TWI805825B - Photosensitive resin composition, cured film, laminate, production method of cured film, semiconductor device - Google Patents

Abstract

The present invention provides a photosensitive resin composition capable of providing a film excellent in storage stability and elongation at break, a cured film using the photosensitive resin composition, a laminate, a method for producing a cured film, and a semiconductor device. The photosensitive resin composition includes a thermal base generator and a polyimide precursor. The thermal base generator generates a base at a temperature below 200°C, and has a polymeric group at the site of the generated salt.

Description

Photosensitive resin composition, cured film, laminate, production method of cured film, 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.

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

An attempt was made to use polyimide as a protective film for the interlayer insulating film as described above. Patent Document 1 discloses a resin composition containing a polyimide precursor and 2,4,6-trimethylpyridinium p-toluenesulfonate. Patent Document 2 discloses a resin composition containing a polyimide precursor, a compound that generates radicals by irradiation with actinic rays, a specific compound having an oxirane group, and a solvent. Patent Document 3 discloses a photosensitive resin composition containing an N-aromatic glycine derivative having a specific structure and a polymer precursor. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-108053 [Patent Document 2] Japanese Patent Laid-Open No. 2014-201695 [Patent Document 3] Japanese Patent Laid-Open No. 2006-282880 [Non-patent literature]

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

As described in the above-mentioned patent documents, etc., polyimide precursors or polybenzoxazole precursors (hereinafter, these may be collectively referred to as "polymer precursors") are cyclized (ring-closed) as described above , whereby the resin composition can be cured. The polymer precursor is cyclized by heating, but if a base is present at this time, the polymer precursor acts as a catalyst to accelerate the cyclization and harden rapidly. Therefore, it is conceivable to promote the cyclization reaction of the polymer precursor by containing a thermal base generator that generates a base when heated. With regard to such a thermal base generator, it is also required not to release a base before heating to avoid hardening due to unintentional cyclization, and to achieve stability during storage. In addition, among the conventional thermal base generators, the base molecules generated by them are relatively small and volatile. Therefore, in an environment heated to a predetermined temperature, the base may volatilize from the system. If the base volatilizes from the composition, the effect of cyclizing the polymer precursor by the use of the base cannot be expected, resulting in poor elongation at break of the resulting film.

In view of the technical problems in these photosensitive resin compositions, an object of the present invention is to provide a photosensitive resin composition capable of achieving sufficient heating curability for a photosensitive resin composition containing a polymer precursor, and A cured film, a laminate, a method for producing a cured film, and a semiconductor device using the photosensitive resin composition. In particular, an object thereof is to provide a photosensitive resin composition having excellent storage stability and excellent elongation at break when used as a cured film, and a method for producing a cured film, a laminate, and a cured film using the photosensitive resin composition and semiconductor devices.

As a result of studies conducted by the inventors of the present invention, they studied the provision of a polymerizable group to the generated base. That is, a polymerizable group is introduced into the thermal base generator, and the decomposed base has a polymerizable group structure. The generated base is polymerized with other molecules through the polymerizable group, so that the base exists in the system in a state of maintaining its activity and in a higher molecular state than before. Thereby, it was found that the volatilization of the base can be suppressed, and the cyclization of the polymer precursor during heat hardening can be effectively promoted. Specifically, the above-mentioned problems are solved by the following means.

式（N1）中，X為單鍵或2價的連結基，R¹ 分別獨立地表示氫原子或有機基團，n1及n2為1或2，n1+n2為3，n3為0或1，n3為1時，X不是單鍵，n1為2時，2個［ ］內的基團可以彼此相同亦可以不同，n2為2時，2個R¹ 可以彼此相同亦可以不同，2個R¹ 可以彼此連結而形成環狀結構，R¹ 中的至少一個具有聚合性基； [化學式2]

式（N2）中，R² 表示氫原子或有機基團，R³ 表示有機基團，n4及n5為1或2，n4+n5為3，n4為2時，（ ）內的基團可以彼此相同亦可以不同，n5為2時，2個R² 可以彼此相同亦可以不同，2個R² 可以彼此連結而形成環狀結構，R² 中的至少一個具有聚合性基； [化學式3]

