TWI802670B - Photosensitive resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Abstract

The present invention provides a photosensitive resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device, wherein the photosensitive resin composition contains a heterocycle-containing polymer precursor, a thermal base generator, and a free radical A polymerizable compound, the precursor of the above-mentioned heterocycle-containing polymer has a radically polymerizable group, and the above-mentioned free-radically polymerizable compound includes a compound having 4 or more polymerizable functional groups and a compound having 3 polymerizable functional groups and a molecular weight of It is at least 1 radically polymerizable compound in the group of 400 or less compounds.

Description

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

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

Heterocycle-containing polymers such as polyimide and polybenzoxazole are excellent in heat resistance and insulation, and thus are used in insulating films of semiconductor devices and the like. In addition, in order to form the film or form it, it is often necessary to dissolve the precursors before the cyclization reaction with high solvent solubility, such as polyimide precursors and polybenzoxazole precursors, etc. in a solvent. use in the state. After applying this resin composition to a board|substrate etc., it heats and cyclizes the said precursor, and can form a cured film.

As a resin composition of such a precursor of a heterocycle-containing polymer, for example, Patent Document 1 discloses a thermosetting resin composition containing a specific thermal base generator and a precursor of a heterocycle-containing polymer. It is described that thereby, a thermosetting resin composition capable of cyclization of the thermosetting resin at low temperature and excellent in stability is provided. [Prior Art Literature] [Patent Document]

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

Through the development of a composition containing a precursor of a heterocyclic polymer as described above, it has been attempted to improve performance corresponding to its needs and improve manufacturing adaptability in many applications. However, many parts of these resins and the precursors are unknown, and various properties are required, which are yet to be researched and developed. For example, in the case of an insulating film of a semiconductor device, metal etching and the like are performed, and various chemical treatments are performed in order to form the device structure. Therefore, resistance to drug handling is required. In addition, in consideration of the durability and impact resistance of the device, sufficient elongation at break is also required. Generally, when the chemical resistance is improved, the elongation at break tends to decrease, and it is difficult to achieve both. Therefore, the object of the present invention is to provide a photosensitive resin composition capable of achieving both chemical resistance and excellent elongation at break of the cured resin. Moreover, it aims at providing the cured film which used the said photosensitive resin composition, the laminated body, the manufacturing method of the cured film, and a semiconductor device.

式（101）及式（102）中，R¹ ～R⁶ 分別獨立地表示氫原子或烴基，R⁹ 表示烴基。 ＜4＞如＜1＞至＜3＞中任一項所述之感光性樹脂組成物，其中上述含雜環聚合物的前驅物包括聚醯亞胺前驅物或聚苯并噁唑前驅物。 ＜5＞如＜1＞至＜3＞中任一項所述之感光性樹脂組成物，其中上述含雜環聚合物的前驅物包括聚醯亞胺前驅物。 ＜6＞如＜1＞至＜5＞中任一項所述之感光性樹脂組成物，其中上述含雜環聚合物的前驅物包含由下述式（1）表示之構成單元； [化學式2]

式（1）中，A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹¹ 表示2價的有機基團，R¹¹⁵ 表示4價的有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價的有機基團。 ＜7＞如＜6＞項中記載之感光性樹脂組成物，其中上述R¹¹³ 及上述R¹¹⁴ 中的至少1個包含自由基聚合性基。 ＜8＞如＜6＞或＜7＞項中記載之感光性樹脂組成物，其中上述R¹¹⁵ 包含芳香環。 ＜9＞如＜6＞至＜8＞中任一項所述之感光性樹脂組成物，其中上述R¹¹¹ 由-Ar⁰ -L⁰ -Ar⁰ -表示，各Ar⁰ 分別獨立地為包含芳香環之2價的基團，L⁰ 為單鍵、可以被氟原子取代的碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO₂ -、-NHCO-及組合該等基團中的2個以上而成之基團。 ＜10＞如＜6＞至＜9＞中任一項所述之感光性樹脂組成物，其中上述R¹¹¹ 為由下述式（51）或式（61）表示之基團； [化學式3]

式（51）中，R⁵⁰ ～R⁵⁷ 分別獨立地為氫原子､氟原子或1價的有機基團，R⁵⁰ ～R⁵⁷ 中的至少1個為氟原子､甲基､氟甲基､二氟甲基或三氟甲基， [化學式4]

式（61）中，R⁵⁸ 及R⁵⁹ 分別獨立地為氟原子､氟甲基､二氟甲基或三氟甲基。 ＜11＞如＜1＞至＜10＞中任一項所述之感光性樹脂組成物，其含有光聚合起始劑。 ＜12＞如＜1＞至＜11＞中任一項所述之感光性樹脂組成物，其中上述熱鹼產生劑與上述自由基聚合性化合物的質量比為1.0～80。 ＜13＞如＜1＞至＜12＞中任一項所述之感光性樹脂組成物，其中使用相對於上述含雜環聚合物的前驅物100質量份用為2.5質量份以上62.5質量份以下的上述自由基聚合性化合物。 ＜14＞如＜1＞至＜13＞中任一項所述之感光性樹脂組成物，其還含有溶劑。 ＜15＞如＜1＞至＜14＞中任一項所述之感光性樹脂組成物，其用於使用含有90質量%以上的有機溶劑之顯影液進行之顯影。 ＜16＞如＜1＞至＜15＞中任一項所述之感光性樹脂組成物，其使用於再配線層用層間絕緣膜的形成。 ＜17＞一種硬化膜，使＜1＞～＜16＞中任一項所述之感光性樹脂組成物硬化而成。 ＜18＞一種積層體，其具有兩層以上的＜17＞項所述之硬化膜。 ＜19＞如＜18＞項所述之積層體，在上述硬化膜之間具有金屬層。 ＜20＞如＜18＞或＜19＞項所述之積層體，其具有3～7層上述硬化膜。 ＜21＞一種硬化膜的製造方法，其包括：將＜1＞至＜16＞中任一項所述之感光性樹脂組成物應用於基板來形成感光性樹脂組成物層之感光性樹脂組成物層形成製程；及將上述感光性樹脂組成物層進行曝光之曝光製程。 ＜22＞如＜21＞項所述之硬化膜的製造方法，其還具有在上述曝光製程之後，將上述感光性樹脂組成物層進行顯影之顯影製程。 ＜23＞如＜22＞項所述之硬化膜的製造方法，其中上述顯影製程使用含有90質量%以上的有機溶劑之顯影液來進行顯影。 ＜24＞如＜22＞或＜23＞項所述之硬化膜的製造方法，其包括在上述顯影製程之後，將上述感光性樹脂組成物層在50～450℃的溫度下加熱之顯影後加熱製程。 ＜25＞如＜24＞項所述之硬化膜的製造方法，其中上述加熱溫度為50～250℃。 ＜26＞如＜21＞至＜25＞中任一項所述之硬化膜的製造方法，上述硬化膜的膜厚為1～30μm。 ＜27＞一種半導體器件，其具有＜17＞項所述之硬化膜或＜18＞至＜20＞中任一項所述之積層體。 [發明效果]Based on the above-mentioned problems, as a result of intensive research by the present inventors, it was found that a specific compound was selected as a radical polymerizable compound, and a precursor of a heterocyclic polymer containing a radical polymerizable group was used in combination with a thermal base generator. , thereby solving the above-mentioned problems. Specifically, the above-mentioned problems are solved by the following method <1>, preferably <2> to <27>. <1> A photosensitive resin composition comprising a precursor of a heterocyclic polymer, a thermal base generator, and a radically polymerizable compound, wherein the precursor of the heterocyclic polymer has a radically polymerizable group, and the radical The radically polymerizable compound includes at least one radically polymerizable compound selected from the group consisting of compounds having 4 or more polymerizable functional groups and compounds having 3 polymerizable functional groups and a molecular weight of 400 or less. <2> The photosensitive resin composition according to <1>, wherein the polymerizable functional groups are each independently a group selected from vinylphenyl, vinyl, and (meth)acryl. <3> The photosensitive resin composition as described in <1> or <2>, wherein the thermal base generator has a cation represented by formula (101) or formula (102); [Chemical formula 1]

In formula (101) and formula (102), R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and R ⁹ represents a hydrocarbon group. <4> The photosensitive resin composition according to any one of <1> to <3>, wherein the precursor of the heterocycle-containing polymer includes a polyimide precursor or a polybenzoxazole precursor. <5> The photosensitive resin composition according to any one of <1> to <3>, wherein the precursor of the heterocycle-containing polymer includes a polyimide precursor. <6> The photosensitive resin composition according to any one of <1> to <5>, wherein the precursor of the heterocyclic ring-containing polymer includes a structural 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 hydrogen Atom or monovalent organic group. <7> The photosensitive resin composition as described in the item <6>, wherein at least one of the above-mentioned R ¹¹³ and the above-mentioned R ¹¹⁴ contains a radical polymerizable group. <8> The photosensitive resin composition as described in item <6> or <7>, wherein the above-mentioned R ¹¹⁵ contains an aromatic ring. <9> The photosensitive resin composition according to any one of <6> to <8>, wherein the above-mentioned R ¹¹¹ is represented by -Ar ⁰ -L ⁰ -Ar ⁰ -, and each Ar ⁰ is independently aromatic A divalent ring group, L ⁰ is a single bond, an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, -NHCO- and a group formed by combining two or more of these groups. <10> The photosensitive resin composition according to any one of <6> to <9>, wherein the above R ¹¹¹ is a group represented by the following formula (51) or formula (61); [Chemical formula 3]

In formula (51), 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, di Fluoromethyl or trifluoromethyl, [chemical formula 4]

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group. <11> The photosensitive resin composition as described in any one of <1>-<10> which contains a photoinitiator. <12> The photosensitive resin composition according to any one of <1> to <11>, wherein the mass ratio of the thermal base generator to the radical polymerizable compound is 1.0-80. <13> The photosensitive resin composition according to any one of <1> to <12>, wherein the amount used is not less than 2.5 parts by mass and not more than 62.5 parts by mass relative to 100 parts by mass of the precursor of the heterocyclic ring-containing polymer. The above radical polymerizable compound. <14> The photosensitive resin composition according to any one of <1> to <13>, which further contains a solvent. <15> The photosensitive resin composition as described in any one of <1>-<14> used for image development using the developing solution containing 90 mass % or more of organic solvents. <16> The photosensitive resin composition as described in any one of <1>-<15> used for formation of the interlayer insulating film for rewiring layers. <17> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <16>. <18> A laminate having two or more layers of the cured film described in the item <17>. <19> The laminate according to <18>, which has a metal layer between the cured films. <20> The laminate according to item <18> or <19>, which has 3 to 7 layers of the above cured film. <21> A method for producing a cured film, comprising: applying the photosensitive resin composition described in any one of <1> to <16> to a substrate to form a photosensitive resin composition layer a layer forming process; and an exposure process for exposing the photosensitive resin composition layer. <22> The manufacturing method of the cured film as described in <21> item which further has the development process of developing the said photosensitive resin composition layer after the said exposure process. <23> The manufacturing method of the cured film as described in <22> term which develops using the developing solution containing 90 mass % or more of organic solvents in the said image development process. <24> The method for producing a cured film according to <22> or <23>, which includes post-development heating of heating the photosensitive resin composition layer at a temperature of 50 to 450° C. after the development step Process. <25> The method for producing a cured film according to <24>, wherein the heating temperature is 50 to 250°C. <26> The method for producing a cured film according to any one of <21> to <25>, wherein the thickness of the cured film is 1 to 30 μm. <27> A semiconductor device comprising the cured film according to <17> or the laminate according to any one of <18> to <20>. [Invention effect]

According to the present invention, it is possible to provide a photosensitive resin composition capable of taking into account the chemical resistance and high elongation at break of the hardened resin. Moreover, the cured film using the said photosensitive resin composition, a laminated body, the manufacturing method of a cured film, and a semiconductor device can be provided.

