. The upper limit is actually 100 mol% or less.

The weight average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 10,000 to 50,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 800-250,000, More preferably, it is 2,000-50,000, More preferably, it is 4,000-25,000. The molecular weight dispersion (Mw/Mn) of the polyimide precursor is preferably 1.5-3.5, and 2-3 is still more preferable.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. It is preferably obtained after halogenating dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent, and then reacting it with diamine. In the method for producing a polyimide precursor, it is preferable to use an organic solvent for the reaction. The organic solvent may be one kind, or two or more kinds. As an organic solvent, it can be set suitably according to a raw material, Pyridine, diglyme (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone can be illustrated.

When producing the polyimide precursor, it is preferable to include the step of precipitating solid. Specifically, the polyimide precursor in the reaction liquid is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, whereby solid precipitation can be performed.

R¹²¹ 表示2價有機基團，R¹²² 表示4價有機基團，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價有機基團。<<Polybenzoxazole precursor>> It is preferable that the polybenzoxazole precursor contains a structural unit represented by the following formula (2). [chemical formula 15]

R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

R ¹²¹ represents a divalent organic group. The divalent organic groups include aliphatic groups (preferably 1-24 carbons, more preferably 1-12, particularly preferably 1-6) and aromatic groups (preferably 6-22 carbons, 6 -14 is more preferred, 6-12 is particularly preferred) at least one group is preferred. Examples of the aromatic group constituting R ¹²¹ include R ¹¹¹ in the above formula (1). As the aforementioned aliphatic group, a straight-chain aliphatic group is preferred. R ¹²¹ is preferably derived from 4,4'-oxodibenzoyl chloride. In formula (2), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, the definition is the same as that of R ¹¹⁵ in the above formula (1), and the preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group, and their definitions are the same as those of R ¹¹³ and R ¹¹⁴ in the above formula (1), and their 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 repeating structural units. It is preferable that the precursor contains a diamine residue represented by the following formula (SL) as another type of repeating structural unit from the viewpoint of suppressing the occurrence of warpage of the cured film accompanying ring closure.

式（SL）中，Z具有a結構和b結構，R^1s 為氫原子或碳數1～10的烴基（較佳為碳數1～6，更佳為碳數1～3），R^2s 為碳數1～10的烴基（較佳為碳數1～6，更佳為碳數1～3），R^3s 、R^4s 、R^5s 、R^6s 中的至少一個為芳香族基（較佳為碳數6～22，更佳為碳數6～18，特佳為碳數6～10），剩餘部分為氫原子或碳數1～30（較佳為碳數1～18，更佳為碳數1～12，特佳為碳數1～6）的有機基團，且可以分別相同亦可以不同。a結構及b結構的聚合可以為嵌段聚合或隨機聚合。Z部分中，較佳為a結構為5～95莫耳%，b結構為95～5莫耳%，a+b為100莫耳%。[chemical formula 16]

In formula (SL), Z has structure a and structure b, R ^1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbons (preferably 1 to 6 carbons, more preferably 1 to 3 carbons), and R ^2s is A hydrocarbon group with 1 to 10 carbons (preferably 1 to 6 carbons, more preferably 1 to 3 carbons), at least one of R ^3s , R ^4s , R ^5s and R ^6s is an aromatic group (preferably carbon number 6-22, more preferably carbon number 6-18, particularly preferably carbon number 6-10), the remainder is hydrogen atoms or carbon number 1-30 (preferably carbon number 1-18, more preferably carbon number 1 to 12, particularly preferably an organic group with carbon number 1 to 6), and may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. In the Z fraction, preferably, the a structure is 5-95 mol%, the b structure is 95-5 mol%, and a+b is 100 mol%.

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the structure b are phenyl groups. Moreover, the molecular weight of the structure represented by formula (SL) is preferably 400-4,000, more preferably 500-3,000. The molecular weight can be determined by the commonly used gel permeation chromatography. By setting the molecular weight to the above range, it is possible to reduce the modulus of elasticity after dehydration and ring closure of the polybenzoxazole precursor, suppress warpage, and improve solubility.

When the precursor contains a diamine residue represented by the formula (SL) as another type of repeating structural unit, it also contains tetracarboxylic Acid residues are preferred as repeating structural units. Examples of such tetracarboxylic acid residues include the example of R ¹¹⁵ in formula (1).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 10,000 to 50,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 800-250,000, More preferably, it is 2,000-50,000, More preferably, it is 4,000-25,000. The molecular weight dispersion (Mw/Mn) of the polybenzoxazole precursor is preferably 1.5-3.5, more preferably 2-3.

The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably at least 20% by mass, more preferably at least 30% by mass, and still more preferably at least 40% by mass, based on the total solid content of the composition. It is more preferably 50 mass % or more, 60 mass % or more is still more preferable, and 70 mass % or more is still more preferable. In addition, the content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and still more preferably 98% by mass or less with respect to the total solid content of the composition. Preferably, 95% by mass or less is more preferred, and 95% by mass or less is still more preferred. The photosensitive resin composition of the present invention may contain only one kind of polymer precursor, or may contain two or more kinds. When two or more types are contained, it is preferable that the total amount is within the above-mentioned range.

＜Compounds that decrease acidity when heated (acid disappearing agent)＞ The acid disappearing agent is a compound whose acidity decreases when heated at 400°C is preferred, 300°C is further preferred, 250°C is further preferred, 200°C is further preferred, 180°C is further preferred, 150°C is still more preferred °C is especially further preferred. The lower limit is not particularly limited, but is actually 80°C. The above heating time is, for example, 1 hour. In addition, heating is carried out under a nitrogen atmosphere, and the pressure at this time is preferably 1 atmosphere. In addition, it is preferable that the acidity of the acid disappearing agent used in the present invention is lowered at the temperature in the heating step described later. In addition, the purpose of the acid disappearing agent used in the present invention is to exclude compounds whose acidity does not decrease as long as the temperature is higher than the heat resistance temperature of the cured film. In this specification, the case where acidity falls is measured and defined as follows. Specific compounds were heated at 1 atmosphere under nitrogen for 1 hour. Dissolve in a solvent containing water to make a 0.1mol/L aqueous solution. By measuring pH with a pH meter, it is possible to confirm the decrease in acidity.

Before heating (for example, heating at 200° C.) of the acid disappearing agent, the pKa of the compound is preferably not less than -10, more preferably not less than -5, and still more preferably not less than -3. As an upper limit, for example, 5.0 or less is preferable, 2.5 or less is more preferable, and 1.8 or less is still more preferable. It is preferable from the point which suppresses the hydrolysis reaction of a polymer precursor by making pKa more than the said lower limit. It is preferable from the viewpoint of inhibiting the cyclization reaction of a polymer precursor by setting it as below the said upper limit. The pKa described in the present specification means that the equilibrium constant Ka is represented by a negative common logarithm pKa in consideration of the dissociation reaction of releasing hydrogen ions from oxygen. The lower the pKa, the stronger the acid. Unless otherwise stated, pKa is set to the calculated value based on ACD/ChemSketch. Alternatively, the values described in "Chemical Handbook, Basic Edition, Revised 5th Edition" edited by the Chemical Society of Japan can be referred to. The increase in pKa by heating (ΔpKa) (difference in pKa before and after heating) is preferably 2.0 or more, more preferably 5.0 or more, and still more preferably 8.0 or more.

The molecular weight of the acid disappearing agent is preferably 2000 or less, more preferably 1000 or less, and more preferably 500 or less. The lower limit is not particularly limited, but is actually 80 or more.

The acid disappearing agent is preferably a compound represented by any one of formulas A1 to A3, more preferably a compound represented by formula A1 or formula A2, and even more preferably a compound represented by formula A1.

(X) _m -L ^A -(Y) _n ････Formula A1 In the formula, X represents -COOH, -SO ₃ H or -PO ₃ H ₂ , L ^A represents the m+n valent linking group, Y represents- OH, -COOH, or -NH( ^RN ). R ^N is a hydrogen atom or an organic group, m represents an integer of 1-4, and n represents an integer of 1-4. The organic group of ^RN is alkyl (preferably 1-12 carbons, more preferably 1-6, further preferably 1-3), aryl (preferably 6-22 carbons, 6-18 more preferably, 6-10 is further preferred) or aralkyl (carbon number 7-23 is preferred, 7-19 is more preferred, 7-11 is further preferred) is preferred, hydrogen atom or alkyl More preferably, a hydrogen atom or a methyl group is further preferred, and a hydrogen atom is further preferred. The organic group of ^RN may have a substituent T described later. When there are plural organic groups in R ^N , they may be bonded to each other or via a linker L defined below to form a ring. As the formed ring, alicyclic ring, cycloalkyl ring or cycloalkenyl ring or linking group Lh with heteroatoms interposed therein (preferably 1 to 12, more preferably 1 to 6, 1 ~ 3 rings are more preferable) rings are even better. The carbon number of the alicyclic ring is preferably 3-22, more preferably 3-12, and still more preferably 3-8. Alicyclic rings can be formed as polycyclic rings or spiro rings. Hereinafter, the ring that can be formed is referred to as ring K in this specification. Still, in the present invention, it is preferable that the organic group of R ^N has no substituent T.

L ^A represents an m+n-valent linking group selected from the group consisting of -CO-, -O-, -NH-, aliphatic linking group, aryl linking group, and combinations thereof, preferably. The aliphatic linking group is related to the alkane linking group (preferably 1-12 carbons, more preferably 1-6, further preferably 1-3), olefin linking group (preferably 2-12 carbons, 2-6 6 is more preferred, 2 to 3 are further preferred), aryl linking group (6 to 22 carbons is preferred, 6 to 18 is more preferred, 6 to 10 is further preferred) or a combination thereof The linker is preferred. Here, the alkane linking group refers to a linking group composed of alkane (saturated hydrocarbon). When the alkane linking group is a divalent linking group, it becomes an alkylene group. The same applies to olefinic linking groups, aryl linking groups, and the like. In L ^A , linking group Lh having the following heteroatoms may be contained within the scope of exerting the effect of the present invention, and the number of contained heteroatoms is preferably 0 to 3, 0 or 1 is more preferable, and 0 is further better. Also, L ^A is preferably a linking group with 3 or more atoms connecting X and Q. The upper limit of the number of atoms connecting X and Q is not particularly limited, but is actually 6 or less. The above-mentioned number of atoms in the connection refers to the minimum number of atoms in the path between the structural parts specified in the connection (for example, X and Q) and related to the connection. For example, in the case of -CH ₂ -C(=O)-O-, the number of atoms connected becomes three.

R ^N may form a ring by bonding with LA via linker ^L or not via a linker L within the range of exerting the effect of the present invention. The ring K to be formed includes the aforementioned ring K. However, it is more preferable that R ^N forms ^a ring without being bonded to LA.

m is preferably 1 or 2, and 1 is more preferred. The n is 1 or 2 is preferable, and 1 is more preferable. The m+n system is preferably 2 to 4, and 2 is still more preferable. In addition, in formula A1, m≤n is preferable, and m<n may also be satisfied. n-m is more preferably 0 or 1. When m is 2 or more, a plurality of Xs may be the same or different. When n is 2 or more, a plurality of Ys may be the same or different.

In Formula A1, X is -SO ₃ H is preferred. Also, -NH(R ^N ) is preferable, and -NH ₂ is more preferable. Also, in the present invention, in formula A1, L ^A is preferably a linking group having 3 or more atoms connected thereto. The upper limit of the number of linked atoms is not particularly limited, but is actually 6 or less. By setting these ranges, the group represented by Y and the acid represented by X easily react on an intramolecular basis.