式（N3）中，R⁴ 表示n8價的有機基團，R⁵ 及R⁶ 分別獨立地表示氫原子或烴基，R⁷ ～R⁹ 分別獨立地表示烴基，A表示m價的酸陰離子，m為1～4的整數，n7表示1～12的整數，n8及n9表示1～12的整數，且n8=n9，R⁵ 與R⁶ 可以連結而形成環狀結構，R⁷ ～R⁹ 中的2個以上可以分別連結而形成環狀結構，R⁷ ～R⁹ 中的至少一個具有聚合性基。 ＜3＞如＜1＞或＜2＞所述之感光性樹脂組成物，其中， 上述成為所產生之鹼之部位所具有之聚合性基為環氧基、氧環丁烷基、乙烯性不飽和基或由下述式（Z）表示之基團； [化學式4]

式（Z）中，Rc表示氧原子、氮原子或（n+2）價的芳香族基，Ra及Rb分別獨立地表示氫原子或有機基團，n表示0～6的整數，Rc為氧原子的情況下，n為0，Rc為氮原子的情況下，n為1，*表示鍵結鍵。 ＜4＞如＜1＞～＜3＞中任一項所述之感光性樹脂組成物，其中， 上述聚合物前驅物包含聚醯亞胺前驅物。 ＜5＞如＜4＞所述之感光性樹脂組成物，其中， 上述聚醯亞胺前驅物具有由下述式（1）表示之構成單元； [化學式5]

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。 ＜6＞如＜5＞所述之感光性樹脂組成物，其中， 上述式（1）中的R¹¹³ 及R¹¹⁴ 中的至少一個包含自由基聚合性基團。 ＜7＞如＜1＞～＜6＞中任一項所述之感光性樹脂組成物，其用於再配線層用層間絕緣膜的形成。 ＜8＞一種硬化膜，其使＜1＞～＜7＞中任一項所述之感光性樹脂組成物硬化而成。 ＜9＞一種積層體，其具有2層以上且7層以下的＜8＞所述之硬化膜，且在該硬化膜之間具有金屬層。 ＜10＞一種硬化膜的製造方法，其包括將＜1＞～＜7＞中任一項所述之感光性樹脂組成物應用於基板而形成膜之膜形成步驟。 ＜11＞如＜10＞所述之硬化膜之製造方法，其包括在80～450℃下對上述膜進行加熱之加熱步驟。 ＜12＞如＜10＞或＜11＞所述之硬化膜的製造方法，其具有對上述膜進行曝光之曝光步驟及對上述膜進行顯影之顯影步驟。 ＜13＞一種半導體器件，其具有＜8＞所述之硬化膜或＜9＞所述之積層體。 [發明效果]<1> A photosensitive resin composition comprising a thermal base generator, a polymer precursor selected from polyimide precursors and polybenzoxazole precursors, a photopolymerization initiator, and a polymerizable compound, wherein , The thermal base generator generates a base below 200°C, and has a polymerizable group at the site of the generated salt. <2> The photosensitive resin composition according to <1>, wherein the thermal base generator has a structure represented by any one of the following formulas (N1) to (N3); [Chemical formula 1]

In formula (N1), X is a single bond or a divalent linking group, R ¹ independently represents a hydrogen atom or an organic group, n1 and n2 are 1 or 2, n1+n2 is 3, n3 is 0 or 1, When n3 is 1, X is not a single bond. When n1 is 2, the groups in the two [ ] can be the same or different from each other. When n2 is 2, the two R ¹ can be the same or different from each other. Two R ¹ can be connected to each other to form a ring structure, at least one of ^R1 has a polymerizable group; [chemical formula 2]

In formula (N2), R ² represents a hydrogen atom or an organic group, R ³ represents an organic group, n4 and n5 are 1 or 2, n4+n5 is 3, and n4 is 2, the groups in ( ) can be mutually The same or different, when n5 is 2, the two ^R2 can be the same or different from each other, the two ^R2 can be connected to each other to form a ring structure, at least one of the ^R2 has a polymerizable group; [chemical formula 3]