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 such embodiments. Regarding the notation of a group (atomic group) in this specification, the notation of substituted and unsubstituted includes both those not having a substituent and those having 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). In this specification, "actinic ray" means, for example, the bright-line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In addition, in the present invention, "light" refers to actinic rays or radiation. "Exposure" in this specification unless otherwise stated, exposure includes not only exposure using mercury lamps, far ultraviolet rays represented by excimer lasers, X-rays, EUV light, etc., but also exposure using particles such as electron beams and ion beams. The description of the bundle. In this specification, the numerical range represented by "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. 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 "process" is not only an independent process, but it is also included in this term if it can achieve the expected effect of the process even if it cannot be clearly distinguished from other processes. In this specification, the solid content concentration refers to the mass percentage of the mass of components other than the solvent with respect 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, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super One or more of HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) was used to obtain it. Unless otherwise specified, the eluent was measured using 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 is characterized in that it contains a precursor of a heterocyclic polymer, a thermal base generator, and a radical polymerizable compound, the precursor of the heterocyclic polymer has a radical polymerizable group, The radically polymerizable compound includes at least one radically polymerizable compound selected from the group consisting of compounds having 4 or more polymerizable functional groups and compounds having 3 polymerizable functional groups and a molecular weight of 400 or less. The photosensitive resin composition containing the precursor of the heterocycle-containing polymer and the thermal base generator can improve chemical resistance by using a polyfunctional radical polymerizable compound. However, only by the above method, there is a tendency for the elongation at break to decrease. Therefore, it is expected that in the present invention, in addition to the polymerizable compound, the polymer and the thermal base generator also intervene in the crosslinking, and it is expected that the crosslinking will be properly cut along with the cyclization. For this reason, it is preferable that the site that is favorable for the cyclization reaction has a radically polymerizable group, and the above constitution was found. In addition, the description of the relevant mechanism includes speculation, and the present invention is not limited thereby.

＜Specific radically polymerizable compound＞ The radically polymerizable compound used in the present invention (in this specification, sometimes referred to as "specific radically polymerizable compound") is selected from compounds containing four or more polymerizable functional groups and compounds having three polymerizable functional groups. And at least one radically polymerizable compound in the group of compounds having a molecular weight of 400 or less. The polymerizable functional group is preferably a group selected from vinylphenyl, vinyl, and (meth)acryl groups (in this specification, these polymerizable functional groups are referred to as "polymerizable functional group Ps"). . When there are 4 or more polymerizable functional groups, the number of functional groups of the specific radical polymerizable compound is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less. Moreover, the molecular weight of the radically polymerizable compound which has 4 or more polymerizable functional groups is preferably 1000 or less, more preferably 800 or less, still more preferably 600 or less. The lower limit is actually 400 or more. By setting it as the said range, the crosslink density of a film becomes optimum, and elongation at break and chemical resistance improve. The specific radical polymerizable compound preferably has a linking group having a linear chain structure of 2 or more atoms, and the radical polymerizable groups are preferably separated from each other. When the polymerizable functional group is 3, the molecular weight of the specific radical polymerizable compound is further preferably 370 or less, more preferably 340 or less, and still more preferably 300 or less. The lower limit is actually 150 or more. By setting it as the said range, the crosslink density of a film becomes optimum, and a breaking elongation and chemical resistance improve.

式（P-1）中，Ps分別獨立地為選自乙烯基苯基、乙烯基及（甲基）丙烯醯基之基團，R^B1 為氫原子或取代基（其中聚合性官能基除外），L^P 分別獨立地為單鍵或連接基。L^Q 為連接基。The trifunctional radical polymerizable compound is preferably a compound represented by the following formula (P-1). [chemical formula 5]

In formula (P-1), Ps are independently selected from vinylphenyl, vinyl, and (meth)acryl, and R ^B1 is a hydrogen atom or a substituent (excluding polymerizable functional groups) , L ^P are each independently a single bond or a linker. L ^Q is a linker.

In the formula, Ps is preferably a (meth)acryl group. R ^B1 is an alkyl group which may have any substituent (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), -NH-Ps or -CH ₂ -OL ^P - Ps is better. As an optional substituent, a hydroxyl group, a carboxyl group, or a group combining these with the linking group ^LP is exemplified.

When L ^P is a linking group, examples of the linking group include an oxygen atom, a sulfur atom, an amino group (NH), a carbonyl group, an (oligo)alkylene group, an alkylene group, a (oligo)alkylene group, and a combination thereof. and other related linking bases. The (oligo)alkyleneoxy group preferably includes (oligo)methyleneoxy, (oligo)ethyleneoxy, and (oligo)propyleneoxy. The linking group may be substituted with a substituent such as a hydroxyl group. In addition, the (oligo)alkylene group means a single alkylene group or an oligoalkylene group in which a plurality of alkylene groups are repeated. The number of repetitions of the (oligo)alkyleneoxy group is preferably 1-8, more preferably 1-4, still more preferably 1-2. The number of carbon atoms in the alkylene group is preferably 1-12, more preferably 1-6, and still more preferably 1-3. The alkylene group may be substituted with a substituent such as a hydroxyl group. The (oligo)alkylene amino group is preferably a (oligo)methylidene group, a (oligo)ethylidene group, or a (oligo)propylidene group. The (oligo)alkylene amino groups may be substituted with substituents such as hydroxyl groups. The repeating number of (oligo)alkylene amino groups is preferably 1-12, more preferably 1-6, and still more preferably 1-3. The number of bonding atoms for the intervening removal of hydrogen atoms in the divalent linking group formed by ^LP is preferably 1-30, more preferably 2-20, and still more preferably 3-16. L ^Q is a linking group, and specific examples thereof include linking groups exemplified in L ^P. Among them, an alkylene group is preferable, 1-12 carbon atoms are more preferable, 1-6 carbon atoms are more preferable, and 1-3 carbon atoms are still more preferable. In particular, a methylene group or an ethylene group is preferable, and a methylene group is more preferable.

式（P-2）中，Ps分別獨立地為選自乙烯基苯基、乙烯基及（甲基）丙烯醯基之基團，R^B2 為氫原子或取代基（其中聚合性官能基除外），L^P 分別獨立地為單鍵或連接基，pm為1～6的整數，pn為1或2。 Ps、R^B2 、L^P 、L^Q 各自的定義與式（P-1）中之Ps、R^B1 、L^P 、L^Q 的定義相同，較佳範圍亦相同。 pn為1時，R^B2 為氫原子或取代基（其中聚合性官能基除外）。作為取代基，烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）為較佳。 pn為2時，R^B2 成為2價的連接基。作為2價的連接基，可列舉伸烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、氧原子、羰基、胺基（NH）或與該等組合相關之基團。It is preferable that the radically polymerizable compound having four or more functions is a compound represented by the following formula (P-2). [chemical formula 6]

In formula (P-2), Ps are independently selected from vinylphenyl, vinyl and (meth)acryl groups, and R ^B2 is a hydrogen atom or a substituent (excluding polymerizable functional groups) , L ^P are each independently a single bond or a linking group, pm is an integer of 1-6, and pn is 1 or 2. The definitions of Ps, R ^B2 , L ^P and L ^Q are the same as those of Ps, R ^B1 , L ^P and L ^Q in the formula (P-1), and the preferred ranges are also the same. When pn is 1, R ^B2 is a hydrogen atom or a substituent (except for a polymerizable functional group). As a substituent, an alkyl group (preferably 1-12 carbon atoms, more preferably 1-6 carbon atoms, still more preferably 1-3 carbon atoms) is preferable. When pn is 2, ^RB2 becomes a divalent linking group. Examples of divalent linking groups include alkylene groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), oxygen atoms, carbonyl groups, amino groups (NH) or Groups related to these combinations.

式（P-3）中，Ps分別獨立地為選自乙烯基苯基、乙烯基及（甲基）丙烯醯基之基團，L^q 為rm+1價的連接基，rm為0～12的整數。 式中，Ps為（甲基）丙烯醯基為較佳。 L^q 為伸烷基（碳數1～60為較佳，3～40為更佳，4～24為進一步較佳）、胺基（NH）、羰基、氧原子、（低聚）伸烷氧基（例如，（低聚）伸甲基氧基、（低聚）伸乙基氧基、（低聚）伸丙基氧基、重複數的較佳的數為1～24為較佳，3～18為更佳，4～14為進一步較佳）、（低聚）伸烷胺（NH）基（例如，（低聚）伸甲胺基、（低聚）伸乙胺基、（低聚）伸丙胺基、重複數的較佳的數為1～24為較佳，3～18為更佳，4～14為進一步較佳）或該等的組合為較佳。 Ps不僅可以在L^q 的末端取代，亦可以在中間取代。L^q 為比較長的鏈的基團為較佳，作為干預去除氫原子之鍵結之原子的數，5以上且100以下為較佳，6以上且50以下為更佳，7以上且40以下為進一步較佳。 rm為0～12的整數，1～8為較佳，1～6為更佳。It is also preferable that the radically polymerizable compound having four or more functions is a compound represented by the following formula (P-3). [chemical formula 7]

In formula (P-3), Ps are independently selected from vinylphenyl, vinyl and (meth)acryl groups, L ^q is a linking group with a valence of rm+1, and rm is 0 to 12 an integer of . In the formula, Ps is preferably a (meth)acryl group. L ^q is an alkylene group (preferably 1 to 60 carbons, more preferably 3 to 40, and further preferably 4 to 24), amino (NH), carbonyl, oxygen atom, (oligomeric) alkylene oxide (for example, (oligomeric) methyleneoxy, (oligomeric) ethyloxyl, (oligomeric) propyleneoxyl, the preferred number of repetitions is 1 to 24, and 3 ~18 is more preferable, 4~14 is further preferable), (oligo)alkylene amine (NH) group (for example, (oligo)methylidene, (oligo)ethylidene, (oligo) ) the propylimino group, the number of repetitions is preferably 1 to 24, more preferably 3 to 18, and still more preferably 4 to 14) or a combination of these is preferred. Ps can be substituted not only at the end of L ^q , but also in the middle. L ^q is preferably a group having a relatively long chain, and the number of bonded atoms intervening in the removal of a hydrogen atom is preferably 5 or more and 100 or less, more preferably 6 or more and 50 or less, and 7 or more and 40 or less for further improvement. rm is an integer of 0-12, preferably 1-8, more preferably 1-6.

In the radically polymerizable compound represented by any one of the formulas (P-1) to (P-3), it is preferable that the linking group represented by L ^P + L ^Q or L ^q in the compound exists with a corresponding length. When this length is expressed as a ratio of mass in one molecule, the ratio represented by the formula weight of L ^p + L ^Q or L ^q / the molecular weight of the radically polymerizable compound × 100 is 5% by mass or more and 80% by mass or less It is more preferable that it is 10 mass % or more and 70 mass % or less, and it is still more preferable that it is 15 mass % or more and 50 mass % or less.