Regarding the compound represented by formula A1, in its preferred form, it is explained that the group represented by Y reacts with the acid represented by X based on the intramolecular reaction, and the acidity decreases due to the change of X.

[化學式18]

Hereinafter, the compound represented by Formula A1 is illustrated. It goes without saying that the compound represented by formula A1 is not limited to these. [chemical formula 17]

[chemical formula 18]

(X) _m -L ^A -(Q) _n ････Formula A2 In the formula, X represents -COOH, -SO ₃ H or -PO ₃ H ₂ , L ^A represents m+n valent linking group, Q represents borrow A group that releases the base component by heating. The heating temperature is the same as the above-mentioned temperature for reducing the acidity. Q represents -CONH(R ^N ), -OCONH(R ^N ), -N(R ^N )CONH(R ^N ) or -N(R ^N ) ₃ ⁺ A ^- . A ^- is an atom or group of atoms forming a counter ion, such as a halogen atom. The definitions of X, LA, m, n, and R ^N are the same as those of ^X , LA, m, n, and R ^N in Formula ^A1 , respectively, and the preferred ranges are also the same. In the compound represented by formula A2, in its preferred form, it is explained that the group represented by Q decomposes by heat and releases the amine component, and by neutralizing the acid group represented by X Reducers of acidity.

Hereinafter, the compound represented by Formula A2 is illustrated. It goes without saying that the compound represented by formula A2 is not limited thereto. [chemical formula 19]

Z-(LC -COOH) _nz ････Formula A3 In the formula, Z represents an nz-valent organic group, and L ^C represents * ¹ -( ^C =O)C(R ^a ) ₂ -* ² , -CH( R ^b )- or -C(R ^b ) ₂ -, R ^a represents hydrogen atom, alkyl, alkenyl, aryl or aralkyl, R ^b represents alkyl, alkenyl, aryl or aralkyl, * ¹ represents the bonding position on the Z side, * ² represents the bonding position on the COOH side, and nz is an integer of 1-4. Z and R ^a or R ^b may be bonded to form a ring.

R ^a represents a hydrogen atom, an alkyl group (preferably 1-12 carbons, more preferably 1-6, further preferably 1-3), alkenyl (preferably 2-12 carbons, 2-6 More preferably, 2-3 is further preferred), aryl group (6-22 carbon number is preferred, 6-18 is more preferred, 6-10 is further preferred) or aralkyl group (carbon number 7-23 is Preferably, 7 to 19 are more preferred, and 7 to 11 are further preferred), hydrogen atoms, alkyl groups, and aryl groups are more preferred, hydrogen atoms or alkyl groups are further preferred, and hydrogen atoms are further preferred. R ^b represents alkyl (preferably 1-12 carbons, more preferably 1-6, further preferably 1-3), alkenyl (preferably 2-12 carbons, more preferably 2-6, 2-3 is more preferred), aryl group (6-22 carbon number is preferred, 6-18 is more preferred, 6-10 is further preferred) or aralkyl group (7-23 carbon number is preferred, 7-19 are more preferable, 7-11 are still more preferable), alkyl and aryl are more preferable, and alkyl is still more preferable. When R ^a and R ^b are plural, they may be the same as or different from each other. Z, R ^a , and R ^b may be bonded to each other (when there are plural R ^a and R ^b , substituents of the same type may be bonded) or bonded via a linking group L to form a ring. Preferred rings include The aforementioned ring K.

Z-series alkane linking group (preferably 1-12 carbons, more preferably 1-6, further preferably 1-3), olefin linking group (preferably 2-12 carbons, more preferably 2-6 , 2 to 3 are further preferred), aryl linking group (6 to 22 carbons is preferred, 6 to 18 is more preferred, 6 to 10 is further preferred), carboxyl, carbonyl and oxygen atoms or include these A combined linking group is preferred, an alkane linking group, an aryl linking group, a carbonyl group or a linking group comprising these combinations is more preferred. nz is 1 to 4, preferably 1 or 2, more preferably 1. Among the compounds represented by the formula A3, in its preferred form, it is explained that the COOH group causes a decarboxylation reaction by heating, and the acidity decreases.

Formula A3 is preferably any one of the following formulas A3-1 to A3-3. Z ¹ -(CHR ^b -COOH) _nz ････Formula A3-1 Z ¹ -(CR ^b ₂ -COOH) _nz ････Formula A3-2 Z ² -(CO-CR ^a ₂ -COOH) _nz ････Formula A3-3 In the formula, the definitions of R ^a , R ^b , and nz are the same as those of R ^a , R ^b , and nz in Formula A3, respectively, and the preferred ranges are also the same. When there are a plurality of R ^a and R ^b , they may be bonded to each other to form a ring, and the ring K mentioned above is mentioned as a preferable ring. R ^a and R ^b may be bonded to Z ¹ or Z ² to form a ring, and ring K is a preferred ring. When R ^a and R ^b are plural, they may be the same as or different from each other. Z ¹ is an alkane linker, an alkene linker, an aryl linker, or an aralkyl group. Among them, the aryl linking group is preferable, and if represented by a ring structure, examples of the above-mentioned aromatic Aro can be mentioned, and a naphthalene ring or a benzene ring is particularly preferable. The definition of the preferable range of the alkane linking group etc. is the same as the preferable range of the alkane linker etc. in Z mentioned above. Z is more ^preferably an alkane linking group, an aryl linking group, a carbonyl group or a linking group comprising a combination thereof. The definition of the preferable range of the alkane linking group etc. is the same as the preferable range of the alkane linker etc. in Z mentioned above. R ^a , R ^b , Z ¹ , and Z ² may further have a substituent T. When there are plural substituents T, they may be bonded to each other or bonded to R ^a , R ^b , Z ¹ , and Z ² in the formula via or not via a linker L to form a ring. ^The alkyl chains and alkenyl chains ^of Z1 and Z2 may contain linking groups Lh with heteroatoms, the number of which is 1-12 is preferred, 1-6 is more preferred, and 1-3 is further preferred. good. Of course, R ^a , R ^b , Z ¹ , and Z ² may not have a substituent.

Hereinafter, the compound represented by Formula A3 is illustrated. It goes without saying that the compound represented by formula A3 is not limited to these. [chemical formula 20]

Examples of the substituent T include alkyl (preferably 1 to 24 carbons, more preferably 1 to 12, particularly preferably 1 to 6), alkenyl (preferably 2 to 24 carbons, 2 to 12 is more preferred, 2-6 is particularly preferred), alkoxy group (1-12 carbon number is preferred, 1-6 is more preferred, 1-3 is further preferred), aralkyl group (carbon number 7-23 is more preferred, 7-19 is more preferred, 7-11 is further preferred), hydroxyl group, amino group (preferably carbon number 0-24, 0-12 is more preferred, 0-6 is particularly preferred), sulfur Alcohol group, carboxyl group, acyl group (preferably 2-12 carbons, more preferably 2-6, particularly preferably 2-3), acyloxy groups (preferably 2-12 carbons, more preferably 2-6 preferably, 2-3 is particularly preferred), aryl group (7-23 carbon number is better, 7-19 is more preferred, 7-11 is particularly preferred), aryloxy group (7-23 carbon number is more preferred) best, 7-19 is more preferable, 7-11 is especially preferable), (meth)acryl group, (meth)acryloxy group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom ), oxo group (=O), imino group (=NR), alkylene group (=C(R) ₂ ), etc. The alkylene chain of the substituent T may contain heteroatoms. The alkyl group, alkenyl group, aryl group, and aralkyl group contained in the substituent T may be substituted with other substituents. The definition of R is the same as that of ^RN above.

The linking group L is alkylene (preferably 1-12 carbons, more preferably 1-6, further preferably 1-3), alkenylene (preferably 2-12 carbons, 2-6 more preferably), arylylene (preferably 6-22 carbons, more preferably 6-18, further preferably 6-10), heteroarylylene (preferably 1-12 carbons, 1-6 More preferably, 1 to 4 are still more preferable; Examples of heteroatoms include a nitrogen atom, an oxygen atom, a sulfur atom), an oxygen atom, a sulfur atom, a carbonyl group, -NR-, or a group including a combination thereof. In addition to hydrogen atoms, the number of atoms constituting the linking group L is preferably 1-24, more preferably 1-12, and particularly preferably 1-6. The number of atoms connected by the linking group is preferably 10 or less, more preferably 8 or less. The lower limit is 1 or more. The definition of R is the same as that of ^RN above.

Examples of the linking group Lh containing a heteroatom include an oxygen atom, a sulfur atom, a carbonyl group, a thiocarbonyl group, a sulfonyl group, -NR-, or a linking group containing a combination thereof. The number of atoms constituting the heteroatom-containing linking group Lh is preferably 1-12, more preferably 1-6, and particularly preferably 1-3. The number of atoms interposed in the specific group of the linking group Lh containing a heteroatom is preferably 1-12, more preferably 1-6, and particularly preferably 1-3. The definition of R is the same as that of ^RN above.

The acid disappearing agent used in the present invention may be two or more compounds corresponding to formulas A1 to A3. For example, the structure represented by (X) ₂ -linking group-(Y)(Q) exemplifies compounds corresponding to both formula A1 and formula A2, and the like.

As an example of the embodiment of the present invention, it is also possible to blend two or more types of acid disappearing agents at which the temperature at which the acidity decreases is different. With these configurations, the acidity decreases stepwise, and the cyclization reaction of the polymer precursor during heating can be more efficiently progressed. In the embodiment, it is preferable to blend two or more types of acid disappearing agents having a difference of 20 to 200° C. in the temperature at which the acidity decreases.

The amount of the acid disappearing agent in the photosensitive resin composition is preferably at least 0.0025% by mass, more preferably at least 0.01% by mass, and still more preferably at least 0.02% by mass. As an upper limit, for example, 2.5 mass % or less is preferable, 1.5 mass % or less is more preferable, 0.25 mass % or less is still more preferable. In the photosensitive resin composition, the ratio of the acid disappearing agent in the solid content is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, and still more preferably at least 0.1% by mass. As an upper limit, for example, 10.0 mass % or less is preferable, 5.0 mass % or less is more preferable, and 1.0 mass % or less is further more preferable. The blending ratio of the acid disappearing agent to 100 parts by mass of the polymer precursor is preferably at least 0.015 parts by mass, more preferably at least 0.075 parts by mass, and still more preferably at least 0.15 parts by mass. As an upper limit, for example, it is preferable that it is 15.0 mass parts or less, it is more preferable that it is 7.5 mass parts or less, and it is still more preferable that it is 1.5 mass parts or less. Favorable storage stability can be ensured by making content of an acid disappearing agent more than the said lower limit, and it is preferable from this point. By setting it as below the said upper limit, it is preferable from this point that the corrosion resistance of metal can be ensured. One type of acid disappearing agent may be used, and plural types may be used. When using plural types, the total amount is within the range prescribed above.

<Solvent> It is preferable that the photosensitive resin composition of this invention contains a solvent. As the solvent, known solvents can be used arbitrarily. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, phenylenes, and amides. As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, etc. Esters, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g. methyl alkoxyacetate, Ethyl alkoxyacetate, butyl alkoxyacetate (e.g. 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, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionates (for example, 2- Methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2- Ethyl alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate Esters, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve. 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 monopropylene ether acetate etc. As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are mentioned as preferable ones. Examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene, and the like as preferred ones. As the thionines, for example, dimethyl thionine is preferable. As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Dimethylformamide, etc.