In formula (N3), R ⁴ represents an organic group with a valence of n8, R ⁵ and R ⁶ independently represent a hydrogen atom or a hydrocarbon group, R ⁷ to R ⁹ each independently represent a hydrocarbon group, A represents an acid anion with a valence of m, m is an integer of 1 to 4, n7 represents an integer of 1 to 12, n8 and n9 represent an integer of 1 to 12, and n8=n9, R ⁵ and R ⁶ can be linked to form a ring structure, R ⁷ to R ⁹ Two or more of them may be linked together to form a ring structure, and at least one of R ⁷ to R ⁹ has a polymerizable group. <3> The photosensitive resin composition as described in <1> or <2>, wherein the polymerizable group at the base to be generated is an epoxy group, an oxetanyl group, an ethylenic non- A saturated group or a group represented by the following formula (Z); [Chemical formula 4]

In the formula (Z), Rc represents an oxygen atom, a nitrogen atom or an aromatic group with a valence of (n+2), Ra and Rb independently represent a hydrogen atom or an organic group, n represents an integer from 0 to 6, and Rc represents oxygen In the case of an atom, n is 0, in the case of Rc being a nitrogen atom, n is 1, and * represents a bond. <4> The photosensitive resin composition according to any one of <1> to <3>, wherein the polymer precursor includes a polyimide precursor. <5> The photosensitive resin composition according to <4>, wherein the polyimide precursor has a structural unit represented by the following formula (1); [Chemical formula 5]

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. <6> The photosensitive resin composition according to <5>, wherein at least one of R ¹¹³ and R ¹¹⁴ in the formula (1) includes a radical polymerizable group. <7> The photosensitive resin composition as described in any one of <1>-<6> used for formation of the interlayer insulating film for rewiring layers. <8> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <7>. <9> A laminate having two or more and seven or less cured films according to <8>, and having a metal layer between the cured films. <10> A method for producing a cured film, including a film forming step of applying the photosensitive resin composition according to any one of <1> to <7> to a substrate to form a film. <11> The method for producing a cured film according to <10>, which includes a heating step of heating the film at 80 to 450°C. <12> The manufacturing method of the cured film as described in <10> or <11> which has the exposure process of exposing the said film, and the image development process of developing the said film. <13> A semiconductor device comprising the cured film described in <8> or the laminate described in <9>. [Invention effect]

According to the present invention, it is possible to provide a photosensitive resin composition capable of realizing sufficient heating curability for a photosensitive resin composition containing a polymer precursor, and a cured film, a laminate, and a cured film using the photosensitive resin composition. A method for producing a cured film, a method for producing a laminate, and a semiconductor device. In particular, it is possible to provide a photosensitive resin composition that is excellent in storage stability and excellent in mechanical properties (elongation at break) as a cured film, and a cured film, a laminate, and a cured film using the photosensitive resin composition. Manufacturing method and semiconductor device.

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

The description of the constituent requirements in the present invention described below may be based on representative embodiments of the present invention, but the present invention is not limited to these embodiments. Regarding the notation of a group (atomic group) in this specification, the notation of substitution and non-substitution includes both those without a substituent and those with a substituent. For example, "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In addition, when called an alkyl group, it may be a chain or a ring, and when a chain is called, it may be a straight chain or a branched chain. These meanings are also the same for alkenyl, alkylene, and alkenylene. Unless otherwise specified, "exposure" in this specification includes not only exposure by light but also drawing by particle beams such as electron beams and ion beams. In addition, as the light used for exposure, there are usually actinic rays or radiation such as bright line spectrum of a mercury lamp, excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid". Both or any of them, "(meth)acryl" means both or either of "acryl" and "methacryl". In this specification, the term "step" is not only an independent step, but also includes in this term as long as the expected action of the step can be achieved even when it cannot be clearly distinguished from other steps. Unless otherwise specified, the physical property values in the present invention are values at a temperature of 23° C. and an air pressure of 101325 Pa. In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as styrene-equivalent values based on gel permeation chromatography (GPC measurement). In this specification, for weight average molecular weight (Mw) and number average molecular weight (Mn), for example, HLC-8220 (manufactured by TOSOH CORPORATION) can be used, and guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, It calculated|required using TSKgel Super HZ3000 and TSKgel Super HZ2000 (made by TOSOH CORPORATION). Unless otherwise specified, the eluent was measured with THF (tetrahydrofuran). In addition, unless otherwise specified, detection was performed using a detector with a wavelength of 254 nm of UV rays (ultraviolet rays).