[化學式9]

[化學式10]

[化學式11]

[化學式12]

[化學式13]

[化學式14]

l～o分別獨立地為1～3的自然數。 [化學式15]

B-8為上述4官能化合物或3官能化合物的單獨化合物或上述化合物的混合物。 [化學式16]

[化學式17]

l～q分別獨立地為1～3的自然數。 [化學式18]

[化學式19]

[化學式20]

[化學式21]

Examples of specific radically polymerizable compounds are listed below, but the present invention is not limited thereto. [chemical formula 8]

[chemical formula 9]

[chemical formula 10]

[chemical formula 11]

[chemical formula 12]

[chemical formula 13]

[chemical formula 14]

l to o are each independently a natural number of 1 to 3. [chemical formula 15]

B-8 is a single compound of the above-mentioned tetrafunctional compound or trifunctional compound or a mixture of the above-mentioned compounds. [chemical formula 16]

[chemical formula 17]

l to q are each independently a natural number of 1 to 3. [chemical formula 18]

[chemical formula 19]

[chemical formula 20]

[chemical formula 21]

The content of the specific radically polymerizable compound is preferably at least 2% by mass, more preferably at least 5% by mass, and still more preferably at least 10% by mass, in the solid content of the photosensitive resin composition. The upper limit is preferably at most 50% by mass, more preferably at most 30% by mass, and still more preferably at most 20% by mass. The ratio of the precursor of the heterocycle-containing polymer to the specific radically polymerizable compound is preferably 2.5 parts by mass or more, more preferably 6.2 parts by mass or more, based on 100 parts by mass of the precursor of the heterocycle-containing polymer , 12.5 parts by mass or more is further preferred. As an upper limit, it is preferable that it is 62.5 mass parts or less, it is more preferable that it is 37.5 mass parts or less, and it is still more preferable that it is 25 mass parts or less. One type of specific radical polymerizable compound may be used, or plural types may be used. When using plural types, the total amount is within the above-mentioned range.

In addition, in the present invention, polymerizable compounds other than the specific radical polymerizable compound (hereinafter also referred to as other polymerizable compounds) and precursors of heterocyclic ring-containing polymers described below may or may not be included. One embodiment of the present invention is an aspect containing other polymerizable compounds exceeding 10% by mass of the content of the specific radically polymerizable compound. In this embodiment, the content of other polymerizable compounds is preferably more than 10% by mass and 30% by mass or less of the content of the specific radically polymerizable compound. As another polymerizable compound, a compound having a polymerizable functional group Ps can be used. As for the number of polymeric groups which other polymeric compounds have, 1 or 2 are mentioned, for example. The molecular weight of other polymerizable compounds is preferably at most 2,000, more preferably at most 1,500, and still more preferably at most 900. The lower limit of the molecular weight of the polymerizable compound is preferably 100 or more. Moreover, as another polymeric compound, the compound which has a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; an epoxy compound; an oxetane compound; Specific examples of other polymerizable compounds include compounds described in paragraphs 0102 to 0126 of International Publication No. 2017/104672 that do not correspond to specific radically polymerizable compounds, and these are incorporated in this specification. One embodiment of the present invention is an aspect that does not substantially contain other radically polymerizable compounds. Not containing substantially means that the content of other polymerizable compounds other than the specific radically polymerizable compound is 10% by mass or less, preferably 5% by mass or less, and 3% by mass or less of the content of the specific radically polymerizable compound. It is still more preferable, and 1 mass % or less is still more preferable.

＜Precursors of Heterocyclic Polymers＞ The precursor of the heterocycle-containing polymer used in the present invention has a radical polymerizable group. The radically polymerizable group may be bonded to the side chain of the precursor of the heterocycle-containing polymer, or may be bonded to the main chain. It is preferably bonded to a side chain. As the precursor of the heterocycle-containing polymer, it is preferable to include a polyimide precursor or a polybenzoxazole precursor. 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價的有機基團，R¹¹⁵ 表示4價的有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價的有機基團。<<Polyimide Precursor>> The polyimide precursor used in the present invention has a radical polymerizable group. It is preferable to have a radical polymerizable group in a side chain. It is more preferable to contain a structural unit represented by the following formula (1) as a polyimide precursor. By setting it as such a structure, the composition more excellent in film strength can be obtained. [chemical formula 22]

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 hydrogen Atom or monovalent organic group.

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

R ¹¹¹ represents a divalent organic group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, aromatic heterocyclic groups, or combinations thereof, with carbon numbers of 2 to A linear aliphatic group with 20 carbons, 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 thereof The group is preferably an aromatic group with 6 to 20 carbon atoms. 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. As an example of an aromatic group, the following aromatic group is mentioned.

[chemical formula 23]

In the formula, A is a single bond or selected from aliphatic hydrocarbon groups with 1 to 10 carbons that can be substituted with fluorine atoms, -O-, -C(=O)-, -S-, -S(=O) ₂ - , -NHCO- and the groups in these combinations are preferred, a single bond or an alkylene group with 1 to 3 carbons that can be substituted with a fluorine atom, -O-, -C(=O)-, -S The groups in - 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 group of _2- is further preferred.

As the diamine, specifically, 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 Hexane 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'-diamine-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) fennel, 4,4'-dimethyl -3,3'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5-di Aminobenzoyloxy)ethyl methacrylate, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetyl Guanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane alkanes, 2,7-diamino terpene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzaniline, diaminobenzoic acid Esters, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluoro Butane, 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-amine phenyloxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)benzene base] hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl , 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethyl phenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'- At least one diamine selected from bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobenzidine and 4,4'-diaminoquaterphenyl.

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

[chemical formula 24]

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 preferably a combination of diamines containing two or more of ethylene glycol chains and propylene glycol chains, or both in one molecule, and more preferably a diamine containing no aromatic rings. 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-Aminopropane Oxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., But it is 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 25]

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

In the formula (1), R ¹¹¹ is represented by -Ar ⁰ -L ⁰ -Ar ⁰ -, each Ar ⁰ is independently a divalent group including an aromatic ring, and L ⁰ is a single bond that may be substituted by a fluorine atom An aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, and a combination of two or more of these groups are preferred. The carbon number of Ar ⁰ is preferably from 6 to 22, more preferably from 6 to 18, still more preferably from 6 to 10, particularly preferably a phenylene group. The definition of the preferable range of ^L0 is the same as the definition of A in the above-mentioned AR-8.

式（51）中，R⁵⁰ ～R⁵⁷ 分別獨立地為氫原子､氟原子或1價的有機基團，R⁵⁰ ～R⁵⁷ 中的至少1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價的有機基團，可列舉碳數1～10（較佳為碳數1～6）的未經取代之烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式27]

式（61）中，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，可列舉二甲基-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 26]

In formula (51), 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, di Fluoromethyl or trifluoromethyl; As the monovalent organic group of R ⁵⁰ to R ⁵⁷ , unsubstituted alkyl groups with 1 to 10 carbons (preferably 1 to 6 carbons) and carbons are listed. 1-10 (preferably C1-6) fluorinated alkyl groups, etc. [chemical formula 27]

In formula (61), 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 may be used, or two or more may be used in combination.

R¹¹² 的定義與A的定義相同，較佳範圍亦相同。R ¹¹⁵ in formula (1) represents a tetravalent organic group. As the tetravalent organic group, a group including an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. [chemical formula 28]

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

R¹¹⁵ 表示4價的有機基團。R¹¹⁵ 的定義與式（1）的R¹¹⁵ 的定義相同。As for the tetravalent organic group represented by R ¹¹⁵ in the formula (1), specifically, a tetracarboxylic acid residue remaining after removing an acid dianhydride group from a tetracarboxylic dianhydride, etc. are mentioned. Tetracarboxylic dianhydride may be used only by 1 type, and may use 2 or more types. It is preferable that tetracarboxylic dianhydride is a compound represented by following formula (7). [chemical formula 29]

R ¹¹⁵ represents a tetravalent organic group. The definition of R ¹¹⁵ is the same as that of R ¹¹⁵ in 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 30]

R ¹¹³ and R ¹¹⁴ in formula (1) each independently represent a hydrogen atom or a monovalent organic group. At least one of R ¹¹³ and R ¹¹⁴ preferably contains a radical polymerizable group, and more preferably two 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 group having an ethylenically unsaturated bond is exemplified as a preferable example. 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 31]

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 alkylene, carbon The number is preferably 1-12, more preferably 1-6, and particularly preferably 1-3; the number of repetitions is preferably 1-12, more preferably 1-6, and particularly preferably 1-3). In addition, the (poly)oxyalkylene group represents an oxyalkylene group or a polyoxyalkylene group. Preferred examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene Methyl, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, ethylidene, propylidene, trimethylene, -CH ₂ CH(OH)CH ₂ - are more preferred . It is particularly preferred that R ²⁰⁰ is a methyl group, and R ²⁰¹ is an ethylenyl group. The polymerizable group equivalent (weight average molecular weight divided by the number of polymerizable groups) of the radically polymerizable group is preferably 0.0001 or more, more preferably 0.0005 or more, still more preferably 0.001 or more. The upper limit is preferably at most 0.05, more preferably at most 0.001, and still more preferably at most 0.005. In addition, the number of polymerizable groups can be estimated from the compounding quantity of the raw material at the time of synthesis.

As an embodiment of the polyimide precursor in the present invention, aliphatic groups, aromatic groups, and aralkyl groups having 1, 2 or 3 acid groups as monovalent organic groups of R ¹¹³ or R ¹¹⁴ can be cited. Base etc. 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 acid group and a benzyl group having an acid group. The acid group can be a hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ may be 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 developing solution can be used. From the viewpoint of solubility in an aqueous developer, R ¹¹³ or R ¹¹⁴ may be a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, or 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ may be a monovalent organic group. The monovalent organic group may include a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or an alkyl group substituted with an aromatic group. The carbon number of the alkyl group may be 1 to 30 (3 or more when it is 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, 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. As a monocyclic cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned, for example. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, bornyl, camphenyl (camphenyl), decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, camphenyl Acyl, dicyclohexyl and pinenyl. Among them, a cyclohexyl group is exemplified from the viewpoint of achieving both high sensitivity. Also, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later may be used. As an aromatic group, an aromatic hydrocarbon group or an aromatic heterocyclic group is mentioned. Specific examples of the aromatic hydrocarbon group include substituted or unsubstituted benzene rings, naphthalene rings, pentalene rings, indene rings, azulene rings, heptalene rings, indacene rings, Perylene ring, condensed pentaphenyl ring, ethane-naphthalene (acenaphthene) ring, phenanthrene ring, anthracene ring, condensed tetraphenyl ring, chrysene ring, biterphenylene ring, fenene ring, biphenyl ring, etc. have aromatic Groups of hydrocarbon rings. Examples of the aromatic heterocyclic group include substituted or unsubstituted pyrrole rings, furan rings, thiophene rings, pyrazole rings, imidazole rings, oxazole rings, thiazole rings, pyridine rings, pyrimidine rings, pyrimidine rings, and pyridazine rings. ring, three wells ring, indazine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine (quinolizine) ring, quinoline ring, phthalazine ring, naphthyridine ring, quinol Oxaline ring, quinoxazoline (quinoxazoline) ring, isoquinoline ring, carbazole ring, phenanthidine ring, acridine ring, phenanthroline (phenanthroline) ring, thienium ring, chromene (chromene) ring, mouth mountain mouth A group with an aromatic heterocycle such as a xanthene ring, a phenoxathiine ring, a phenothiazine ring, or a phenazine ring.