Regarding the solvent, it is also preferable to mix two or more forms from the viewpoint of improving the coating surface shape and the like. In the present invention, selected from methyl 3-ethoxy propionate, ethyl 3-ethoxy propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate , Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfide, ethyl carbitol acetate, butyl carbitol One solvent among acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or a mixed solvent consisting of two or more of them is preferred. It is particularly preferable to use dimethylsulfoxide and γ-butyrolactone at the same time.

The content of the solvent is preferably in an amount of 5 to 80% by mass, and preferably in an amount of 5 to 75% by mass, of the total solid content concentration of the photosensitive resin composition of the present invention from the viewpoint of coatability. More preferably, it is still more preferable to set it as the quantity of 10-70 mass %, and it is still more preferable to set it as 40-70 mass %. The content of the solvent may be adjusted according to the desired thickness and coating method. A solvent may contain only 1 type, and may contain 2 or more types. When two or more solvents are contained, their total is preferably within the above range.

＜Photoactive compounds＞ In the present invention, the photosensitive resin composition contains a photoactive compound. As an example of a photoactive compound, a photoinitiator, a photoacid generator, and a photohardening accelerator are mentioned.

＜＜Photopolymerization Initiator＞＞ The photosensitive resin composition of this invention may contain a photoinitiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The radical photopolymerization initiator that can be used in the present invention is not particularly limited, and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to rays from an ultraviolet region to a visible region is preferable. Also, it can be an active agent that interacts with a photoexcited sensitizer to generate active free radicals. It is preferable that the photoradical polymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300-800 nm (preferably 330-500 nm). The molar absorptivity of a compound can be measured by a known method. For example, it is preferable to perform measurement at a concentration of 0.01 g/L with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co., Ltd.) using ethyl acetate solvent.

Since the photosensitive resin composition of the present invention contains a photoradical polymerization initiator, after the photosensitive resin composition of the present invention is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, by irradiating light, a Hardening due to the generated free radicals can reduce the solubility in the light-irradiated part. Therefore, for example, there is an advantage that, by exposing the photosensitive resin composition layer through a photomask having a pattern that shields only the electrode portion, regions having different solubility can be easily produced depending on the electrode pattern.

As the photoradical polymerization initiator, known compounds can be used arbitrarily, for example, halogenated hydrocarbon derivatives (such as compounds having a triazole skeleton, compounds having a oxadiazole skeleton, compounds having a trihalomethyl group, etc. ), acyl phosphine compounds such as acyl phosphine oxide, hexaarylbiimidazole, oxime derivatives and other oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone Compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc. For such details, the description in paragraphs 0165 to 0182 of JP-A-2016-027357 can be referred to, and the content is incorporated into this specification.

As the ketone compound, for example, compounds described in paragraph 0087 of JP-A-2015-087611 can be exemplified, and the content thereof is incorporated in the present specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in JP-A-4225898 can also be used. As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCURE 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: all are manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, commercially available IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all are manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, compounds described in Japanese Patent Application Laid-Open No. 2009-191179 whose maximum absorption wavelength matches a light source with a wavelength of 365 nm or 405 nm can also be used. Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. Moreover, commercially available IRGACURE-819 or IRGACURE-TPO (trade name: both are made by BASF Corporation) can be used. As a metallocene compound, IRGACURE-784 (manufactured by BASF Corporation) etc. are illustrated.

市售品中，還可較佳地使用IRGACURE OXE 01、IRGACURE OXE 02、IRGACURE OXE 03、IRGACURE OXE 04（以上為BASF公司製）、ADEKA OPTOMER N-1919（ADEKA CORPORATION製、日本特開2012-14052號公報中所記載之光自由基聚合起始劑2）。又，能夠使用TR-PBG-304（常州強力電子新材料有限公司製）、ADEKAARKLS NCI-831及ADEKAARKLS NCI-930（ADEKA CORPORATION製）。又，能夠使用DFI-091（DAITO CHEMIX Co.,Ltd.製）。 進而，還能夠使用具有氟原子之肟化合物。作為該等肟化合物的具體例，可舉出日本特開2010-262028號公報中所記載之化合物、日本特表2014-500852號公報的0345段中所記載之化合物24、36～40、日本特開2013-164471號公報的0101段中所記載之化合物（C-3）等。 作為最佳之肟化合物，可舉出日本特開2007-269779號公報中所示出之具有特定取代基之肟化合物或日本特開2009-191061號公報中所示出之具有硫芳基之肟化合物等。More preferably, an oxime compound is mentioned as a photoradical polymerization initiator. By using an oxime compound, exposure latitude can be improved more effectively. Among the oxime compounds, since the exposure latitude (exposure margin) is wide and also functions as a photocuring accelerator, it is particularly preferable. As specific examples of oxime compounds, compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, and compounds described in JP-A-2006-342166 can be used. . As preferred oxime compounds, for example, compounds of the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetyloxyiminobutan-2-one, 3-Propionyloxyiminobutan-2-one, 2-Acetyloxyiminopentan-3-one, 2-Acetyloxyimino-1-phenylpropane-1- Ketones, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-tosyloxy)iminobutan-2-one, and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. In the photosensitive resin composition of the present invention, it is preferable to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime-based photopolymerization initiator has a >C=NOC(=O)- linking group in the molecule. [chemical formula 21]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, JP 2012-14052 Photoradical polymerization initiator 2) described in the No. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), ADEKAARKLS NCI-831, and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. Moreover, DFI-091 (made by DAITO CHEMIX Co., Ltd.) can be used. Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, JP-A-2014-500852, Compound (C-3) and the like described in Paragraph 0101 of Publication No. 2013-164471. The most preferable oxime compounds include oxime compounds having specific substituents shown in JP-A-2007-269779 or oximes having a thioaryl group shown in JP-A-2009-191061 compound etc.

式（I）中，R^I00 係碳數1～20的烷基、藉由1個以上的氧原子而中斷之碳數2～20的烷基、碳數1～12的烷氧基、苯基、由碳數1～20的烷基、碳數1～12的烷氧基、鹵素原子、環戊基、環己基、碳數2～12的烯基藉由因1個以上的氧原子而中斷之碳數2～18的烷基及碳數1～4的烷基中的至少一個取代之苯基或聯苯基，R^I01 係由式（II）表示之基團，或者係與R^I00 相同的基團，R^I02 ～R^I04 各自獨立地係碳數1～12的烷基、碳數1～12的烷氧基或鹵素。 [化學式23]

式中，R^I05 ～R^I07 與上述式（I）的R^I02 ～R^I04 相同。From the viewpoint of exposure sensitivity, photoradical polymerization initiators are selected from the group consisting of trihalomethyl tristannium 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 - Compounds in the group of benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds. More preferable photoradical polymerization initiators are trihalomethyl trisalpine 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 selected from the group consisting of trihalomethyl tristannium compounds, α-aminoketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds It is further preferred to use at least one compound among them, it is further preferred to use a metallocene compound or an oxime compound, and it is further preferred to use an oxime compound. In addition, as the photoradical polymerization initiator, N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-perolylphenyl)-butanone-1 ,2-methyl-1-[4-(methylthio)phenyl]-2-pornolinyl-acetone-1 and other aromatic ketones, alkylanthraquinones and other quinones formed by condensation with aromatic rings Benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. Moreover, the compound represented by following formula (I) can also be used. [chemical formula 22]

In formula (I), R ^I00 is an alkyl group with 1 to 20 carbon atoms, an alkyl group with 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group with 1 to 12 carbon atoms, and a phenyl group , by alkyl with 1 to 20 carbons, alkoxy with 1 to 12 carbons, halogen atom, cyclopentyl, cyclohexyl, alkenyl with 2 to 12 carbons interrupted by one or more oxygen atoms A phenyl or biphenyl group substituted by at least one of an alkyl group with 2 to 18 carbons and an alkyl group with 1 to 4 carbons, R ^I01 is a group represented by formula (II), or is the same as R ^I00 R ^I02 to R ^I04 are each independently an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, or a halogen. [chemical formula 23]

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 in the above formula (I).

In addition, as the photoradical polymerization initiator, compounds described in paragraphs 0048 to 0055 of International Publication WO2015/125469 can also be used.

When a photopolymerization initiator is included, its content is preferably 0.1-30% by mass relative to the total solid content of the photosensitive resin composition of the present invention, more preferably 0.1-20% by mass, and even more preferably 0.5-20% by mass. 15% by mass, more preferably 1.0 to 10% by mass. A photoinitiator may contain only 1 type, and may contain 2 or more types. When two or more types of photopolymerization initiators are contained, it is preferable that the total is within the above-mentioned range.

＜＜Photoacid generator＞＞ The composition of the present invention may contain a photoacid generator. Since a photoacid generator is contained, an acid is generated in an exposed part, and the solubility with respect to the alkali aqueous solution of an exposed part increases, Therefore It can be used as a positive photosensitive resin composition. Examples of the photoacid generator include quinonediazide compounds, percite salts, phosphonium salts, diazonium salts, and iodonium salts. Among them, roll diazide compounds are preferably used from the viewpoint that a positive-type composition exhibiting an excellent dissolution inhibiting effect, high sensitivity, and low film reduction can be obtained. Moreover, you may contain 2 or more types of photoacid generators. Thereby, the ratio of the dissolution rate of an exposed part and an unexposed part can be made large, and the highly sensitive positive photosensitive resin composition can be obtained. Specifically, descriptions in paragraphs 0209 to 0215 of WO2017/110982 can be referred to, and these contents are incorporated into the present specification.

The content of the photoacid generator is preferably 3 to 40 parts by mass relative to 100 parts by mass of the polymer precursor. Higher sensitivity can be realized by making content of a photoacid generator into this range. Furthermore, a sensitizer may be contained as needed. A photoacid generator may use only 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.

＜＜Photohardening Accelerator＞＞ The photosensitive resin composition used in the present invention may contain a photohardening accelerator. The photohardening accelerator in the present invention is one that generates a base by exposure, and does not show activity under normal temperature and pressure conditions, but as long as it generates a base (alkaline substance) when it is irradiated with electromagnetic waves and heated as an external stimulus are not particularly limited. The base generated by exposure functions as a catalyst when the polymer precursor is heated and hardened, so it can be preferably used. In this invention, a well-known thing can be used as a photocuring accelerator. For example, transition metal compound complexes, those having a structure such as an ammonium salt, those in which the amidine moiety is latent by forming a salt with a carboxylic acid, and ions in which the alkali component is neutralized by forming a salt Nonionic compounds in which the alkali component is latent through a urethane bond or an oxime bond, etc.

As the photohardening accelerator of the present invention, for example, photohardening accelerators having a cinnamic acid amide structure as disclosed in JP-A-2009-080452 and International Publication No. 2009/123122, such as JP-A 2006-189591 A and JP 2008-247747 A photohardening accelerator having a urethane structure, as disclosed in JP 2007-249013 A and JP 2008-003581 A Such photocuring accelerators having an oxime structure and a carbamoxime structure, etc., are not limited to these, and other structures of known photocuring accelerators can be used.

In addition, examples of photohardening accelerators include the compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of JP-A-2012-093746, and compounds described in paragraphs 0022-0069 of JP-A-2013-194205. The compounds described in paragraphs, the compounds described in paragraphs 0026 to 0074 of JP-A-2013-204019, and the compounds described in paragraph 0052 of International Publication WO2010/064631.

Commercially available photocuring accelerators include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB -172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167 and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.).

When a photocuring accelerator is used, the content of the photocuring accelerator in the composition is preferably 0.1 to 50% by mass relative to the total solid content of the composition. 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. One type or two or more types of photohardening accelerators can be used. When two or more kinds are used, it is preferable that the total amount is within the above-mentioned range.