The photosensitive resin composition of the present invention (hereinafter, sometimes simply referred to as "the composition of the present invention" or "the resin composition of the present invention") is characterized by containing a thermal base generator (hereinafter, sometimes referred to as "specific thermal base generator"), polymer precursors, photopolymerization initiators, and polymerizable compounds. Hereinafter, the present invention will be described in detail according to preferred embodiments.

＜Specific heat base generator＞ The specific thermal base generator generates a base at 200° C. or lower and has a polymeric group at the site of the generated salt. Base generation at 200° C. or lower means that the compound is isomerized or decomposed at a temperature of 200° C. or lower to become a compound having a larger pKa of the conjugate acid than the original compound. The temperature at which the above-mentioned specific thermal base generator generates base (thermal base generation temperature) is preferably 180°C or lower, and may be 150°C or lower. The lower limit of the heat alkali generation temperature is preferably 50°C or higher, more preferably 60°C or higher, still more preferably 70°C or higher, and still more preferably 80°C or higher. It is preferable to set the temperature of the base that generates the thermal base generator below the above-mentioned upper limit to generate the base and harden the resin with lower energy consumption than when the base is generated at a higher temperature. On the other hand, it is preferable to set the temperature at which the base is generated to be equal to or higher than the above-mentioned lower limit to decompose the compound during storage at room temperature or the like to generate a base, thereby suppressing or preventing hardening of the resin. Moreover, it is preferable that a specific thermal base generator generates a base in the said temperature range in the heating process mentioned later. In addition, it is preferable that the specific thermal base generator is a compound that generates bases below the heat-resistant temperature of the cured film.

As an embodiment of the present invention, it is also possible to blend two or more specific thermal base generators having different base generation temperatures. With such a configuration, for example, a base is generated stepwise, so that the cyclization reaction of the polymer precursor during heating can proceed more efficiently.

<<polymerizable group>> The specific thermal base generator has a polymerizable group. The polymerizable group is located at the site that becomes the generated base. The number of polymerizable groups that a specific thermal base generator has is not particularly limited, and may be one or plural. From the viewpoint of suppressing the molecular weight of the specific thermal base generator, the number of polymerizable groups in one molecule is preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less. The lower limit value is not particularly limited, and may be 1 or more. Examples of the polymerizable group include those that undergo radical polymerization, polyaddition, and polycondensation, and those that undergo radical polymerization and polyaddition are preferred, and those that undergo radical polymerization are more preferred. Examples of the polymerizable group include an epoxy group (including a glycidyl group), an oxetanyl group, an ethylenically unsaturated group, or a group represented by the following formula (Z). Examples of ethylenically unsaturated groups include vinyl, vinyloxy, allyl, methallyl, propenyl, butenyl, vinylphenyl, (meth)acryl, (methyl) ) acryloxy, (meth)acrylamine, etc., among them, vinyl, vinylphenyl, (meth)acryl, (meth)acryloxy, (meth)acryl Amino groups are preferred. The amine group of (meth)acrylamine is not limited to -NH-, it can be -NR ^N - (R ^N is an alkyl, alkenyl, aryl, arylalkyl or heterocyclic group, specifically In other words, selected from the structure of the alkyl group described in the substituent T described later). R ^N may be linked to the linking group to which the polymerizable group is linked or to the parent structure of the thermal base generator to form a ring. Examples of the formed ring include the ring Cn described later. In this specification, the ethylenically unsaturated group exemplified here is called Et, and the polymeric group containing this ethylenically unsaturated group is called Ps.