Moreover, it is also preferable that the 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, more preferably at most 20% by mass. Although the upper limit is not limited, it is actually 50% by mass or less.

Moreover, for the purpose of improving the adhesiveness with a board|substrate, you may copolymerize the aliphatic group which has a siloxane structure, and the structural unit represented by Formula (1). Specifically, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are mentioned as a diamine component.

A¹ 、A² 、R¹¹¹ 、R¹¹³ 及R¹¹⁴ 的定義分別獨立地與式（1）中的A¹ 、A² 、R¹¹¹ 、R¹¹³ 及R¹¹⁴ 定義相同，較佳範圍亦相同。R¹¹² 的定義式（5）中的R¹¹² 定義相同，較佳範圍亦相同。The structural unit represented by formula (1) is preferably a structural unit represented by formula (1-A). [chemical formula 32]

The definitions of A ¹ , A ² , 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. Definition of R ¹¹² R ¹¹² in the formula (5) has the same definition, 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. Also, structural isomers represented by the formula (1) as only structural units may be included. In addition, the polyimide precursor may contain other types of structural units in addition to the structural unit of the above-mentioned formula (1).

As an embodiment of the polyimide precursor in the present invention, it is exemplified that the total constituent units are 50 mol% or more, and a further part is 70 mol% or more, especially 90 mol% or more. Formula (1) The structural unit represented by , and at least one (preferably two) of R ¹¹³ and R ¹¹⁴ is a radical polymerizable polyimide precursor. 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 (weight average molecular weight/number average molecular weight) of the polyimide precursor is preferably 1.5-3.5, more preferably 2-3.

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

When producing the polyimide precursor, it is better to include the process of precipitating solid. Specifically, solid precipitation can be performed by precipitating the polyimide precursor in the reaction solution in water and dissolving it in a solvent such as tetrahydrofuran that can dissolve the polyimide precursor.

R¹²¹ 表示2價的有機基團，R¹²² 表示4價的有機基團，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價的有機基團。<<Polybenzoxazole Precursor>> The polybenzoxazole precursor used in the present invention has a radically polymerizable group. It is preferable to have a radical polymerizable group in a side chain. It is more preferable that the polybenzoxazole precursor contains the structural unit represented by following formula (2). [chemical formula 33]

R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, 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 group includes aliphatic groups (preferably 1-24 carbons, more preferably 1-12, particularly preferably 1-6) and aromatic groups (preferably 6-22 carbons, 6 to 14 are more preferred, and 6 to 12 are 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, its definition is the same as that of R ¹¹⁵ in the above formula (1), and the preferred 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.

The polybenzoxazole precursor may contain other types of structural units in addition to the structural units of the above formula (2). It is preferable that the precursor contains a diamine residue represented by the following formula (SL) as another type of structural unit from the viewpoint of being able to suppress warpage of the cured film accompanying ring closure.

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1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），其餘為氫原子或碳數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，可以是分別相同，亦可以分別不同。a結構及b結構的聚合可以是嵌段聚合亦可以是無規聚合。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 34]

Z has a structure and b structure, 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), R ^2s is a hydrocarbon group with 1 to 10 carbons Hydrocarbon group (preferably 1-6 carbons, more preferably 1-3 carbons), at least one of R ^3s , R ^4s , R ^5s , R ^6s is an aromatic group (preferably 6-22 carbons , more preferably 6-18 carbons, particularly preferably 6-10 carbons), and the rest are hydrogen atoms or 1-30 carbons (preferably 1-18 carbons, more preferably 1-12 carbons, especially Preferably, they are organic groups having 1 to 6 carbon atoms, which 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), preferable Z includes those in which R ^5s and R ^6s in the b structure 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 making the said molecular weight into the said range, the elasticity modulus after the dehydration ring closure of a polybenzoxazole precursor can be reduced, the effect of suppressing warpage, and the effect of improving solubility can be combined.

When the precursor contains a diamine residue represented by the formula (SL) as another type of structural unit, it also includes a tetracarboxylic acid residue remaining after removing the acid dianhydride from the tetracarboxylic dianhydride from the viewpoint of improving alkali solubility. It is preferable to use a base as a constituent unit. As an example of such a tetracarboxylic acid residue, the example of ^R115 in Formula (1) is mentioned.

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 dispersion degree 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. More preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably 70% by mass or more. 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 still more preferable, and 95% by mass or less is still more preferably. The photosensitive resin composition of the present invention may contain one type of polymer precursor, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is within the above-mentioned range.

＜Heat Alkali Generator＞ The photosensitive resin composition of the present invention contains a thermal base generator. By using the thermal base generator, when the heating process of the ring-closing reaction of the precursor of the heterocyclic polymer is carried out, the base species that promote the ring-closing reaction can be generated, so the ring-closing rate is further improved. On the other hand, if the cyclization is promoted by a thermal base generator, the number of crosslinking points of the polymer precursor will decrease. On the other hand, in the present invention, part of the crosslink is cut off after cyclization and is supplemented by multi-site crosslinking agent, thereby contributing to the improvement of the effect of the present invention.

Tertiary amine compounds are mentioned as a thermal base generator used in this invention. For example, it is a compound represented by the following formula (A1). (R ^A1 )N(R ^A2 ) ₂ (A1) In the formula, R ^A1 is an alkyl group (preferably 1-12 carbons, more preferably 1-6 carbons, more preferably 1-3 carbons), alkenyl ( Carbon number 2-12 is preferred, 2-6 is more preferred, 2-3 is further preferred), aryl group (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred) preferably), aralkyl (preferably 7-23 carbons, more preferably 7-19, further preferably 7-11), and aryl is more preferred. R ^A2 is an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms) which may have an acidic group (especially preferably a carboxyl group).

式（101）及式（102）中，R¹ ～R⁶ 分別獨立地表示氫原子或烴基，R⁹ 表示烴基。 在此，其中的烴基表示在發揮本發明的效果之範圍內可以具有羥基、鹵素原子、氧代基（=O）等。 R¹ 與R² 、R³ 與R⁴ 、R⁵ 與R⁶ 、R⁵ 與R⁹ 、R⁶ 與R⁹ 可以分別鍵結而形成環。 R¹ ～R⁶ 的烴基為烷基（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）或芳烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳）為較佳。 R⁹ 的烴基為伸甲基或伸烷基（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）為較佳。伸甲基、伸烷基可以由胺基（NH₂ ）取代。該胺基在形成環時可以構成連接基（NH）。作為R¹ 與R² 、R³ 與R⁴ 、R⁵ 與R⁶ 、R⁵ 與R⁹ 、R⁶ 與R⁹ 所形成之環^， 可列舉4員至8員的含氮雜環。作為式（102）中由R⁵ 與R⁶ 、R⁵ 與R⁹ 鍵結而形成環之化合物，可列舉二吖雙環十一烯、二吖雙環壬烯等。As the thermal base generator used in the present invention, ammonium salts (including pyridinium bases) are preferred. Specifically, it is preferable to contain a cation represented by the following formula (101) or formula (102), and a base of the cation and anion is more preferable. The anion may be bonded to any part of the ammonium cation (specifically, betaine) via a covalent bond, or may exist outside the ammonium cation molecule, but is preferably present outside the ammonium cation molecule. In addition, the existence of an anion outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the extramolecular anions of the cationic portion are also referred to as counter anions. [chemical formula 35]

In formula (101) and formula (102), R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and R ⁹ represents a hydrocarbon group. Here, the hydrocarbon group here means that it may have a hydroxyl group, a halogen atom, an oxo group (=O), etc. within the range which exhibits the effect of this invention. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁵ and R ⁹ , and R ⁶ and R ⁹ may be bonded to each other to form a ring. The hydrocarbon groups of R ¹ to R ⁶ are alkyl (preferably 1 to 12 carbons, more preferably 1 to 6, further preferably 1 to 3), alkenyl (preferably 2 to 12 carbons, 2 to 6 is more preferred, 2 to 3 is further preferred), aryl (6 to 22 carbons is preferred, 6 to 18 is more preferred, 6 to 10 is further preferred) or aralkyl group (7 to 10 carbons is preferred) 23 is preferable, 7-19 is more preferable, 7-11 is still more preferable) is more preferable. The hydrocarbon group of R ⁹ is methylene or alkylene (preferably 2-12 carbons, more preferably 2-6 carbons, further preferably 2-3 carbons). Methylene groups and alkylene groups may be substituted by amino groups (NH ₂ ). This amine group can constitute a linker (NH) when forming a ring. Examples of rings formed by R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁵ and R ⁹ , and R ⁶ and R ^{9 include} nitrogen-containing heterocycles with 4 to 8 members. Examples of compounds in the formula (102) in which R ⁵ and R ⁶ , and R ⁵ and R ⁹ are bonded to form a ring include diacribicycloundecene, diacribicyclononene, and the like.

The ammonium cation is preferably represented by any one of the following formulas (Y1-1) to (Y1-5). [chemical formula 36]

In formulas (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and the definitions of R ¹ and R ⁷ are the same as those of R ¹ in formula (101) or formula (102). Among them, R ¹⁰¹ is a group with an alkane structure (preferably with 1 to 12 carbons, more preferably with 1 to 6, and further preferably with 1 to 3), a group with an alkene structure (with 2 to 12 carbons Preferably, 2 to 6 are more preferred, 2 to 3 are further preferred), aryl structure groups (6 to 22 carbons are preferred, 6 to 18 are more preferred, 6 to 10 are further preferred) More preferably, a group with an aryl structure (especially a group with a benzene ring structure) is more preferred. In the formulas (Y1-1) to (Y1-4), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group (preferably 6-22 carbons, more preferably 6-18, further preferably 6-10) , n represents an integer of 1 or more, and m represents an integer of 0-5. In the formula (Y1-3), two R ¹ bonds may form a bicyclic ring. Examples of bis compounds include diacribicycloundecene, diacribicyclononene, and the like.

In this embodiment, the ammonium salt preferably has an anion and an ammonium cation with a pKa1 of 0-4. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and is still more preferably 3.2 or less. The lower limit is preferably at least 0.5, more preferably at least 1.0. As long as the pKa1 of the anion is in the above-mentioned range, it is possible to cyclize the precursor of the heterocyclic ring-containing polymer and the like at a lower temperature, and further, the stability of the photosensitive resin composition can be improved. As long as pKa1 is 4 or less, the stability of the thermal base generator is good, and generation of base is suppressed without heating, and the stability of the photosensitive resin composition is good. As long as pKa1 is 0 or more, the generated base is less likely to be neutralized, and the cyclization efficiency of the heterocycle-containing polymer precursor and the like is good. The type of anion is preferably one selected from carboxylate anion, phenol anion, phosphate anion, and sulfate anion, and carboxylate anion is more preferable because it can balance salt stability and thermal decomposability. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion. The carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, more preferably an anion of a divalent carboxylic acid. According to this aspect, it can be set as a thermal alkali generator which can further improve the stability, curability, and developability of a photosensitive resin composition. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the photosensitive resin composition can be further improved. In this embodiment, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. It is more preferable that pKa1 is 3.5 or less, and it is still more preferable that it is 3.2 or less. According to this aspect, the stability of the photosensitive resin composition can be further improved. Here, pKa1 is a value calculated from the structural formula using ACD/pKa (manufactured by LA Systems Inc.) software.