＜Thermal radical polymerization initiator＞ The photosensitive resin composition of this invention may contain a thermal radical polymerization initiator in the range which does not deviate from the summary of this invention. Thermal free radical polymerization initiators are compounds that generate free radicals by thermal energy and initiate or accelerate the polymerization reaction of polymerizable compounds. By adding a thermal radical polymerization initiator, the cyclization of the polymer precursor can proceed, and the polymerization reaction of the polymer precursor can proceed, so higher heat resistance can be realized. Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.

When a thermal radical polymerization initiator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.1 to 20% by mass relative to the total solid content of the photosensitive resin composition of the present invention. 5 to 15% by mass. A thermal radical polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more types of thermal radical polymerization initiators are contained, it is preferable that the total is within the above-mentioned range.

＜Coincidental compounds＞ ＜＜Radical polymerizable compound＞＞ It is preferable that the photosensitive resin composition of this invention contains a radically polymerizable compound. As the radical polymerizable compound, a compound having a radical polymerizable group can be used. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as vinylphenyl, vinyl, (meth)acryl, and allyl. The radical polymerizable group is preferably a (meth)acryloyl group.

The number of radical polymerizable groups that the radical polymerizable compound has can be 1 or more than 2. The radical polymerizable compound has more than 2 radical polymerizable groups. It is better to have 3 or more radical polymerizable groups. More than one is better. The upper limit is preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less.

The molecular weight of the radically polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.

From the viewpoint of developability, the photosensitive resin composition of the present invention preferably contains at least one bifunctional or higher radical polymerizable compound containing two or more polymerizable groups, and at least one trifunctional or higher radical polymerizable compound. A polymeric compound is more preferable. Moreover, it may be a mixture of a bifunctional radically polymerizable compound and a trifunctional or more radically polymerizable compound. In addition, the number of functional groups of a radical polymerizable compound means the number of radical polymerizable groups in 1 molecule.

Specific examples of radically polymerizable compounds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters, amides , preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyamine compounds. Also, it is also preferable to use unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl groups, amino groups, mercapto groups, and monofunctional or polyfunctional isocyanates or epoxy. Dehydration condensation reaction products of functional or polyfunctional carboxylic acids, etc. Also, addition reaction products of unsaturated carboxylates or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, alcohols, and halogen groups or toluenesulfonate Substitution reaction products of unsaturated carboxylic acid esters or amides with detachable substituents such as acyloxy groups and monofunctional or polyfunctional alcohols, amines, and alcohols are also preferred. Also, as another example, instead of the above-mentioned unsaturated carboxylic acid, a compound group substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, and the like can be used. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and these contents are incorporated into this specification.

Moreover, it is also preferable that a radical polymerizable compound has a boiling point of 100 degreeC or more under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol tri (Meth)acrylate, Neopentylthritol tetra(meth)acrylate, Dineopentylthritol penta(meth)acrylate, Dineopentylthritol hexa(meth)acrylate, Hexylene glycol (meth)acrylate base) acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. in polyfunctional alcohols Compounds that undergo (meth)acrylation after adding ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Application Publication No. 51-037193 (Meth)acrylic urethanes described in the gazette, Japanese Patent Application Publication No. 48-064183, Japanese Patent Publication No. 49-043191, polyester acrylic acid described in Japanese Patent Publication No. 52-030490 Esters, polyfunctional acrylates or methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Moreover, the polyfunctional (meth)acrylate obtained by reacting polyfunctional carboxylic acid and the compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, etc. are mentioned. In addition, as preferred radically polymerizable compounds other than the above-mentioned ones, there can also be used those with fenugreek described in JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. A compound or a cardo resin having two or more ethylenically unsaturated bond-containing groups. Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 1-040337, Japanese Patent Publication No. 1-040336, Japanese Patent Laid-Open No. 2 -Vinylphosphonic acid-based compounds described in Publication No. 025493, etc. Also, compounds containing a perfluoroalkyl group described in JP-A-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, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 can also be preferably used, and these contents are incorporated in this specification.

In addition, the following compounds described in Japanese Patent Application Laid-Open No. 10-062986 as formula (1) and formula (2) together with specific examples thereof can also be used as radical polymerizable compounds, which are added to polyfunctional alcohols. A compound obtained by (meth)acrylic esterification after forming ethylene oxide or propylene oxide.

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

As a radically polymerizable compound, diperythritol triacrylate (as a commercial item, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), diperythritol tetraacrylate (as a commercial item, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), diperythritol penta(meth)acrylate (the commercially available product is KAYARAD D -310; manufactured by Nippon Kayaku Co., Ltd.), diperythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and the structure in which (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues is preferable. These oligomer types can also be used.

As a commercial product of the radically polymerizable compound, for example, SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four ethoxylate chains, and SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains, Sartomer Company, Inc. SR-209, 231, 239 of functional methyl acrylate, DPCA-60 of Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 TPA-330, urethane oligomer UAS-10, urethane oligomer 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 (manufactured by Nippon Kayaku Co., Ltd. ), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

As the radical polymerizable compound, as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 2-032293, and Japanese Patent Publication No. 2-016765 Urethane acrylates, 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. Oxyethane-based urethane compounds are also preferred. Furthermore, as a radically polymerizable compound, compounds having an amino group in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-1-105238 can also be used. Compounds with structure or sulfide structure.

The radically polymerizable compound may be a radically polymerizable compound having an acidic group such as a carboxyl group or a phosphoric acid group. Among radically polymerizable compounds having acid groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, which have acid groups by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides. A radically polymerizable compound is more preferable. Among the radically polymerizable compounds having an acid group by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride, the aliphatic polyhydroxy compound is neopentyl glycol and/or dipentyl glycol. compound. As a commercial item, M-510, M-520, etc. are mentioned, for example as TOAGOSEI CO., Ltd. polyacid-modified acrylic oligomer. The preferable acid value of the radically polymerizable compound which has an acid group is 0.1-40 mgKOH/g, especially preferably 5-30 mgKOH/g. If the acid value of a radically polymerizable compound exists in the said range, it will be excellent in manufacture and handleability, and also will be excellent in developability. Moreover, polymerizability is also favorable.

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

<<Polymerizable compounds other than the radically polymerizable compounds mentioned above>> The photosensitive resin composition of the present invention may contain polymerizable compounds other than the above-mentioned radically polymerizable compounds. Examples of polymerizable compounds other than the above-mentioned radically polymerizable compounds include compounds having a methylol, alkoxymethyl, or acyloxymethyl group; epoxy compounds; oxetane compounds; compound.

(compounds with hydroxymethyl, alkoxymethyl or acyloxymethyl) 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 preferable.

（式中，t表示1～20的整數，R¹⁰⁴ 表示碳數1～200的t價有機基團，R¹⁰⁵ 表示由-OR¹⁰⁶ 或-OCO-R¹⁰⁷ 表示之基團，R¹⁰⁶ 表示氫原子或碳數1～10的有機基團，R¹⁰⁷ 表示碳數1～10的有機基團。）[chemical formula 24]

(In the formula, t represents an integer of 1 to 20, R ¹⁰⁴ represents a t-valent organic group with a carbon number of 1 to 200, R ¹⁰⁵ represents a group represented by -OR ¹⁰⁶ or -OCO-R ¹⁰⁷ , R ¹⁰⁶ represents a hydrogen atom Or an organic group with 1 to 10 carbons, R ¹⁰⁷ represents an organic group with 1 to 10 carbons.)

（式中，R⁴⁰⁴ 表示碳數1～200的2價有機基團，R⁴⁰⁵ 表示由-OR⁴⁰⁶ 或-OCO-R⁴⁰⁷ 表示之基團，R⁴⁰⁶ 表示氫原子或碳數1～10的有機基團，R⁴⁰⁷ 表示碳數1～10的有機基團。）[chemical formula 25]

(In the formula, R ⁴⁰⁴ represents a divalent organic group with 1 to 200 carbons, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , R ⁴⁰⁶ represents a hydrogen atom or an organic group with 1 to 10 carbons group, R ⁴⁰⁷ represents an organic group with 1 to 10 carbons.)

（式中，u表示3～8的整數，R⁵⁰⁴ 表示碳數1～200的u價有機基團，R⁵⁰⁵ 表示由-OR⁵⁰⁶ 或、-OCO-R⁵⁰⁷ 表示之基團，R⁵⁰⁶ 表示氫原子或碳數1～10的有機基團，R⁵⁰⁷ 表示碳數1～10的有機基團。）[chemical formula 26]

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

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above are trade names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC , DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol (2,6-dimethoxymethyl-4-t-butylphenol) , 2,6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacethoxymethyl-p-cresol (2,6-diacetoxymethyl-p-cresol cresol), etc.

In addition, 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 (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.).

(epoxy compounds (compounds with epoxy groups)) The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy undergoes a cross-linking reaction at a temperature below 200°C, and since it does not cause a dehydration reaction derived from cross-linking, it is difficult to cause film shrinkage. Therefore, low-temperature hardening and warpage of the composition can be effectively suppressed by containing the epoxy compound.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the modulus of elasticity is further lowered, and warpage can be suppressed. The polyethylene oxide group means that the number of constituent units of ethylene oxide is 2 or more, and the number of constituent units is preferably 2-15.

Examples of epoxy compounds include alkylene glycol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and propylene glycol diglycidyl ether; Alkylene glycol-type epoxy resins; epoxy-containing silicones such as polymethyl(glycidoxypropyl) siloxane, etc., but not limited to them. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) Trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (the above are trade names, manufactured by DIC Corporation), RIKARESIN (registered Trademark) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above are trade names, manufactured by ADEKA CORPORATION), etc. Among these, the epoxy resin containing a polyethylene oxide group is preferable from the point which suppresses warpage and is excellent in heat resistance. For example, since EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups, they are preferable.

(Oxetane compounds (compounds having an oxetanyl group)) Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxetane, 1,4-bis{ [(3-Ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzene dicarboxylic acid-bis[(3-ethyl-3-oxetanyl)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 can be used alone or in combination. more than one species.

(Benzozoline compounds (compounds having a polybenzoxazolyl group)) The benzoyl compound is preferable because it does not generate outgassing during hardening due to the crosslinking reaction derived from the ring-opening addition reaction, thereby reducing heat shrinkage and suppressing warpage.

Preferable examples of benzophenone compounds include B-a type benzophenone, B-m type benzophenone (the above are trade names, manufactured by Shikoku Chemicals Corporation), polyhydroxystyrene resin benzophenone Adducts, novolak-type dihydrobenzo㗁𠯤 compounds. These may be used alone, or two or more kinds may be mixed.

When a polymeric compound is contained, its content is preferably more than 0 mass % and 60 mass % or less with respect to the total solid content of the photosensitive resin composition of this invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably at most 50% by mass, and is still more preferably at most 30% by mass. Other polymerizable compounds may be used alone or in combination of two or more. When using 2 or more types simultaneously, it is preferable that the total amount becomes the said range.

＜Migration Inhibitor＞ It is preferable that the photosensitive resin composition of the present invention further includes a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress migration of metal ions originating in the metal layer (metal wiring) into the photosensitive resin composition layer. The migration inhibitor is not particularly limited, and examples include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, Azole ring, pyridine ring, pyranyl ring, pyrimidine ring, pyranyl ring, piperidine ring, piperyl ring, portoline ring, 2H-pyran ring and 6H-pyran ring, tri-alpha ring) compounds, with Thiourea and mercapto compounds, hindered phenolic compounds, salicylic acid derivatives, hydrazide derivatives. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

In addition, an ion-trapping agent that traps anions such as halogen ions can also be used.