式（Z）中，Rc表示氧原子、氮原子或（n+2）價的芳香族基。Ra及Rb分別獨立地表示氫原子或有機基團。n表示0～6的整數。Rc為氧原子的情況下，n為0。Rc為氮原子的情況下，n為1。Rc例如為苯環的情況下，n為0～4的整數。*表示鍵結鍵。 作為（n+2）價的芳香族基，可舉出芳香族烴基（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1～24為較佳，1～12為更佳，1～6為進一步較佳），更具體而言，可舉出包含後述之芳香族烴環Ary及芳香族雜環Aro之基團。 Ra及Rb為有機基團時，作為其有機基團，可舉出分別獨立地為烷基（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）、芳基烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳）。其中，烷基為較佳，具體而言，可舉出後述之Alk的例子。[chemical formula 6]

In formula (Z), Rc represents an oxygen atom, a nitrogen atom, or an aromatic group having a valence of (n+2). Ra and Rb each independently represent a hydrogen atom or an organic group. n represents an integer of 0-6. When Rc is an oxygen atom, n is 0. When Rc is a nitrogen atom, n is 1. For example, when Rc is a benzene ring, n is an integer of 0-4. * Indicates a bonded bond. As the (n+2) valent aromatic group, an aromatic hydrocarbon group (preferably 6 to 22 carbons, more preferably 6 to 18, more preferably 6 to 10) or an aromatic heterocyclic group ( The carbon number is preferably 1 to 24, more preferably 1 to 12, and still more preferably 1 to 6), and more specifically, a group including an aromatic hydrocarbon ring Ary and an aromatic heterocyclic ring Aro as described later . When Ra and Rb are organic groups, examples of the organic groups independently include alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms), Alkenyl (preferably 2-12 carbons, more preferably 2-6, further preferably 2-3), aryl (preferably 6-22 carbons, more preferably 6-18, 6-10 is still more preferred), arylalkyl (with 7 to 23 carbons is preferred, 7 to 19 is more preferred, and 7 to 11 is further preferred). Among these, an alkyl group is preferable, and specifically, the example of Alk mentioned later can be mentioned.

The group represented by the above formula (Z) is preferably a group represented by the following (Z1), (Z2) or (Z3).

式中的Ra¹ 為有機基團。作為有機基團的例，可舉出烷基（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）、芳基烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳）。其中，烷基為較佳，具體而言，可舉出後述之Alk的例子。 Rb¹ 為氫原子或甲基。 nb為1～5的整數。na為成為5-nb之整數。*為鍵結鍵。 Ar¹ 可舉出芳香族烴基（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1～24為較佳，1～12為更佳，1～6為進一步較佳），更具體而言，可舉出包含後述之芳香族烴環Ary及芳香族雜環Aro之基團。其中，Ar¹ 為苯基為較佳。[chemical formula 7]

^Ra in the formula is an organic group. Examples of organic groups include alkyl (preferably having 1 to 12 carbons, more preferably 1 to 6, and still more preferably 1 to 3), alkenyl (preferably having 2 to 12 carbons, 2 to 6 are more preferred, 2 to 3 are further preferred), aryl (6 to 22 carbons are preferred, 6 to 18 are more preferred, 6 to 10 are further preferred), arylalkyl (carbon number The number is preferably 7 to 23, more preferably 7 to 19, and still more preferably 7 to 11). Among these, an alkyl group is preferable, and specifically, the example of Alk mentioned later can be mentioned. Rb ¹ is a hydrogen atom or a methyl group. nb is an integer of 1-5. na is an integer of 5-nb. * is the bond key. Ar ¹ can be an aromatic hydrocarbon group (preferably 6-22 carbons, more preferably 6-18, further preferably 6-10) or an aromatic heterocyclic group (preferably 1-24 carbons, 1 -12 is more preferable, and 1-6 is still more preferable), More specifically, the group containing the aromatic hydrocarbon ring Ary and the aromatic heterocyclic ring Aro mentioned later is mentioned. Among them, ^Ar is preferably phenyl.

Among them, the polymerizable group is preferably an epoxy group (which may or may not contain a glycidyl group), an oxetanyl group or an ethylenically unsaturated group, and more preferably an epoxy group or an ethylenically unsaturated group.