式（X1）中，EWG表示吸電子基。The carboxylic acid anion is preferably represented by the following formula (X1). [chemical formula 37]

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

In the present embodiment, an electron-withdrawing group refers to a Hammett substituent constant σm showing a positive value. Among them, σm is described in detail in Yuso Tono, Journal of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965), pp. 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 groups (σm=0.43), CF ₃ CO groups (σm=0.63), HC≡C groups (σm=0.21), CH ₂ =CH groups (σm =0.06), Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), PhCO group (σm=0.34), H ₂ NCOCH ₂ group (σm=0.06), etc. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (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為芳香族基，芳香族烴基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）或芳香族雜環基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳，雜原子可列舉氮原子、硫原子、氧原子）為較佳。Ar可以具有取代基，例如，可以具有1～5個R^x1 的基。 Np為1～6為較佳，1～3為更佳，1或2為特佳。EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6). [chemical formula 38]

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 is an aromatic group, an aromatic hydrocarbon group (6-22 carbons is preferred, 6-18 is more preferred, 6-10 is further preferred) or aromatic A heterocyclic group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, nitrogen atom, sulfur atom, and oxygen atom are examples of the heteroatom) are preferred. Ar may have a substituent, for example, may have 1 to 5 ^Rx1 groups. Np is preferably 1-6, more preferably 1-3, and particularly preferably 1 or 2.

式（XA）中，L¹⁰ 表示單鍵或伸烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、伸烯基（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）、芳香族基（芳香族烴基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）或芳香族雜環基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳、雜原子可列舉氮原子、硫原子、氧原子））、-NR^X -及選自該等的組合之2價的連接基，R^X 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）或芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）。In this embodiment, the carboxylic acid anion is preferably represented by the following formula (XA). Formula (XA) [Chemical Formula 39]

In the formula (XA), L ¹⁰ represents a single bond or an alkylene group (preferably with 1 to 12 carbons, more preferably with 1 to 6, more preferably with 1 to 3), alkenyl (with 2 to 12 carbons) is preferred, 2-6 is more preferred, 2-3 is further preferred), aromatic group (aromatic hydrocarbon group (6-22 carbon number is preferred, 6-18 is more preferred, 6-10 is further preferred) preferably) or aromatic heterocyclic group (preferably 1 to 12 carbons, more preferably 1 to 6, further preferably 1 to 3, heteroatoms include nitrogen atom, sulfur atom, oxygen atom)), -NR ^X - and a divalent linking group selected from these combinations, R ^X represents a hydrogen atom, an alkyl group (preferably 1-12 carbons, more preferably 1-6, and further preferably 1-3), Alkenyl (preferably 2-12 carbons, more preferably 2-6, further preferably 2-3) or aryl (preferably 6-22 carbons, more preferably 6-18, 6-10 for further improvement).

Specific examples of the carboxylic acid anion include a maleic acid anion, a phthalic acid anion, an N-phenyliminodiacetate anion, and an oxalic acid anion.

[化學式41]

Specific examples of the thermal base generator include the following compounds. [chemical formula 40]

[chemical formula 41]

[化學式43]

[chemical formula 42]

[chemical formula 43]

It is preferable that content of the thermal base generator in the photosensitive resin composition of this invention is 0.1-50 mass % with respect to the total solid content of a photosensitive resin composition. The lower limit is more preferably at least 0.5% by mass, more preferably at least 0.85% by mass, and still more preferably at least 1% by mass. The upper limit is more preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, may be 5% by mass or less, or may be 4% by mass or less. The mass ratio of the thermal base generator to the specific radical polymerizable compound (specific radical polymerizable compound/thermal base generator) is preferably 1.0 to 80. As a lower limit, 1.5 or more is preferable, 2 or more is more preferable, and 3 or more is still more preferable. As an upper limit, 50 or less is preferable, 20 or less is more preferable, and 10 or less is still more preferable. By making this ratio slightly within the above-mentioned range, the values of elongation at break and chemical resistance become optimum. One type or two or more types of thermal base generators can be used. When using two or more kinds, it is preferable that the total amount is within the above-mentioned range.

＜Other Components of Photosensitive Resin Composition＞ The photosensitive resin composition of the present invention may contain components other than the above. Specifically, a photopolymerization initiator, a solvent, a polymerization inhibitor, and the like are exemplified. In addition, impurities or the like derived from raw materials used in the synthesis of the precursor of the heterocycle-containing polymer may be contained.

＜＜Photopolymerization Initiator＞＞ It is preferable that the photosensitive resin composition of this invention contains a photoinitiator. The photopolymerization initiator that can be used in the present invention is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, a photopolymerization 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 photopolymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 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.

The photosensitive resin composition of the present invention contains a photopolymerization initiator, whereby 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, the photosensitive resin composition is caused by irradiation with light. The hardening caused by 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 photopolymerization initiator, any known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (such as compounds having a three-well skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole Oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, Metal compounds, organic boron 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 are 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 photopolymerization 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 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. Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF Corporation) and the like.

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2012-014052號公報中所記載之光聚合起始劑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，還能夠使用DFI-091（DAITO CHEMIX Co., Ltd.製）。 進而，還能夠使用具有氟原子之肟化合物。作為該種肟化合物的具體例，可列舉日本特開2010-262028號公報中所記載之化合物、日本特表2014-500852號公報的0345～0348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。 作為最佳的肟化合物，可列舉日本特開2007-269779號公報中所示出之具有特定取代基之肟化合物、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 photoinitiator. By using an oxime compound, exposure latitude can be improved more effectively. It is preferable that the exposure latitude (exposure margin) of an oxime compound is wide. As specific examples of oxime compounds, compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, 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-phenylpropan-1-one , 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-tosyloxy)iminobutan-2-one and 2-ethoxycarbonyloxy imino-1-phenylpropan-1-one, etc. [chemical formula 44]

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 2012-014052 The photopolymerization initiator 2 described in the Publication 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. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can also 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 paragraphs 0345-0348 of JP-A-2014-500852, Japanese Compound (C-3) and the like described in paragraph 0101 of JP-A-2013-164471. Preferred oxime compounds include oxime compounds having specific substituents shown in JP-A-2007-269779 and oxime compounds having a thioaryl group shown in JP-A-2009-191061 wait.

式（I）中，R⁵⁰ 為碳數1～20的烷基、因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、由鹵素原子、環戊基、環己基、碳數2～12的烯基、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1個取代之苯基或聯苯基，R⁵¹ 為由式（II）表示之基團，或者為與R⁵⁰ 相同的基團，R⁵² ～R⁵⁴ 各自獨立地為碳數1～12的烷基、碳數1～12的烷氧基或鹵素。 [化學式46]

式中，R⁵⁵ ～R₅₇ 與上述式（I）的R⁵² ～R⁵⁴ 相同。From the viewpoint of exposure sensitivity, the photopolymerization initiator is selected from the group consisting of trihalomethyl three well compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and acyl phosphine compounds. , phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene - Compounds in the group of iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds. More preferable photopolymerization initiators are trihalomethyl three well compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds , benzophenone compound, acetophenone compound, at least one selected from the group consisting of trihalomethyl three well compounds, α-aminoketone compound, oxime compound, triaryl imidazole dimer, benzophenone compound It is more preferable to use a single compound, it is still more preferable to use a metallocene compound or an oxime compound, and it is especially preferable to use an oxime compound. In addition, as the photopolymerization initiator, N,N' such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone) can also be used. -Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2- Aromatic ketones such as methyl-1-[4-(methylthio)phenyl]-2-morpholino-acetone-1, quinones such as alkyl anthraquinones condensed with aromatic rings, benzoin Benzoin ether compounds such as base 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 45]

In formula (I), R ⁵⁰ is an alkyl group with 1 to 20 carbons, an alkyl group with 2 to 20 carbons interrupted by one or more oxygen atoms, an alkoxy group with 1 to 12 carbons, phenyl, At least one of halogen atoms, cyclopentyl, cyclohexyl, alkenyl with 2 to 12 carbons, alkyl with 2 to 18 carbons interrupted by one or more oxygen atoms, and alkyl with 1 to 4 carbons One substituted phenyl or biphenyl group, R ⁵¹ is a group represented by formula (II), or the same group as R ⁵⁰ , R ⁵² to R ⁵⁴ are each independently an alkyl having 1 to 12 carbons group, alkoxy group with 1 to 12 carbon atoms or halogen. [chemical formula 46]

In the formula, R ⁵⁵ to R ₅₇ are the same as R ⁵² to R ⁵⁴ in the above formula (I).

In addition, as the photopolymerization initiator, compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used.

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 1 to 5% by mass, based on the total solid content of the photosensitive resin composition of the present invention. Still more preferably, it is 1-4 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, the total is preferably within the above-mentioned range.

＜＜Solvent＞＞ It is preferable that the photosensitive resin composition of this invention contains a solvent. As a solvent, a known one 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, azoles, and amides. As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate are listed as preferable ones. , butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (e.g., methyl alkoxyacetate, alkanes Ethyl oxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionates (e.g., 2-alkoxy Methyl oxypropionate, 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-alkane Ethyl oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate , ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve ethyl ether, etc. Ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetate etc. As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are mentioned as preferable ones. As aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are mentioned as preferable. As the thirines, for example, dimethyl argon is exemplified as a preferable one. As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-di Methylformamide, 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. Wherein, it is 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 ethyl A mixed solution of two or more of acid ester, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferred. It is particularly preferable to use dimethylsulfoxide and γ-butyrolactone at the same time.

Regarding the content of the solvent, from the viewpoint of coatability, the total solid content concentration of the photosensitive resin composition of the present invention is preferably 5 to 80% by mass, more preferably 5 to 70% by mass. , 10 to 60% by mass is particularly preferred. 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.

＜＜Migration Inhibitor＞＞ It is preferable that the photosensitive resin composition further includes a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the migration of metal ions from the metal layer (metal wiring) into the photosensitive resin composition layer. The migration inhibitor is not particularly limited, and examples include heterocyclic rings (pyrrole rings, furan rings, thiophene rings, imidazole rings, oxazole rings, thiazole rings, pyrazole rings, isoxazole rings, isothiazole rings, and tetrazole rings). ring, pyridine ring, pyridazine ring, pyrimidine ring, pyridine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, three well ring) compounds, with sulfur Urea and mercapto compounds, hindered phenolic compounds, salicylic acid derivatives, hydrazine derivatives. In particular, triazole-based compounds such as triazole (for example, 1,2,4-triazole), benzotriazole, and tetrazole-based compounds such as tetrazole and benzotetrazole 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 1H-1,2,3-triazole and 1H-tetrazole.

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% by mass relative to the total solid content of the photosensitive resin composition. % is further preferred. The migration inhibitor may be one kind or two or more kinds. When there are two or more types of migration inhibitors, the total of them is preferably within the above-mentioned range.