As other migration inhibitors, rust inhibitors described in paragraph 0094 of JP 2013-015701 A, compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, JP 2011 - Compounds described in paragraph 0052 of Japanese Patent Application Laid-Open No. 059656, compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, and the like.

Specific examples of migration inhibitors include the following compounds. [chemical formula 27]

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

當本發明的感光性樹脂組成物具有聚合抑制劑時，聚合抑制劑的含量相對於本發明的感光性樹脂組成物的總固體成分係0.01～5質量%為較佳，0.02～3質量%為更佳，0.05～2.5質量%為進一步較佳。 聚合抑制劑可以為僅一種，亦可以為兩種以上。當聚合抑制劑為兩種以上時，其合計為上述範圍為較佳。<Polymerization inhibitor> It is preferable that the photosensitive resin composition of this invention contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4- Methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylidene diphenylamine Amine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, ethylene glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxy Quinoline, 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 inhibitors described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication WO2015/125469 can also be used. Moreover, the following compound (Me is a methyl group) can also be used. [chemical formula 28]

When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass % relative to the total solid content of the photosensitive resin composition of the present invention, and 0.02 to 3 mass % is More preferably, 0.05 to 2.5 mass % is still more preferable. The polymerization inhibitor may be used alone, or may be used in combination of two or more. When there are two or more kinds of polymerization inhibitors, it is preferable that the total thereof is within the above-mentioned range.

＜Metal Adhesion Improver＞ It is preferable that the photosensitive resin composition of this invention contains the metal adhesion improvement agent for improving the adhesion with the metal material used for an electrode, wiring, etc. As a metal adhesion improving agent, a silane coupling agent etc. are mentioned.

Examples of silane coupling agents include compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, compounds described in paragraphs 0063-0071 of International Publication WO2011/080992A1, JP-A Compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-41264, and compounds described in paragraph 0055 of International Publication WO2014/097594. Moreover, it is also preferable to use different 2 or more types of silane coupling agents as described in paragraph 0050-0058 of Unexamined-Japanese-Patent No. 2011-128358. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulae, Et represents an ethyl group. [chemical formula 29]

In addition, as the metal adhesion improving agent, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfides described in paragraphs 0032-0043 of JP-A-2013-072935 can also be used.

The content of the metal adhesion improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass relative to 100 parts by mass of the polymer precursor. The adhesiveness of the cured film after a curing process and a metal layer becomes favorable by making it more than the said lower limit, and the heat resistance of the cured film after a curing process, and a mechanical characteristic become favorable by being below the said upper limit. The metal adhesion improving agent may be used alone or may be used in combination of two or more. When using 2 or more types, it is preferable that the sum total is the said range.

<Hardening accelerator> The photosensitive resin composition of this invention may contain a hardening accelerator. The hardening accelerator may be a thermal hardening accelerator or a light hardening accelerator. The photocuring accelerator in the present invention is preferably one that generates a base by heat or exposure (base generator). <<Thermal curing accelerator>> The thermal curing accelerator is preferably a salt of a quaternary ammonium cation and a carboxylic acid anion. The quaternary ammonium cation is preferably represented by any one of the following formulas (Y1-1) to (Y1-4). [chemical formula 30]

R ^Y1 represents an organic group with a valence of n ^Y (n ^Y is an integer of 1 to 12), preferably a hydrocarbon group with a valence of n ^Y. As the hydrocarbon group, n ^Y valent groups containing alkanes (1 to 12 carbons are preferred, 1 to 6 are more preferred, 1 to 3 are further preferred), n ^Y valent groups containing alkenes (carbons 2-12 is preferred, 2-6 is more preferred, 2-3 is further preferred), n ^Y -valent groups containing aromatic hydrocarbons (6-22 carbons are preferred, 6-18 are preferred , 6 to 10 are further preferred) or a combination thereof. R ^Y1 is preferably an aromatic hydrocarbon group. R ^Y1 may have the aforementioned substituent T within a range not impairing the effect of the present invention. R ^Y2 to R ^Y5 independently represent a hydrogen atom or a hydrocarbon group (preferably 1 to 36 carbons, more preferably 1 to 24, further preferably 1 to 12), alkyl (preferably 1 to 36 carbons) , 1 to 24 is more preferred, 1 to 23 is further preferred), alkenyl (2 to 36 carbons is preferred, 2 to 24 is more preferred, 2 to 23 is further preferred), alkynyl (carbon number 1-36 is preferable, 1-24 is more preferable, 1-23 is still more preferable), aryl group (6-22 is preferable, 6-18 is more preferable, 6-10 is still more preferable) is better. The alkyl, alkenyl and alkynyl groups may be cyclic or chain, and when chain, may be linear or branched. R ^Y6 is alkyl (preferably 1-36 carbons, more preferably 2-24, further preferably 4-18), alkenyl (preferably 2-36 carbons, more preferably 2-24, 4-18 is more preferred), alkynyl (2-36 carbons is preferred, 2-24 is more preferred, 4-18 is further preferred), aryl (6-22 carbons is preferred, 6 ～18 is more preferred, 6～10 is further preferred). An alkyl group, an alkenyl group, and an alkynyl group may be cyclic or chain, and when chain, may be linear or branched. In an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, a linking group Lh containing a heteroatom may be interposed between groups and the core nucleus. n ^Y represents the integer of 1-12, the integer of 1-6 is more preferable, and the integer of 1-3 is still more preferable. n ^X represents the integer of 1-12, the integer of 1-6 is preferable, and the integer of 1-3 is more preferable. Two or more of each of R ^Y2 to R ^Y6 may be bonded to each other to form a ring.

R ^Y7 to R ^Y16 are groups defined the same as R ^N . In the formula ( ^Y1-2 ), ^RY7 and RY8 are carboxyalkyl groups (preferably 1-12 carbons, more preferably 1-6, more preferably 1-3; the number of carboxyl groups is 1-12 Preferably, 1 to 6 are more preferred, 1 to 3 are still more preferred) are more preferred. R ^Y9 is preferably an aromatic group, more preferably an aryl group (preferably having 6-22 carbon atoms, more preferably having 6-18 carbon atoms, and further preferably having 6-10 carbon atoms). Alternatively, an alkoxycarbonyl group substituted by an aromatic group is more preferable (the carbon number of the alkoxy group is 1-12 is preferable, 1-6 is more preferable, 1-3 is further preferable, aromatic group The carbon number of the cluster is preferably 6-22, more preferably 6-18, and still more preferably 6-14). In the formula (Y1-3), R ^Y11 and R ^Y13 are preferably hydrogen atoms. Two of R ^Y14 and R ^Y15 may be combined to form a substituent of the form =C(NR ^N ₂ ) ₂ (= refers to a double bond and is bonded to a nitrogen atom). In the formula (Y1-4), ^RY13 is preferably a hydrogen atom, and ^RY10 , ^RY11 , ^RY12 , and ^RY16 are alkyl groups (preferably 1-12 carbons, more preferably 1-6, 1-6 3 is further preferred) is preferred. In this case, it is preferable that ^RY11 and ^{RY16 and RY10 and RY12} are bonded to form a ring and form a bicyclic compound. Specifically, diazabicyclononene and diazabicycloundecene are mentioned.

式（X1）中，EWG表示吸電子基。In this embodiment, the carboxylate anion paired with the quaternary ammonium cation of the above formula (Y1-1), formula (Y1-3) and formula (Y1-4) is preferably represented by the following formula (X1) . [chemical formula 31]

In formula (X1), EWG represents an electron-withdrawing group.

The electron-withdrawing group in the present embodiment refers to a Hammett substituent constant σm showing a positive value. Among them, σm is described in detail in Mr. Tsuno Yuuo, Journal of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965), p.631-642. In addition, the electron-withdrawing group in this embodiment is not limited to the substituents described in the above-mentioned documents. 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) Wait. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same).

式（EWG-1）～（EWG-6）中，R^x1 ～R^x3 分別獨立地表示氫原子、烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、烯基（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、羥基或羧基。Ar表示芳香族基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）。當R^x1 ～R^x3 為烷基、烯基、芳基時，可以形成環，形成環時可以於取中途夾雜上述連接基L或上述具有雜原子之連接基Lh。於不損害本發明的效果之範圍內，該等烷基、烯基、芳基及Ar可以具有取代基T。其中，Ar尤其具有羧基（較佳為1～3個）為較佳。*表示鍵結位置。 Np表示1～6的整數，1～3的整數為較佳，1或2為更佳。EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6). [chemical formula 32]

In the formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 independently represent a hydrogen atom and an alkyl group (preferably 1 to 12 carbons, more preferably 1 to 6, and furthermore 1 to 3 preferably), alkenyl (preferably 2-12 carbons, more preferably 2-6, further preferably 2-3), aryl (preferably 6-22 carbons, more preferably 6-18 , 6-10 are further preferred), hydroxyl or carboxyl. Ar represents an aromatic group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 10 carbon atoms). When R ^x1 to R ^x3 are alkyl groups, alkenyl groups, or aryl groups, a ring may be formed, and the above-mentioned linking group L or the above-mentioned linking group Lh having a heteroatom may be inserted in the middle of the ring. These alkyl groups, alkenyl groups, aryl groups, and Ar may have a substituent T within the range that does not impair the effects of the present invention. Among them, Ar particularly preferably has a carboxyl group (preferably 1 to 3). * Indicates bond position. Np represents an integer of 1-6, preferably an integer of 1-3, more preferably 1 or 2.

The molecular weight of the thermosetting accelerator in the present invention is preferably from 100 to less than 2000, more preferably from 200 to 1000. As specific examples of the thermosetting accelerator in the present invention, in addition to the compounds used in the examples described later, acidic compounds that generate a base when heated to 40°C or higher described in WO2015/199219 and pKa1 of 0 are exemplified. ~4 and ammonium salts having anions and ammonium cations, and these are incorporated into this specification.

When a thermosetting accelerator is used, the content of the thermosetting accelerator in the composition is preferably 0.01 to 50% by mass relative to the total solid content of the composition. The lower limit is more preferably at least 0.05% by mass, and more preferably at least 0.1% by mass. The upper limit is more preferably at most 10% by mass, and more preferably at most 5% by mass. One type or two or more types of thermosetting accelerators can be used. When two or more kinds are used, it is preferable that the total amount is within the above-mentioned range. Moreover, the composition of this invention can be set as the structure which does not contain a thermosetting accelerator substantially. Substantially not containing means that it is less than 0.01% by mass, more preferably less than 0.005% by mass relative to the total solid content of the composition.

＜Other additives＞ The photosensitive resin composition of the present invention can be used for various additives, such as sensitizing pigments, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, hardeners, etc. Additives, hardening catalysts, fillers, antioxidants, UV absorbers, aggregation inhibitors, etc. When compounding these additives, it is preferable to set the total compounding amount to be 3% by mass or less of the solid content of the composition.

＜＜Thermal acid generator＞＞ The photosensitive resin composition of the present invention may contain a thermal acid generator. The thermal acid generator generates acid by heating, and promotes the cyclization of the polymer precursor to further improve the mechanical properties of the cured film. Examples of thermal acid generators include compounds described in paragraph 0059 of JP-A-2013-167742, and the like.

The content of the thermal acid generator is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the polymer precursor, more preferably 0.1 parts by mass or more. When the thermal acid generator is contained in an amount of 0.01 parts by mass or more, the crosslinking reaction and the cyclization of the polymer precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. Moreover, from the viewpoint of the electrical insulation of a cured film, content of a thermal acid generator is preferably 20 parts by mass or less, More preferably, it is 15 parts by mass or less, More preferably, it is 10 parts by mass or less. As the thermal acid generator, only one kind may be used, or two or more kinds may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.