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為0.01～5質量%為較佳。 聚合抑制劑可以僅為一種，亦可以為兩種以上。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 polymerization inhibitors, for example, hydroquinone, p-methoxyphenol (1,4-methoxyphenol), di-tert-butyl-p-cresol, pyrogallol, p- tert-butylcatechol, p-benzoquinone (1,4-benzoquinone), diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol ), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitroso Diphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4 -methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N- Ethyl-N-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 No. 2015/125469 can also be used. Moreover, the following compound (Me is a methyl group) can also be used. [chemical formula 47]

When the photosensitive resin composition of this invention has a polymerization inhibitor, it is preferable that content of a polymerization inhibitor is 0.01-5 mass % with respect to the total solid content of the photosensitive resin composition of this invention. The polymerization inhibitor may be only one kind, or may be two or more kinds. 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 the present invention contains a metal adhesion improving agent for improving the adhesion with metal materials used for electrodes, wiring, and the like. 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 No. 2011/080992, JP-A Compounds described in paragraphs 0060 to 0061 of Publication No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, compounds described in paragraph 0055 of International Publication No. 2014/097594 . 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 48]

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 modifier 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, relative to 100 parts by mass of the heterocycle-containing polymer precursor. By setting it as 0.1 mass part or more, the adhesiveness of the cured film after a curing process and a metal layer becomes favorable, and by setting it as 30 mass parts or less, the heat resistance of the cured film after a curing process, and a mechanical characteristic become favorable. The metal adhesion improving agent may be only one kind, or may be two or more kinds. When using 2 or more types, it is preferable that the sum total is the said range.

>>Other additives>> To the photosensitive resin composition of the present invention, various additives can be added as required, such as thermal acid generators, sensitizing pigments, chain transfer agents, surfactants, higher fatty acid derivatives, within the range that does not impair the effects of the present invention. , inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. are blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the photosensitive resin composition.

＜＜＜Thermal Acid Generator＞＞＞ The photosensitive resin composition of the present invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating, and promotes the cyclization of the precursor of the heterocyclic polymer 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, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the heterocyclic polymer-containing precursor. Containing 0.01 parts by mass or more of the thermal acid generator promotes the crosslinking reaction and the cyclization of the precursor of the heterocycle-containing polymer, 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, Most 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 contacts with thermal base generators, thermal radical polymerization initiators, radical polymerization initiators, etc., and produces electron transfer, energy transfer, and heat generation. Thereby, the thermal base generator, the thermal radical polymerization initiator, and the radical 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, more preferably 0.1 to 15% by mass, relative to the total solid content of the photosensitive resin composition of the present invention. Preferably, 0.5-10 mass % is 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 the 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-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, classes, etc.).

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

<<<surfactant>>> Various surfactants can be added to the photosensitive resin composition of the present invention from the viewpoint of improving applicability. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicon-based surfactants can be used. Moreover, the following surfactants are also preferable. [chemical formula 49]

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. %. Surfactant may be only one kind, and may be two or more kinds. When there are two or more types of surfactants, the total range thereof is preferably the above-mentioned range.

＜＜＜Advanced 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. on the surface of the photosensitive resin composition. When the photosensitive resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass % with respect to the total solid content of the photosensitive resin composition of the present invention. Higher fatty acid derivatives may be only one kind, or two or more kinds. When there are two or more higher fatty acid derivatives, the total range is preferably the above range.

>>About the restriction of other contained substances>> 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 particularly 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 For the best. 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. Also, as a method for reducing the metal impurities unintentionally 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 contributes 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 contamination as much as possible.

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 particularly preferably less than 200 mass ppm. 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 particularly preferably less than 0.5 mass ppm. As a halogen atom, a chlorine atom and a bromine atom are mentioned. 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.

＜Preparation of photosensitive resin 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. Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the photosensitive resin composition. 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 material is preferably polytetrafluoroethylene, polyethylene or nylon. Filters can be used pre-cleaned with organic solvents. In the filtration process of the filter, multiple types of filters can be used in parallel or in series. When using multiple types of filters, 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 cyclic filtering. In addition, filtration may be performed after pressurization. When filtering is performed after pressurization, the pressure for pressurization is preferably 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 their manufacturing methods> Next, the cured film, laminated body, semiconductor device, and their manufacturing methods will be described. The cured film of the present invention is formed by curing the photosensitive resin composition of the present 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 to form a laminate, and furthermore, 3 to 7 layers may be laminated to form a laminate. It is preferable that the laminated body in the cured film of this invention which has two or more layers has a metal layer between cured films. Such a metal layer can be preferably used as metal wiring such as a redistribution layer.

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 process of forming a photosensitive resin composition layer by applying the photosensitive resin composition of the present invention to a substrate to form a photosensitive resin composition layer; and exposing the photosensitive resin composition layer to light Process. Preferably, the manufacturing method of a cured film further has the image development process which develops the said photosensitive resin composition layer after the said exposure process. After the development, heating (preferably at 50-450° C. (more preferably 50-250° C.) heating) is included, so that the exposed resin layer can be further hardened. In addition, as described above, when using a photosensitive resin composition, the composition can be hardened by exposure in advance, and then can be further hardened by heating by performing desired processing (for example, lamination described below) as necessary.

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 method for producing a cured film described above, after the cured film is formed, the film formation process (layer formation process) and heating process of the photosensitive resin composition are further performed again or when photosensitivity is imparted, as described above. It is preferable to perform a film formation process (layer formation process), an exposure process, and a development process (further heating process if necessary) sequentially. In particular, it is preferable to sequentially perform each of the above-mentioned processes multiple times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured film in this way, it can be set as a laminated body. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, between the cured films, or between the two. These will be described in detail below.

＜＜Film Formation Process (Layer Formation Process)＞＞ The manufacturing method of the preferable embodiment of this invention includes the film formation process (layer formation process) which applies a photosensitive resin composition to a board|substrate and makes it into a film (layer form). The type of board can be appropriately determined according to the application, and is not particularly limited to substrates made of semiconductors such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, evaporated films, magnetic films, Reflective film, metal substrates such as Ni, Cu, Cr, Fe, etc., paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, electrode plates of plasma display devices (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. As a method of applying the photosensitive resin composition to a substrate, coating is preferable. Specifically, examples of applicable methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, and 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 having a desired thickness can be obtained by adjusting appropriate solid content concentration and coating conditions according to the method. In addition, the coating method can also 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 preferable, and if it is a rectangular substrate, the slit coating method or A spraying method, an inkjet method, etc. are preferable. In the case of a spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

＜＜Drying process＞＞ The production method of the present invention may also include a process of drying to remove the solvent after the film formation process (layer formation process) after forming the photosensitive resin composition layer. The preferred drying temperature is 50°C to 150°C, more preferably 70°C to 130°C, and even more preferably 90°C to 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 process>> The manufacturing method of the present invention may also include an exposure process of exposing the above-mentioned photosensitive resin composition layer. The exposure amount is not particularly limited as long as it can harden the photosensitive resin composition. For example, in terms of exposure energy at a wavelength of 365 nm, it is preferably 100 to 10000 mJ/cm ² , and more preferably 200 to 8000 mJ/cm ² . The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, preferably 240 to 550 nm. In terms of the relationship with the light source, the exposure wavelengths include (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays ( wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (g, h, i-ray three wavelengths), (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 of the present invention, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by i-rays is preferable. Thereby, a particularly high exposure sensitivity can be obtained.

＜＜Development process＞＞ The manufacturing method of the present invention may include a developing process of developing the exposed photosensitive resin composition layer. By developing, the unexposed part (non-exposed part) can be removed. The developing method is not particularly limited as long as a desired pattern can be formed, for example, developing methods such as flooding, spraying, dipping, and ultrasonic waves can be used. A developing solution is used for developing. The developing solution can be used without particular limitation as long as it can remove the unexposed part (non-exposed part). It is preferable that the developing solution contains an 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 into ChemBioDraw. Organic solvents, as esters, for example, ethyl acetate, n-butyl acetate, pentyl formate, isopentyl acetate, isobutyl acetate, isopentyl acetate, butyl propionate, isopropyl butyrate , ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate (for example: alkoxy Methyl acetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxy ethyl acetate, etc.), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., 3-methoxy methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionate ( For example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate Esters and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.) , methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.; and, as Ethers, for example, preferably include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosol acetate, ethyl cellosol acetate, diethyl cellosol acetate, Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.; And, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. are preferably mentioned; and, As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are preferably mentioned; and as the oxenes, dimethylsulfoxide is preferably mentioned. In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. The developer is preferably an organic solvent in an amount of 50% by mass or more, more preferably an organic solvent in an amount of 70% by mass or more, and still more preferably an organic solvent in an amount of 90% by mass or more. In addition, the developer may be 100% by mass of 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 carry out at 20-40 degreeC. Rinsing may be further performed after processing with a developer. It is preferable to use a solvent different from that of the developer for rinsing. 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 process＞＞ The production method of the present invention preferably includes a film forming process (layer forming process), a drying process, or a process of heating in the development process. During the heating process, the cyclization reaction of the polymer precursor is carried out. Also, the composition of the present invention may contain a radically polymerizable compound other than the polymer precursor, but hardening of the unreacted radically polymerizable compound other than the polymer precursor can also be performed in this process. The heating temperature (maximum heating temperature) of the layer in the heating process is preferably 50°C or higher, more preferably 80°C or higher, still more preferably 140°C or higher, still more preferably 160°C or higher, and 170°C or higher. Further is better. The upper limit is preferably not higher than 500°C, more preferably not higher than 450°C, still more preferably not higher than 350°C, still more preferably not higher than 250°C, and still more preferably not higher than 220°C. 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 temperature increase rate at 1°C/min or more, excessive amine volatilization can be prevented while ensuring productivity, and by setting the temperature increase rate at 12°C/min or less, the residual stress of the cured film can be relaxed. 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 beginning of heating is called the temperature at the beginning of the process of heating to the highest heating temperature. For example, when the photosensitive resin composition is applied to the substrate and then 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 better to raise the temperature gradually. 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., more preferably 180° C. to 260° C., from the viewpoint of the adhesiveness between the layers of the cured film. The reason for this is not clear, but it is considered that by setting this temperature, the acetylene groups of the polymer precursors between the layers undergo a crosslinking reaction.

Heating can be done in stages. As an example, for example, the following pretreatment process can be carried out: the temperature is raised from 25°C to 180°C at 3°C/min, and kept at 180°C for 60 minutes; the temperature is raised from 180°C to 200°C at 2°C/min, and kept at 200°C 120 minutes. As the heating temperature of the pretreatment process, 100-200° C. is preferable, 110-190° C. is more preferable, and 120-185° C. is still more preferable. In this pretreatment process, as described in US Pat. No. 9,159,547, it is also preferable to perform the treatment while irradiating ultraviolet rays. Through this kind of pretreatment process, the characteristics of the film can be improved. The pretreatment process can be performed in a relatively short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment can be set as steps of more than two stages, for example, the pretreatment process 1 is performed in the range of 100-150°C, and then the pretreatment process 2 is performed in the range of 150-200°C. Furthermore, cooling may be performed after heating, and the cooling rate at this time is preferably 1 to 5° C./min.

From the viewpoint of preventing the decomposition of the polymer precursor, it is preferable to conduct the heating process in an atmosphere with a low oxygen concentration and low concentration by flowing an inert gas such as nitrogen, helium, or argon. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

＜＜Metal layer formation process＞＞ The manufacturing method of the present invention preferably includes a metal layer forming process of forming a metal layer on the surface of the developed photosensitive resin composition layer. The metal layer is not particularly limited, and existing metals can be used. Examples thereof 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 employed. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used. For example, photolithography, lift-off, electroplating, electroless plating, etching, printing, methods combining these, and the like can be considered. More specifically, the patterning method which combined sputtering, photolithography, and etching, and the patterning method which combined photolithography and electroplating are mentioned. The thickness of the metal layer is preferably from 0.1 to 50 μm, more preferably from 1 to 10 μm, based on the thickest part.

＜＜Laminated process＞＞ Preferably, the manufacturing method of the present invention also includes a lamination process. The lamination process means that the above-mentioned film forming process (layer forming process) and heating process are performed again on the surface of the cured film (resin layer) or metal layer, or the above-mentioned film forming process (layer forming process) is performed sequentially on the photosensitive resin composition. A series of processes of the exposure process and the above-mentioned development process. Certainly, the above-mentioned drying process and heating process may also be included in the lamination process. After the lamination process, when the lamination process is further performed, the surface activation treatment process may be performed after the above-mentioned heating process, after the above-mentioned exposure process, or after the above-mentioned metal layer forming process. As the surface activation treatment, plasma treatment is exemplified. It is better to carry out the above lamination process 2-5 times, more preferably 3-5 times. For example, the structure of resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably three or more and seven or less resin layers, more preferably three or more and five or less layers. That is, in the present invention, after the metal layer is provided, the film forming process (layer forming process) and the heating process of the photosensitive resin composition are further performed to cover the metal layer, or the photosensitive resin composition is sequentially performed. The above-mentioned film formation process (layer formation process), the above-mentioned exposure process, and the above-mentioned development treatment process (if necessary, a heating process) are preferable. By alternately performing the lamination process of laminating the photosensitive resin composition layer (resin) and the metal layer forming process, 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 in which the photosensitive resin composition of the present invention is used to form 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 , And compile these contents into this manual.

Next, an embodiment of a semiconductor device using the above photosensitive resin composition for an interlayer insulating film for a rewiring layer will be described. The semiconductor element 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a laminate 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are stacked is arranged on a wiring board 120 . In addition, in this embodiment, the case where the number of layers of semiconductor elements (semiconductor wafers) is mainly described is 4 layers, but the number of layers of semiconductor elements (semiconductor wafers) is not particularly limited, for example, it may be 2 layers, 8 layers, 16 floors, 32 floors, etc. Also, one layer may be used.

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

The laminated body 101 has a structure in which a semiconductor element 101a having no penetration electrodes and semiconductor elements 101b to 101d having penetration electrodes 102b to 102d are flip chip bonded. That is, the electrode pad of the semiconductor element 101a having no penetrating electrode and the connection pad on the side of the semiconductor element 101a of the semiconductor element 101b having the penetrating electrode 102b adjacent thereto are connected by metal bumps 103a such as solder bumps, And the connection pad on the other side of the semiconductor element 101b having the through-electrode 102b and the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the adjacent through-electrode 102c are connected by metal bumps 103b such as solder bumps. connect. Similarly, the connection pad on the other side of the semiconductor element 101c having the through-electrode 102c and the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the adjacent through-electrode 102d are connected by metal bumps such as solder bumps. 103c while connected.

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

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

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

The cured film formed from the photosensitive resin composition of the present invention can combine high chemical resistance and high elongation at break. The chemical resistance is, for example, preferably 500 nm/min or less, more preferably 300 nm/min or less, and still more preferably 100 nm/min or less. The upper limit is not particularly limited, but is actually 50000 nm/min or less. The elongation at break is, for example, preferably 40% or more, more preferably 55% or more, and still more preferably 70% or more. The upper limit is not particularly limited, but is actually 150% or less. The measuring methods of chemical resistance and elongation at break follow the measuring methods in Examples described later.

In addition to the above methods, the cured film in the present invention can be widely used in various applications using polyimide or polybenzoxazole. As an applicable field of the cured film of this invention, the insulating film of a semiconductor device, the inter-insulation film for rewiring layers, a stress buffer film, etc. are mentioned. In addition, patterning of a sealing film, a substrate material (base film and cover film of a flexible printed circuit board, an interlayer insulating film) or an insulating film for mounting as above by etching or the like can be mentioned. For such uses, see, for example, Science & technology Co., Ltd. "Highly functionalized and applied technology of polyimide", April 2008, Masaki Kakimoto/Editor-in-Chief, CMC Technical library "Polyimide material "Basic and Development" published in November 2011, Japan Polyimide and Aromatic Polymer Research Society/edited "Latest Polyimide Basics and Applications" NTS Inc, 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. Also, polyimide and polybenzoxazole are very heat-resistant, so the cured film in the present invention can also be preferably used as transparent plastic substrates for display devices such as liquid crystal displays and electronic paper, automotive parts, and heat-resistant coatings. , coating agent, film application, etc. [Example]

Hereinafter, the present invention will be described in more detail with reference to examples. Materials, usage amounts, ratios, processing contents, processing procedures, etc. 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. "Parts" and "%" are mass standards unless otherwise specified.

＜Synthesis of precursor composition (resin) of heterocycle-containing polymer＞ ＜＜Synthesis Example 1＞＞ [Derived from 4,4'-oxodiphthalic dianhydride, 4,4'-diamino group Synthesis of a polyimide precursor of diphenyl ether and 2-hydroxyethyl methacrylate (A-1: a polyimide precursor having a radically polymerizable group)] 20.0 g (64.5 micromole) 4,4'-dioxodiphthalic acid dianhydride (dried 4,4'-oxodiphthalic acid at 140°C for 12 hours), 18.6g (129 micromoles) of methyl 2-hydroxyethyl acrylate, 0.05g of hydroquinone, 10.7g of pyridine, and 140g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60°C for 18 hours, A diester of 4,4'-oxodiphthalic acid and 2-hydroxyethyl methacrylate was thus produced. 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. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08 g (58.7 micromoles) of 4,4'-diaminodiphenyl ether ester dissolved in 100 mL of N-methylpyrrolidone was added dropwise to in the reaction mixture. Then, the reaction mixture was stirred overnight at room temperature. Next, it was added to 5 liters of water to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered, added to 4 liters of water, added to the water, stirred again for 30 minutes, and filtered again. Next, the polyimide precursor was dried at 45° C. for 3 days under reduced pressure to obtain a polyimide precursor (A-1). [chemical formula 50]

<<Synthesis Example 2>> [Polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-2: Synthesis of a polyimide precursor having a radically polymerizable group] 14.06 g (64.5 micromoles) of pyromellitic dianhydride (drying pyromellitic acid at 140°C for 12 hours) , 18.6g (129 micromoles) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 10.7g of pyridine, and 140g of NMP (N-methyl-2-pyrrolidone) were mixed , and stirred at a temperature of 60° C. for 18 hours, thereby producing a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. 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. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08 g (58.7 micromoles) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction at 20 to 23°C over 20 minutes. in the mixture. Then, the reaction mixture was stirred overnight at room temperature. Next, it was added to 5 liters of water to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered, added to 4 liters of water, added to the water, stirred again for 30 minutes, and filtered again. Next, the polyimide precursor was dried at 45° C. for 3 days under reduced pressure to obtain a polyimide precursor (A-2). [chemical formula 51]

＜＜Synthesis Example 3＞＞ [Polyimide precursor (A -3: Synthesis of polyimide precursor with free radical polymerizable groups] 20.0 g (64.5 millimoles) of 4,4'-oxodiphthalic anhydride (oxydiphthalic anhydride Diformic acid dried at 140°C for 12 hours), 18.6g (129mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 10.7g of pyridine and 140g of diglyme The ethers were mixed and stirred at 60° C. for 18 hours to produce a diester of 4,4′-oxodiphthalic acid and 2-hydroxyethyl methacrylate. 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. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution in which 6.34 g (58.7 micromoles) of p-phenylenediamine was dissolved in 100 mL of N-methylpyrrolidone was dropped into the reaction mixture at 20 to 23° C. over 20 minutes. Then, the reaction mixture was stirred overnight at room temperature. Next, it was added to 5 liters of water to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered, added to 4 liters of water, added to the water, stirred again for 30 minutes, and filtered again. Next, the polyimide precursor was dried at 45° C. for 3 days under reduced pressure to obtain a polyimide precursor (A-3). [chemical formula 52]

<<Synthesis Example 4>> [Polyimide precursor derived from pyromellitic dianhydride, m-toluidine, and 2-hydroxyethyl methacrylate (A-4: a radical polymerizable group Synthesis of polyimide precursor)] 14.06g (64.5 micromole) of pyromellitic dianhydride (dried pyromellitic acid at 140°C for 12 hours), 18.6g (129 micromole ) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 10.7g of pyridine, and 140g of NMP (N-methyl-2-pyrrolidone) were mixed and stirred at a temperature of 60°C For 18 hours, a diester of pyromellitic acid and 2-hydroxyethyl methacrylate was produced. 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. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution in which 12.46 g (58.7 micromoles) of m-toluidine was dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23° C. over 20 minutes. Then, the reaction mixture was stirred overnight at room temperature. Next, it was added to 5 liters of water to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered, added to 4 liters of water, stirred again for 30 minutes, and filtered again. Next, the polyimide precursor was dried at 45° C. for 3 days under reduced pressure to obtain a polyimide precursor (A-4). [chemical formula 53]

<<Synthesis Example 5>> [Polyimide precursor composition derived from 4,4'-diaminodiphenyl ether acid dianhydride, 2-hydroxyethyl methacrylate, and the following diamine (a) Synthesis of A-5] 42.4 g of 4,4'-diaminodiphenyl ether acid dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed, and mixed in Stirring was carried out at a temperature of 60°C for 4 hours. Next, the reaction mixture was cooled to -10°C, and a solution of 34.35 g of dicyclohexylcarbodiimide dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5°C over 60 minutes. , and the mixture was stirred for 30 minutes. Next, a solution of 76.0 g of the following diamine (a) dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5°C over 60 minutes, and the mixture was stirred for 1 hour. After that, 20 mL of ethanol and 200 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. 14 L of water was added to the obtained reaction liquid to precipitate the polyimide precursor, filtered, and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polyimide precursor had a weight average molecular weight of 26500 and a number average molecular weight of 9300. The polymeric group equivalent is about 95%. Diamine (a) [Chemical Formula 54]

＜＜Synthesis Example 6＞＞ [Polybenzoxazole precursor composition A-6 derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydibenzoyl chloride Synthesis] 28.0 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was stirred and dissolved in 200 mL of N-methylpyrrolidone. Next, 25.0 g of 4,4'-oxodibenzoyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5°C, and stirring was continued for 60 minutes. 6 L of water was added to the obtained reaction solution to precipitate the polybenzoxazole precursor, and the solid was filtered and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polybenzoxazole precursor had a weight average molecular weight of 28500 and a number average molecular weight of 9800. This polybenzoxazole precursor A-6 is an example not having a radically polymerizable group.

＜＜Synthesis Example A-7＞＞ Regarding the synthesis procedure of the polyimide precursor A-5, the polyimide precursor A-7 was synthesized in the same procedure except that 2-hydroxyethyl methacrylate was not used. This polyimide precursor A-7 is an example not having a radical polymerizable group.

＜Preparation of photosensitive resin composition＞ The resin and the components described in the following table were mixed, and the coating liquid of the photosensitive resin composition was prepared as a uniform solution. Each photosensitive resin composition was passed through a filter made of UPE having a pore width of 0.8 μm, and pressure filtration was performed.