＜＜Sensitizing pigment＞＞ The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and enters an electronically excited state. The sensitizing pigment in an electronically excited state is in contact with thermal hardening accelerators, thermal radical polymerization initiators, photoradical polymerization initiators, etc., to produce electron transfer, energy transfer, and heat generation. Thereby, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator are chemically changed and decomposed to generate radicals, acids, or bases. For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, and the content is incorporated in this specification.

When the photosensitive resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass relative to the total solid content of the photosensitive resin composition of the present invention, and 0.1 to 15% by mass is More preferably, 0.5-10 mass % is still more preferable. One kind of sensitizing pigment may be used alone, or two or more kinds may be used simultaneously.

＜＜Chain transfer agent＞＞ The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in Polymer Dictionary 3rd Edition (ed. The Society of Polymer Science, Japan, 2005) pp. 683-684. As a chain transfer agent, for example, a compound group having SH, PH, SiH and GeH in the molecule is used. These can generate free radicals by donating hydrogen to low-activity free radicals, or can generate free radicals by deprotonation after oxidation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptopolybenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetra azoles, etc.).

When the photosensitive 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, 1 to 10 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. It is more preferable that it is a mass part, and it is still more preferable that it is 1-5 mass parts. The chain transfer agent may be used alone, or may be used in combination of two or more. When there are two or more chain transfer agents, the total range is preferably the above range.

<<surfactant>> Various surfactants can be added to the photosensitive resin composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. Moreover, the following surfactants are also preferable. [chemical formula 33]

When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass relative to the total solid content of the photosensitive resin composition of the present invention. quality%. Surfactants may be used alone or in combination of two or more. When there are two or more surfactants, the total range is preferably the above range.

＜＜Higher fatty acid derivatives＞＞ In order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide can be added to the photosensitive resin composition of the present invention to partially exist in the drying process after coating. the surface of the composition. When the photosensitive 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 photosensitive resin composition of the present invention. The higher fatty acid derivative may be only one kind, or may be two or more kinds. When there are two or more higher fatty acid derivatives, the total range is preferably the above range.

＜Restrictions on other substances contained＞ From the viewpoint of coating surface shape, the water content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and still more preferably less than 0.6% by mass.

From the viewpoint of insulation, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million (parts per million)), more preferably less than 1 mass ppm, and less than 0.5 mass ppm. Further better. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably within the above-mentioned range. In addition, as a method for reducing the metal impurities unexpectedly contained in the photosensitive resin composition of the present invention, it is possible to select a raw material with a low metal content as a raw material constituting the photosensitive resin composition of the present invention, which is beneficial to the composition of the present invention. The raw material of the photosensitive resin composition is filtered through a filter, the interior of the device is lined with polytetrafluoroethylene, and distillation is carried out under conditions that suppress pollution as much as possible.

In consideration of the use as a semiconductor material and from the viewpoint of wiring corrosion, the content of halogen atoms in the photosensitive resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm ppm is further preferred. Among them, those present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atom and bromine atom or chlorine ion and bromide ion is in the above-mentioned range respectively.

A conventionally known storage container can be used as a storage container of the photosensitive resin composition of this invention. Also, as a storage container, for the purpose of preventing impurities from mixing into raw materials or compositions, it is also preferable to use a multi-layer bottle whose inner wall is composed of 6 types of 6-layer resins, or a bottle with 6 types of resins formed into a 7-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

＜Preparation of composition＞ The photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and it can be performed by a conventionally known method. In addition, for the purpose of removing foreign substances such as garbage and fine particles in the composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. Filters can be used pre-cleaned with organic solvents. In the filtration step of the filter, a plurality of types of filters can be used in parallel or in series. When multiple types of filters are used, filters with different pore diameters or materials can be used in combination. Also, various materials can be filtered multiple times. When filtering multiple times, it can be filtered for loops. In addition, filtration may be performed after pressurization. When filtering is performed after pressurization, it is preferable that the pressure for pressurization is 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine filter filtration and impurity removal treatment using an adsorbent. As the adsorbent, known adsorbents can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

<Cured films, laminates, semiconductor devices, and methods of manufacturing them> Next, the cured film, laminated body, semiconductor device, and their manufacturing methods will be described. The cured film of this invention is formed by hardening the photosensitive resin composition of this invention. The film thickness of the cured film of this invention can be 0.5 micrometer or more, for example, and can be 1 micrometer or more. Moreover, as an upper limit, it can be set to 100 micrometers or less, and can also be set to 30 micrometers or less.

Two or more layers of the cured film of the present invention may be laminated, and further 3 to 7 layers may be laminated to form a laminate. It is preferable that the seed layer system having two or more layers of the cured film of the present invention has a metal layer between the cured films. These metal layers can be preferably used as metal wirings such as redistribution layers.

As the field to which the cured film of this invention can be applied, the insulating film of a semiconductor device, the interlayer insulating film for rewiring layers, a stress buffer film, etc. are mentioned. Other examples include sealing films, substrate materials (base film or cover layer of flexible printed circuit boards, interlayer insulating films), or cases where the above-mentioned insulating films for actual mounting are patterned by etching, etc. . For such uses, see, for example, Science & Technology Co., Ltd. "Highly Functional Polyimide and Application Technology", April 2008, Masami Kakimoto/Supervisor, CMC Technical Library "Polyimide Materials "Basic and Development of Polyimide" published in November 2011, Japan Polyimide and Aromatic Polymer Research Society/edited "Basic and Application of Latest Polyimide" NTS, August 2010, etc.

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

The manufacturing method of the cured film of this invention includes the case where the photosensitive resin composition of this invention is used. Specifically, it includes a film forming step of applying the photosensitive resin composition of the present invention to a substrate to form a film (layer forming step) and treating the layered photosensitive resin at 80 to 450°C. A heating step in which the composition is heated. Preferably, the production method of the cured film includes an exposure step of exposing the film after the above-mentioned film forming step (layer forming step) and exposing the above-mentioned exposed photosensitive resin composition layer (film forming step). , that is, the resin layer) is a development treatment step for development treatment. After the development, the resin layer exposed by heating (preferably heating at 80 to 450° C.) can be further cured. In addition, as described above, when using a photosensitive resin composition, the composition can be cured by exposure in advance, and then desired processing (such as lamination described below) can be performed as needed, and then cured by heating.

The manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention. In the method for producing a laminate of the present invention, according to the above-mentioned method for producing a cured film, after forming the cured film, the film forming step (layer forming step) and the heating step of the photosensitive resin composition are sequentially performed again, or photosensitivity is imparted It is preferable to perform a film forming step (layer forming step), an exposure step, and a development treatment step (if necessary, a heating step) in this order. In particular, it is preferable to sequentially perform each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). A laminated body can be formed by laminating a cured film in this way. In the present invention, it is preferable to provide a metal layer on the upper side of the part where the cured film is provided, or between the cured films, or both. These will be described in detail below.

＜＜Film formation step (layer formation step)＞＞ The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) of applying a photosensitive resin composition to a substrate to form a film (layer form). The type of substrate can be appropriately set according to the application, but it is not particularly limited. Examples include substrates made of semiconductors such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, and vapor-deposited films. , magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe, etc., paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrate, electrode plate of plasma display panel (PDP), etc. In the present invention, especially semiconductor substrates are preferred, and silicon substrates are more preferred. Moreover, when forming a photosensitive resin composition layer on the surface of a resin layer or the surface of a metal layer, a resin layer or a metal layer becomes a board|substrate. Coating is preferable as a method of applying the photosensitive resin composition to a substrate. Specifically, examples of applicable methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, Slit coating method and inkjet method, etc. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer with a desired thickness can be obtained by adjusting the appropriate solid content concentration or coating conditions according to the method. 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, the spin coating method, spray coating method, inkjet method, etc. are preferred, and as long as it is a rectangular substrate, the slit coating method is suitable. Or a spraying method, an inkjet method, etc. are preferable. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

＜＜Drying Step＞＞ The production method of the present invention may further include a step of drying to remove the solvent after forming the photosensitive resin composition layer and after the film formation arrangement (layer formation arrangement). The preferred drying temperature is 50-150°C, more preferably 70-130°C, and more preferably 90-110°C. As drying time, 30 seconds - 20 minutes are illustrated, Preferably it is 1 minute - 10 minutes, More preferably, it is 3 minutes - 7 minutes.

<<Exposure step>> The production method of the present invention may include an exposure step of exposing the above-mentioned photosensitive resin composition layer. The exposure amount is not particularly limited within the range capable of curing the photosensitive resin composition. For example, 100-10000 mJ/cm ² is preferably irradiated in terms of exposure energy at a wavelength of 365 nm, and more preferably 200-8000 mJ/cm ² . The exposure wavelength can be appropriately set within the range of 190 to 1000 nm, preferably 240 to 550 nm. Regarding the exposure wavelength, if described in relation to the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g Ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), broad (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm) , ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, etc. Regarding the photosensitive resin composition in the present invention, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by i-rays is preferable. Thereby, especially high exposure sensitivity can be obtained.

＜＜Development processing steps＞＞ The manufacturing method of the present invention may include a development treatment step, which is to perform development treatment on the exposed photosensitive resin composition layer. By developing, the unexposed part (non-exposed part) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, developing methods such as spin-on immersion, spraying, dipping, and ultrasonic waves can be employed. Image development is performed using a developer. There are no particular limitations on the developer as long as it can remove the unexposed portion (non-exposed portion). It is preferable that the developer contains an organic solvent, and it is more preferable that the developer contains more than 90% of the organic solvent. In the present invention, the developer preferably contains an organic solvent with a ClogP value of −1 to 5, and more preferably contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw (chemical biological diagram). Regarding organic solvents, examples of esters include ethyl acetate, n-butyl acetate, amyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyric acid Ethyl ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (example: methyl alkoxyacetate , ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate esters, etc.), 3-alkoxy propionate alkyl esters (eg: 3-alkoxy propionate methyl ester, 3-alkoxy propionate ethyl ester, etc. (eg, 3-methoxy propionate methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (example: 2 - Methyl 2-methoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2 - Ethyl alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate ester, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, for example, Suitably exemplified are diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol mono Methyl 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 ketone For example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and aromatic hydrocarbons , For example, toluene, xylene, anisole, limonene, etc. are suitably mentioned, and as aroxines, dimethylarridine is suitably mentioned. In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. It is preferable that 50 mass % or more of a developer is an organic solvent, it is more preferable that 70 mass % or more is an organic solvent, and it is still more preferable that 90 mass % or more is an organic solvent. In addition, 100% by mass of the developer may be an organic solvent.

As developing time, 10 seconds - 5 minutes are preferable. The temperature of the developing solution at the time of image development is not specifically limited, Usually, it can perform at 20-40 degreeC. Rinsing may be further performed after the processing using the developing solution. Rinsing is preferably carried out with a solvent different from that of the developer. For example, rinsing can be performed using a solvent contained in the photosensitive resin composition. The flushing time is preferably 5 seconds to 1 minute.