<Chemical resistance> Each photosensitive resin composition was passed through a filter with a pore width of 0.8 μm, and after pressure filtration, a photosensitive resin composition layer was formed on a silicon wafer by spin coating . 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 photosensitive resin composition layer with a uniform thickness of 15 μm on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C), expose the photosensitive resin composition layer on the silicon wafer with an exposure energy of 500mJ/ ^cm2 , and expose the photosensitive resin composition layer (resin layer) under a nitrogen atmosphere The cured layer (resin layer) of the photosensitive resin composition layer was obtained by heating at a heating rate of 10° C./minute and heating at the temperature and time described in Table 1 below. The obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated. Drug: 90:10 (mass ratio) mixture of dimethylsulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) solution Evaluation conditions: Immerse the resin layer in the solution at 75°C for 15 minutes , compare the film thickness before and after immersion, and calculate the dissolution rate (nm/min).

<Elongation at break> A photosensitive resin composition layer was formed 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 photosensitive resin composition layer with a uniform thickness of 15 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500mJ/cm ² using a stepper (Nikon NSR 2005 i9C). The exposed photosensitive resin composition layer was heated at a rate of 10° C./min under a nitrogen atmosphere, and heated at the temperature and time listed in Table 1 below to obtain a cured layer of the photosensitive resin composition layer ( resin layer). The resin layer was dipped in a 4.9 volume % hydrofluoric acid solution for 30 minutes, and the resin layer was peeled off from the silicon wafer to obtain a resin layer. Regarding the elongation at break of the resin layer, use a tensile testing machine (Tensilon) at 25°C, 65 Measured in accordance with JIS-K6251 in an environment of %RH (relative humidity). 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 of the elongation at break in the longitudinal direction and the width direction was used. In addition, the formula for the elongation at break is based on JIS, E _b = (L _b - L ₀ )/L ₀ ×100: E _b is the elongation at break (%), L ₀ is the original length (mm) of the test piece, L _b is the length (mm) at the time of rupture.

＜Hardening condition＞ In the above-mentioned tests of chemical resistance and elongation at break, the temperature and time for heating and curing the polymer precursor to obtain a cured film were appropriately determined in Examples and Comparative Examples, respectively. The conditions are described in Table 1.

摻合量：質量基準、（A）～（G）中以固體成分計為100%、（H）中以溶劑計為100%。 [表2]

摻合量：質量基準、（A）～（G）中以固體成分計為100%、（H）中以溶劑為100%。[Table 1]

Blending amount: on a mass basis, in (A) to (G), it is 100% as a solid content, and in (H), it is 100% as a solvent. [Table 2]

Blending amount: on a mass basis, in (A) to (G), the solid content is 100%, and in (H), the solvent is 100%.

(A) Resins (precursors for heterocyclic polymers) A-1 to A-7: Precursors of heterocycle-containing polymers produced in Synthesis Examples 1 to 7

(B) Polymeric compound B-2: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)･･･ Compound B-2 exemplified above B-2 is a mixture with a compound in which one of the acryl groups is substituted with a hydrogen atom, and the hexafunctional compound is the main component. In addition, B-1, B-3 to B-14 are compounds exemplified in the section of the above-mentioned specific radical polymerizable compound.

B-C1: SR-209 (manufactured by Sartomer Company) [chemical formula 55]

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

(D) Thermal base generator D-1: the following compound D-2: the following compound D-3: the following compound [Chemical formula 56]

(E) Polymerization inhibitors E-1: 1,4-Benzoquinone E-2: 1,4-Methoxyphenol

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

(G) Metal adhesion improving agent (silane coupling agent) G-1: the following compound G-2: the following compound G-3: the following compound [Chemical formula 57]

(H) solvent H-1: γ-butyrolactone H-2: Dimethylsulfone H-3: N-methyl-2-pyrrolidone H-4: ethyl lactate

From the above results, it can be seen that in the present invention, the photosensitive resin composition in which the selected specific radical polymerizable compound is used in combination with a precursor of a heterocyclic polymer having a radical polymerizable group and a thermal base generator is used. The cured film formed from this photosensitive resin composition exhibits high chemical resistance and elongation at break, and can achieve both of these characteristics. On the other hand, those using a difunctional radically polymerizable compound that does not satisfy the requirements of the present invention (Comparative Example 3) and those that did not use a thermal base generator (Comparative Examples 1 and 2) had poor chemical resistance, and the elongation at break was poor. The rate is also poor. Also, when the polymer precursor did not contain a polymerizable functional group (Comparative Examples 4 and 5), the chemical resistance was significantly poor, and the value of the elongation at break was low. Thus, in the structure of the present invention, only when a specific radical polymerizable compound, a heterocyclic polymer precursor having a radical polymerizable group, and a thermal base generator are used at the same time, the high effect that cannot be obtained when each component is used alone can be achieved. , in the form of both chemical resistance and elongation at break. This can be regarded as a synergistic effect that the above-mentioned three components act integrally in the cyclization reaction system of the polymer precursor.

<Example 100> After pressure-filtering the photosensitive resin composition of Example 1 through a filter with a pore width of 0.8 μm, a photosensitive resin composition was coated on a silicon wafer by spin coating. Resin composition. The silicon wafer coated with the photosensitive resin composition layer was dried on a heating plate at 100° C. for 5 minutes, and a photosensitive resin composition layer with a uniform thickness of 15 μm was formed 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 , and use cyclopentanone to expose the photosensitive resin composition layer (resin layer) Development was carried out for 60 seconds to form pores with a diameter of 10 μm. Next, in a nitrogen atmosphere, the temperature was raised at a rate of 10° C./min to reach the temperatures listed in Table 1 and Table 2, respectively, and then held for the time listed in Table 1 and Table 2. After cooling to room temperature, a copper thin layer (metal layer) with a thickness of 2 μm was formed on a part of the surface of the photosensitive resin composition layer by vapor deposition so as to cover the hole. Furthermore, the same type of photosensitive resin composition was used again on the surface of the metal layer and the photosensitive resin composition layer, and the process from filtering the photosensitive resin composition to heating the patterned film was carried out again in the same manner as above for 3 hours. In order to produce a laminate composed of resin layer/metal layer/resin layer. This resin layer (interlayer insulating film for rewiring layer) is excellent in insulation. Further, as a result of manufacturing a semiconductor device using this interlayer insulating film for rewiring layer, normal operation was confirmed.

100‧‧‧semiconductor devices 101a～101d‧‧‧semiconductor components 101‧‧‧Laminated body 102b～102d‧‧‧through electrodes 103a～103e‧‧‧Metal bumps 105‧‧‧Redistribution layer 110, 110a, 110b‧‧‧underfill layer 115‧‧‧Insulation film 120‧‧‧Wiring board 120a‧‧‧Surface electrode

FIG. 1 is a schematic diagram showing the structure of one embodiment of a semiconductor device.

100‧‧‧semiconductor devices

101a~101d‧‧‧semiconductor components

101‧‧‧Laminated body

102b~102d‧‧‧through electrode

103a~103e‧‧‧Metal bump

105‧‧‧Redistribution layer

110, 110a, 110b‧‧‧underfill layer

115‧‧‧Insulation film

120‧‧‧Wiring board

120a‧‧‧Surface electrode

Claims (27)

A photosensitive resin composition, which contains a precursor of a heterocyclic polymer, a thermal base generator and a radical polymerizable compound, the precursor of the heterocyclic polymer has a radical polymerizable group, and the radical polymerizable The compound includes a radically polymerizable compound including a compound having 4 or more polymerizable functional groups, and the compound having 4 or more polymerizable functional groups is a compound represented by the following formula (P-3),

In the formula (P-3), Ps are independently selected from vinylphenyl, vinyl and (meth)acryl groups, L ^q is a linking group with valence of rm+1, and rm is 0~12 Integer of , the sum of 3 rms is 4 or more. The photosensitive resin composition as described in claim 1, wherein the polymerizable functional groups are independently selected from vinylphenyl, vinyl and (meth)acryl groups. The photosensitive resin composition as described in item 1 or item 2 of the patent claims, wherein the thermal base generator has a cation represented by formula (101) or formula (102);

In formula (101) and formula (102), R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and R ⁹ represents a hydrocarbon group. The photosensitive resin composition as described in item 1 or item 2 of the patent application, wherein the precursor of the heterocyclic polymer includes a polyimide precursor or a polybenzoxazole precursor. The photosensitive resin composition as described in claim 1 or claim 2, wherein the precursor of the heterocyclic polymer includes a polyimide precursor. The photosensitive resin composition as described in item 1 or item 2 of the scope of the patent application, wherein the precursor of the heterocyclic polymer contains a structural unit represented by the following formula (1);

In formula (1), ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, ^R113 and ^R114 each independently represent hydrogen Atom or monovalent organic group. The photosensitive resin composition as described in Claim 6 of the patent application, wherein at least one of the R ¹¹³ and the R ¹¹⁴ contains a free radical polymerizable group. The photosensitive resin composition as described in item 6 of the scope of the patent application, wherein the R ¹¹⁵ contains an aromatic ring. The photosensitive resin composition as described in item 6 of the scope of the patent application, wherein the R ¹¹¹ is represented by -Ar ⁰ -L ⁰ -Ar ⁰ -, and each Ar ⁰ is independently a divalent group containing an aromatic ring, L ⁰ is a single bond, an aliphatic hydrocarbon group with 1 to 10 carbon atoms that may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, and combinations of these groups A group formed by two or more. The photosensitive resin composition as described in claim 6, wherein the R ¹¹¹ is a group represented by the following formula (51) or formula (61);

In formula (51), 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, a methyl group, a fluoromethyl group, a divalent Fluoromethyl or trifluoromethyl;

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group. The photosensitive resin composition as described in claim 1 or claim 2, which contains a photopolymerization initiator. The photosensitive resin composition as described in claim 1 or claim 2, wherein the mass ratio of the thermal base generator to the free radical polymerizable compound is 1.0-80. The photosensitive resin composition as described in item 1 or item 2 of the scope of patent application, which The radical polymerizable compound is used in a range of 2.5 parts by mass to 62.5 parts by mass relative to 100 parts by mass of the heterocycle-containing polymer precursor. The photosensitive resin composition described in claim 1 or claim 2 further contains a solvent. The photosensitive resin composition described in claim 1 or claim 2, which is used for developing with a developer solution containing more than 90% by mass of an organic solvent. The photosensitive resin composition described in claim 1 or claim 2, which is used to form 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 16 of the patent application. A laminate having two or more layers of the cured film described in claim 17 of the scope of the patent application. The laminate according to claim 18, which has a metal layer between the cured films. The laminated body described in claim 18 of the patent application has 3 to 7 layers of the hardened film. A method for producing a cured film, comprising: applying the photosensitive resin composition described in any one of the first to the sixteenth items of the patent application to a substrate to form a photosensitive resin composition layer of the photosensitive resin composition a layer forming process; and an exposure process for exposing the photosensitive resin composition layer. As the manufacturing method of the cured film described in item 21 of the patent scope, it also has the following functions: After the exposure process, the photosensitive resin composition layer is subjected to a developing process of developing. The method for producing a cured film according to claim 22 of the patent application, wherein the development process uses a developer solution containing more than 90% by mass of an organic solvent for development. The method for producing a cured film as described in claim 22 of the patent application, which includes a post-development heating process of heating the photosensitive resin composition layer at a temperature of 50-450° C. after the development process. The method for producing a cured film as described in claim 24, wherein the heating temperature is 50-250°C. The method for producing a cured film as described in claim 21, wherein the film thickness of the cured film is 1-30 μm. A semiconductor device having the cured film described in Claim 17 or the laminate described in any one of Claims 18 to 20.

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