＜＜Heating step＞＞ The production method of the present invention preferably includes a step of heating after the film forming step (layer forming step), drying step, or developing step. In the heating step, the cyclization reaction of the polymer precursor proceeds. In addition, the composition of the present invention may contain a radically polymerizable compound other than the polymer precursor, and curing of the radically polymerizable compound other than the unreacted polymer precursor can be performed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 to 500°C, more preferably 80 to 450°C, still more preferably 140 to 350°C, still more preferably 160 to 250°C, and 170 ~220°C is the best. The heating is preferably carried out at a rate of temperature increase from the temperature at the start of heating to the maximum heating temperature at a rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and still more preferably 3 to 10°C/min. By setting the rate of temperature increase to 1° C./minute or more, excessive volatilization of amine can be prevented while ensuring productivity, and residual stress of the cured film can be relaxed by setting the rate of temperature increase to 12° C./minute or less. The temperature at the start of heating is preferably from 20°C to 150°C, more preferably from 20°C to 130°C, and still more preferably from 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 highest heating temperature. For example, when the photosensitive resin composition is applied to the substrate and dried, the temperature of the dried film (layer), for example, is 30 to 200°C lower than the boiling point of the solvent contained in the photosensitive resin composition. It is preferable to gradually increase the temperature in °C. The heating time (heating time at the highest heating temperature) is preferably from 10 to 360 minutes, more preferably from 20 to 300 minutes, and still more preferably from 30 to 240 minutes. In particular, when forming a multilayer laminate, it is preferable to heat at a heating temperature of 180° C. to 320° C., and more preferably to heat at 180° C. to 260° C. from the viewpoint of the adhesiveness between layers of a cured film. The reason for this is not certain, but it is considered that by setting this temperature, the acetylene groups of the polymer precursor between the layers undergo a crosslinking reaction.

Heating can be done in stages. As an example, the temperature can be raised from 25°C to 180°C at 3°C/min and kept at 180°C for 60 minutes, and the temperature can be raised from 180°C to 200°C at 2°C/min and kept at 200°C for 120 minutes. . The heating temperature in the pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and still more preferably 120 to 185°C. In this pretreatment step, it is also preferable to perform treatment while irradiating ultraviolet rays as described in US Patent No. 9,159,547. The properties of the film can be improved by these pretreatment steps. The pretreatment step can be carried out within a short period of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be a step of more than two stages. For example, the pretreatment step 1 may be performed at a temperature ranging from 100 to 150°C, and then the pretreatment step 2 may be performed at a temperature ranging from 150 to 200°C. Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5° C./min.

The heating step is preferably performed in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, from the viewpoint of preventing the decomposition of the polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

＜＜Metal layer formation process＞＞ It is preferable that the manufacturing method of the present invention includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment. The metal layer is not particularly limited, and conventional metals can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable, and copper is still more preferable. The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining them can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating are mentioned. The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

＜＜Stacking steps＞＞ It is preferable that the manufacturing method of the present invention further includes a layering step. The lamination step includes performing the above-mentioned film formation step (layer formation step) and heating step again on the surface of the cured film (resin layer) or metal layer, or sequentially performing the above-mentioned film formation step (layer formation step) on the photosensitive resin composition. . A series of steps in the case of the above-mentioned exposure step and the above-mentioned development treatment step. It goes without saying that the above-mentioned drying step, heating step, and the like may also be included in the lamination step. When the layering step is performed after the layering step, the 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. As the surface activation treatment, plasma treatment is exemplified. It is better to carry out the above lamination step 2 to 5 times, more preferably 3 to 5 times. For example, the resin layer structure such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably 3 or more and 7 or less layers, and is more preferably 3 or more and 5 or less layers. That is, in the present invention, after the metal layer is provided, the film forming step (layer forming step) and the heating step of the above-mentioned photosensitive resin composition are further sequentially performed or the above-mentioned film forming step (layer forming step) is sequentially performed on the photosensitive resin composition. Forming step), the above-mentioned exposure step and the above-mentioned development treatment step (and further heating step if necessary), so as to cover the above-mentioned metal layer is preferred. By alternately performing the lamination step of laminating the photosensitive resin composition layer (resin) and the metal layer forming step, the photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses a semiconductor device having the cured film or laminate of the present invention. As a specific example of a semiconductor device using the photosensitive resin composition of the present invention in the formation of an interlayer insulating film for a rewiring layer, reference can be made to the description in paragraphs 0213 to 0218 of JP-A-2016-027357 and the description in FIG. 1 . record and incorporate them into this manual. [Example]

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, usage amounts, ratios, processing contents, and processing steps shown in the following examples can be appropriately changed within the scope not departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise stated, "parts" and "%" are mass benchmarks.

<Synthesis Example 1> [Polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and benzyl alcohol (A-1: no radical polymerizable group Synthesis of polyimide precursor)] Suspend 14.06g (64.5mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours) and 14.22g (131.58mmol) of benzyl alcohol in 50mL N-methylpyrrolidone and dried over molecular sieves. The suspension was heated at 100°C for 3 hours. After a few minutes of heating a clear solution was obtained. 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 were added over 10 minutes while maintaining the temperature at -10±4°C. During the addition of SOCl ₂ the viscosity was increased. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 20 minutes at -5 to 0°C. The resulting solution. Next, after allowing the reaction mixture to react at 0°C for 1 hour, 70 g of ethanol was added, followed by stirring overnight at room temperature. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Next, 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. A-1 [chemical formula 34]

<Synthesis Example 2> [Polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-2: with free 14.06g (64.5mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours), 16.8g (129mmol) ) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 millimoles) and 100 g of diglyme (diethylene glycol dimethyl ether) were mixed , Stirring at a temperature of 60° C. for 18 hours produced a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Then, after the obtained diester was chlorinated by SOCl ₂ , it was converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and 1 The same method obtained the polyimide precursor. The weight average molecular weight of the polyimide precursor was 19,000. A-2 [chemical formula 35]

<Synthesis Example 3> [Polyimide precursor derived from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate ( A-3: Synthesis of polyimide precursor having radically polymerizable groups] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol) of pyridine, and 100 g of diethylene glycol Alcohol dimethyl ether was mixed and stirred at a temperature of 60° C. for 18 hours to manufacture a diester of 4,4′-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. Then, after the obtained diester was chlorinated by SOCl ₂ , it was converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and 1 The same method obtained the polyimide precursor. The weight average molecular weight of the polyimide precursor was 18,000. A-3 [chemical formula 36]

<Synthesis Example 4> [Derived from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (ortho-toluene) and methacrylic acid- Synthesis of polyimide precursor of 2-hydroxyethyl ester (A-4: polyimide precursor with radical polymerizable group)] 20.0 g (64.5 millimoles) of 4,4'- Oxydiphthalic anhydride (stirred 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 millimoles) and 100 g of diglyme, and stirred at 60°C for 18 hours to produce 4,4'-oxydiphthalic anhydride and methacrylic acid-2-hydroxyethyl Diesters of esters. Next, after the obtained diester was chlorinated by SOCl ₂ , it was converted into polyimide by the same method as in Synthesis Example 1 using 4,4'-diamino-2,2'-dimethylbiphenyl Precursor, and obtained polyimide precursor with the same method as Synthetic Example 1. The weight average molecular weight of the polyimide precursor was 19,000. A-4 [chemical formula 37]

<Synthesis Example 5> [Polybenzoxazole precursor derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxodibenzoyl chloride (A-5) Synthesis] To 100 mL of N-methyl-2-pyrrolidone, 13.92 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added and dissolved with stirring. Next, 11.21 g of 4,4'- oxydibenzoyl chlorides were dripped over 10 minutes, keeping temperature 0-5 degreeC, 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 for 15 minutes at a speed of 5000 rpm. The polybenzoxazole precursor was removed by filtration, stirred again in 6 liters of water for 30 minutes and filtered again. Next, the obtained polybenzoxazole precursor was dried at 45° C. for 3 days under reduced pressure. The weight average molecular weight of the polybenzoxazole precursor is 15,000. A-5 [chemical formula 38]

<Synthesis Example 6> [Synthesis of Polymer (RA-1) for Comparative Example] 27.0 g (153.2 mmol) of benzyl methacrylate, 20 g (157.3 mmol) of N-isopropylmethyl Acrylamide, 39 g (309.2 mmol) of allyl methacrylate, 13 g (151.0 mmol) of methacrylic acid, polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) 3.55 g (15.4 millimoles) and 300 g of 3-methoxy-2-propanol were mixed. Under a nitrogen atmosphere, the mixed solution was added dropwise to 300 g of 3-methoxy-2-propanol heated to 75° C. over 2 hours. After completion of the dropwise addition, stirring was carried out at 75° C. for 2 hours under a nitrogen atmosphere. After the reaction, the polymer was precipitated in 5 liters of water and stirred at a speed of 5000 rpm for 15 minutes. The acrylic resin was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the acrylic resin was dried at 45° C. for 3 days under reduced pressure. The polymer had a weight average molecular weight of 25,000. RA-1 [Chemical Formula 39]

＜Example and Comparative Example＞ The components described in the following tables were mixed to obtain each photosensitive resin composition. The obtained photosensitive resin composition was pressure-filtered through a filter having a pore width of 0.8 μm. ＜＜Composition of Photosensitive Resin Composition＞＞ Polyimide precursor: parts by mass recorded in the table Radical polymerization initiator: parts by mass recorded in the table Radical polymerizable compound: parts by mass listed in the table Other ingredients; parts by mass recorded in the table

[比較用化合物] [化學式41]

(B) A compound whose acidity decreases when heated (acid disappearing agent) [Chemical formula 40]

[compound for comparison] [chemical formula 41]

Below, the pKa values before and after heating at 300° C. are shown. [Table 1]

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

D-3：A-TMMT（Shin-Nakamura Chemical Co.,Ltd.製）(D) Radical polymerizable compound D-1: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) D-2: SR-209 (manufactured by Sartomer Company, Inc.) [Chemical formula 42]

D-3: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)

(E) Polymerization inhibitor E-1: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) E-2: p-benzoquinone (Tokyo Chemical Industry Co. , Ltd.) E-3: p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (F) Migration inhibitor F-1: the following compound F-2: the following compound F-3: the following Said compound F-4: the following compound [chemical formula 43]

(G) Metal adhesion improver G-1: The following compound G-2: The following compounds G-3: The following compounds

Et：乙基[chemical formula 44]

Et: ethyl

H-2光硬化促進劑（光鹼產生劑）：下述化合物 Et：乙基 [化學式46]

Me：甲基(H) Hardening accelerator (base generator) H-1 photohardening accelerator (photobase generator): the following compound [chemical formula 45]

H-2 photohardening accelerator (photobase generator): the following compound Et: ethyl [chemical formula 46]

Me: methyl

(I) solvent I-1: γ-butyrolactone (manufactured by SANWAYUKA INDUSTRY CORPORATION) I-2: Dimethylsulfone (manufactured by Wako Pure Chemical Industries, Ltd.) I-3: N-methyl-2-pyrrolidone (manufactured by Ashland Corporation)

＜Storage stability＞ The viscosity (0 day) of the photosensitive resin composition after the said filtration was measured using the E-type viscometer. After allowing the photosensitive resin composition to stand at 25° C. for 14 days in an airtight container, the viscosity was measured again using an E-type viscometer (14 days). The viscosity reduction rate was calculated from the following formula. The lower the viscosity decrease rate, the higher the storage stability. Viscosity reduction rate=100×{1-(viscosity (14 days)/viscosity (0 days))} The measurement of viscosity was performed at 25 degreeC, and it followed JISZ 8803:2011 except that. A: The viscosity reduction rate is 5% or less B: The viscosity reduction rate is greater than 5% and less than 10% C: The viscosity reduction rate is greater than 10% and less than 15% D: The viscosity reduction rate is greater than 15% and less than 20% E: The viscosity reduction rate is greater than 20%

<Elongation at break> The photosensitive resin composition layer was formed by applying each of the above filtered photosensitive resin compositions in a layered form on a silicon wafer by a spin coating method. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to form a uniform photosensitive resin composition layer with a thickness of 20 μm on the silicon wafer. Use a stepper (Nikon NSR 2005 i9C) to expose the photosensitive resin composition layer on the silicon wafer with an exposure energy of 500mJ/ ^cm2 . The temperature of the photosensitive resin composition layer (resin layer) was raised to 250° C., and then the temperature was maintained for 3 hours. The cured resin layer was immersed in a 4.9% hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain the resin film 1 .

Regarding the elongation at break of the resin film 1, use a tensile testing machine (TENSILON) at 25°C and 65% relative humidity for the longitudinal direction and width direction of the film at a crosshead speed of 300 mm/min, a width of 10 mm, and a sample length of 50 mm. The elongation at break was measured in accordance with JIS-K6251:2017 in an environment of (RH). The elongation at break is calculated by E _b = (L _b - L ₀ )/L ₀ (E _b : elongation at the time of cutting, L ₀ : length of the test piece before the test, L _b : test when the test piece has been cut slice length) is calculated. In the evaluation, each of the elongation at break in the longitudinal direction and the width direction was measured five times, and the average value in the longitudinal direction and the width direction was used. A: Elongation at break greater than 80% B: Elongation at break greater than 70% and less than 80% C: Elongation at break greater than 60% and less than 70% D: Elongation at break greater than 50% and less than 60% E: Break Elongation below 50%

<Resolution Evaluation of Minimum Line Width Pattern> Spin-coat each photosensitive resin composition after filtration on a silicon wafer on a heating plate, and dry the silicon wafer to which the photosensitive resin composition is applied at 100°C for 5 Minutes, thereby forming a 20 μm photosensitive resin composition layer with a uniform film thickness on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). Exposure is performed using i-rays at a wavelength of 365nm, with exposure energies of 200, 300, 400, 500, 600, 700, and 800mJ/ ^cm2 , using a line-space mask with a 1μm scale from 5μm to 25μm. A resin layer was obtained.

The above-mentioned resin layer was developed with cyclopentanone for 60 seconds. The smaller the line width of the obtained resin layer (line pattern), the finer the pattern can be formed, and it is a better result. In addition, the less likely the minimum line width that can be formed is changed in response to fluctuations in exposure amount, the more arbitrary the exposure amount in fine pattern formation becomes, which is a preferable result. The measurement limit is 5 μm. A: 5 μm or more and 8 μm or less B: More than 8 μm and 10 μm or less C: More than 10 μm and 15 μm or less D: More than 15 μm and 20 μm or less E: greater than 20μm F: A pattern having a line width with edge sharpness could not be obtained

[表3]

[Table 2]

[table 3]

[Table 4]

From the above results, it can be seen that in the present invention, sufficient curability is maintained and high storage stability is achieved by using the combination of the polymer precursor and the specific acid disappearing agent. In addition, it can be seen that, when necessary, high elongation at break and good resolution of the minimum line width pattern of the cured product are also achieved, and high performance can be exhibited according to requirements. On the other hand, in the comparative example which did not use a specific acid disappearing agent, storage stability was inferior, and elongation at break was also insufficient. It is also clear from this result that the photosensitive resin composition of the present invention exhibits excellent performance in the manufacture of semiconductor devices and their products.

<Example 100> After passing the photosensitive resin composition (1) through a filter with a pore width of 1.0 μm and filtering under pressure, it was spin-formed on the surface of a resin substrate on which a thin copper layer was formed (3500 rpm, 30 seconds clock) and apply. After drying the photosensitive resin composition applied to the resin substrate at 100°C for 2 minutes, exposure was performed using a stepper (manufactured by Nikon Corporation, NSR1505i6). Exposure was performed at a wavelength of 365 nm at an exposure dose of 200 mJ/cm ² through a mask. After exposure, it baked, developed with cyclopentanone for 30 seconds, and rinsed with PGMEA for 20 seconds to obtain a pattern. Next, it heated at 230 degreeC for 3 hours, and formed the interlayer insulating film for rewiring layers. The interlayer insulating film for a rewiring layer is excellent in insulating properties.

none

none.

Claims (32)

A photosensitive resin composition comprising polyimide precursors and polybenzo

The polymer precursor in the azole precursor and the compound whose acidity decreases when heated is a compound represented by any one of formulas A1 to A3; (X) _m -L ^A -( Y) _n ‥‥Formula A1 In the formula, X represents -COOH, -SO ₃ H or -PO ₃ ^H ₂ , and LA represents a group selected from aliphatic linking groups, aryl linking groups and combinations thereof The m+n valent linking group, L ^A can contain the linking group Lh with the following heteroatoms, Lh is oxygen atom, sulfur atom, carbonyl, thiocarbonyl, sulfonyl, or -NR-, R is hydrogen An atom or an organic group, Y represents -OH or -NH(R ^N ), R ^N represents a hydrogen atom, m represents an integer from 1 to 4, and n represents an integer from 1 to 4; (X) _m -L ^A -(Q ) _n ‥‥Formula A2 In the formula, X represents -COOH, -SO ₃ H or -PO ₃ ^H ₂ , LA represents m+n valent linking group, Q represents -CONH(R ^N ), -OCONH(R ^N ) , -N(R ^N )CONH(R ^N ) or -N(R ^N ) ₃ ⁺ A ^- , A ^- is an atom or group of atoms forming a counter ion; Z-( ^LC -COOH) _nz ‥‥Formula A3 Among them, Z represents an nz-valent organic group, L ^C represents * ¹ -(C=O)C(R ^a ) ₂ -* ² , -CH(R ^b )- or -C(R ^b ) ₂ -, R ^a Represents a hydrogen atom, alkyl, alkenyl, aryl or aralkyl, R ^b represents an alkyl, alkenyl, aryl or aralkyl, * ¹ represents the bonding position on the Z side, * ² represents the bond on the COOH side Knot position, nz is an integer from 1 to 4. The photosensitive resin composition as described in item 1 of the scope of the patent application, wherein in the formula A1, X is -SO ₃ H. A photosensitive resin composition comprising polyimide precursors and polybenzo

The polymer precursor in the azole precursor and the compound whose acidity decreases when heated is a compound represented by any one of formulas A1 to A3; (X) _m -L ^A -( Y) _n ‥‥Formula A1 In the formula, X represents -SO ₃ ^H , LA represents m+n valent linking group, Y represents -OH, -COOH or -NH(R ^N ), R ^N is a hydrogen atom or an organic group group, m represents an integer from 1 to 4, and n represents an integer from 1 to 4; (X) _m -LA -(Q) _n ‥‥Formula A2 In the formula, X represents -SO ₃ H, and ^{L A represents} m+n A valent linking group, Q represents a group that releases an alkali component by heating; Z-(L ^C -COOH) _nz ‥‥ Formula A3 In the formula, Z represents an nz-valent organic group, and L ^C represents * ¹ -(C= O)C(R ^a ) ₂ -* ² , -CH(R ^b )- or -C(R ^b ) ₂ -, R ^a represents a hydrogen atom, alkyl, alkenyl, aryl or aralkyl, R ^b Represents an alkyl, alkenyl, aryl or aralkyl group, * ¹ represents the bonding position on the Z side, * ² represents the bonding position on the COOH side, and nz is an integer from 1 to 4. The photosensitive resin composition as described in item 3 of the scope of the patent application, wherein in formula A1, L ^A represents the m+n valence selected from the group consisting of aliphatic linking group, aryl linking group and combinations thereof Connection base. The photosensitive resin composition as described in any one of the first to fourth claims of the patent application, wherein in the formula A1, L ^A is a linking group connecting X and Y with an atomic number of 3 or more and 6 or less. The photosensitive resin composition described in any one of items 1 to 4 of the scope of the patent application, wherein the relationship between m and n in formula A1 is m

n. The photosensitive resin composition as described in any one of the first to fourth claims of the patent application, wherein the content of the compound whose acidity decreases when heated is 0.01% by mass or more and 10.0% by mass in the photosensitive resin composition %the following. The photosensitive resin composition described in any one of items 1 to 4 of the patent claims, wherein the compound whose acidity decreases when heated is a compound whose acidity decreases by heating at 400°C. The photosensitive resin composition as described in any one of the first to fourth claims of the patent claims, wherein the pKa of the compound whose acidity decreases when heated is -5.0 or more and 2.0 or less. The photosensitive resin composition as described in any one of the first to fourth claims of the patent application, wherein the pKa difference before and after heating of the compound whose acidity decreases when heated is 8.0 or more. The photosensitive resin composition described in any one of items 1 to 4 of the patent claims, wherein the compound whose acidity decreases when heated is a compound whose acid group undergoes intramolecular dehydration condensation by heating. The photosensitive resin composition as described in any one of items 1 to 4 of the patent claims, wherein the molecular weight of the compound whose acidity decreases when heated is not less than 80 and not more than 1000. The photosensitive resin composition described in any one of items 1 to 4 of the scope of the patent application further includes a radical polymerization initiator and a radical polymerizable compound. The photosensitive resin composition described in any one of items 1 to 4 of the scope of the patent application, wherein the polymer precursor includes a polyimide precursor. The photosensitive resin composition as described in claim 14, wherein the polyimide precursor has a constituent unit represented by the following formula (1):

In formula (1), A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or 1-valent organic group. The photosensitive resin composition as described in claim 15, wherein at least one of R ¹¹³ and R ¹¹⁴ in the formula (1) contains a radical polymerizable group. The photosensitive resin composition as described in claim 15, wherein R ¹¹⁵ in the formula (1) is a group containing an aromatic ring. The photosensitive resin composition as described in item 15 of the scope of patent application, wherein R ¹¹¹ in the formula (1) is represented by -Ar ⁰ -L ⁰ -Ar ⁰ -; Ar ⁰ independently represents an aromatic group, L ⁰ represents a single bond, an aliphatic hydrocarbon group with 1 to 10 carbons that can be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO- and A group selected from a combination of these. The photosensitive resin composition as described in claim 15, wherein R ¹¹¹ in the formula (1) is represented by the following formula (51) or formula (61);

In formula (51), R ⁵⁰ ~ R ⁵⁷ independently represent a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ ~ R ⁵⁷ represents a fluorine atom, methyl, fluoromethyl, difluoromethane group or trifluoromethyl;

In formula (61), R ⁵⁸ and R ⁵⁹ each independently represent a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group. The photosensitive resin composition described in any one of items 1 to 4 of the scope of the patent application, which is used for development using a developer solution containing more than 90% of an organic solvent. The photosensitive resin composition described in any one of items 1 to 4 of the patent claims, which is used for forming an interlayer insulating film for a rewiring layer. A cured film, which is formed by curing the photosensitive resin composition described in any one of claims 1 to 21. The hardened film as described in item 22 of the patent application, wherein the film thickness is 1 μm to 30 μm. A laminated body having two or more layers of the cured film described in claim 22 or claim 23 of the patent application. A laminate having 3 to 7 layers of the hardened film described in item 22 or item 23 of the scope of the patent application. The laminate according to claim 24, wherein a metal layer is provided between the cured films. A method for producing a cured film, comprising a film forming step of applying the photosensitive resin composition described in any one of claims 1 to 21 to a substrate to form a film. The method for producing a cured film according to claim 27, comprising an exposing step of exposing the film and a developing step of developing the film. The method for producing a cured film as described in claim 28, wherein the developer used in the development contains more than 90% of organic solvent. The method of manufacturing a cured film according to any one of the 27th to 29th claims of the patent application, which includes the step of heating the film at 80°C to 450°C. A method for manufacturing a laminate, which performs the method for manufacturing a cured film described in any one of the 27th to 29th claims of the patent application multiple times. A semiconductor device having the cured film described in Claim 22 or Claim 23, or the laminate described in any one of Claims 24 to 26.