<<Linker>> In the specific thermal base generator, a polymerizable group can be introduced into the compound via a linker. A structure in which a polymerizable group is introduced with or without a linking group can be represented by, for example, the following formula (Zp). In addition, in the present specification, when "having a polymerizable group", "containing a polymerizable group" and the like, as described above, the state in which the polymerizable group is introduced into the parent structure by a linking group is included. *-Zp-Ps formula (Zp) * represents the bonding position with the parent structure of the thermal base generator. The meaning of Ps is the same as that of the above-mentioned polymerizable group Ps. Zp is a single bond or a linker (hereinafter, it may be referred to as linker Zp or abbreviated as Zp in the sense of including a single bond). The structure of the linking group Zp is not particularly limited as long as it can link the polymerizable group to the base structure of the base generator. Therefore, as long as it is not too long or too large, it may be a linker of any structure. For example, when a polymerizable group is introduced into the parent structure of the thermal base generator, it can be appropriately determined in consideration of the reactivity of the linker site, the reactivity with the parent structure or the polymerizable group, and the like. The length of the linking chain of Zp is not particularly limited, but considering the structure of the actual linking group, 0-24 is better, 0-12 is better, and 0-6 is further better (0 means a single bond ). When Zp is a linking group, carbon atoms and hydrogen atoms preferably include heteroatoms (at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom, etc.) as the atoms constituting it as necessary. The number of carbon atoms in the linking group is preferably 1-24, more preferably 1-12, and still more preferably 1-6. Hydrogen atoms may be determined according to the number of carbon atoms or the like. The number of heteroatoms is preferably 0 to 12 independently of oxygen atoms, nitrogen atoms, sulfur atoms, etc., more preferably 0 to 6, and still more preferably 0 to 3. There are a wide variety of specific linking groups, and examples of the linking group L described later can be given. Among them, Zp is an alkylene group (preferably 1-12 carbons, more preferably 1-6, further preferably 1-3), arylylene (preferably 6-22 carbons, 6-18 is More preferably, 6 to 10 are still more preferable), oxygen atom (oxyl group), carbonyl group, -NH-, -NR ^N- , and a combination of these are more preferable. ^RN can be connected with other parts to form a ring structure. Specifically, examples of the ring Cn to be formed include the following ring Cn.

The linker Zp is more preferably a linker represented by the following formulas z1 to z8 or a combination thereof. nz is an integer of 0-12, preferably 0-6, more preferably 0-3. * is the bonding position with the parent structure of the thermal base generator. ** is the bonding position with Ps. R ^M is a hydrogen atom or a group defined by R ^N above. Examples of R ^M in the following formulas z5 to z8 link to the methylene group in the parentheses of nz to form a cyclic structure. Specifically, examples of the following ring Cn are mentioned, and more specifically, a piperidine ring is mentioned. [chemical formula 8]

The specific thermal base generator can be a quaternary ammonium salt, or amide carboxylate and carbamate, but amide carboxylate is preferred. Since the thermal base generator is a carboxylic acid amide structure, the pKa of the conjugate acid before the structure of the compound is changed by heating tends to be low and the storage stability of the composition is improved.

<<Formula (N1)>> It is preferable that the specific heat base generator has a structure represented by the following formula (N1). [chemical formula 9]

In formula (N1), X is a single bond or a divalent linking group. As a divalent linking group, the example of the linking group L mentioned later is mentioned. Among them, hydrocarbon groups are preferred, and alkylene groups, alkenylene groups, arylylene groups or combinations thereof are preferred. When X is a divalent linking group, the carbon number is preferably 2-18, more preferably 2-12, and still more preferably 2-8. When X is a divalent linking group, the linking chain length is preferably 1-12, more preferably 1-8, and still more preferably 1-6. Specific examples thereof include ethylene, propylene, butylene, vinylene, phenylene, phenylenemethylene, phenylene ethylene, and methylenephenylenemethylene. X may have a substituent T suitably within the range which exhibits the effect of this invention. For example, the aspect which has a hydroxyl group or a carboxyl group in a predetermined linking group, etc. are mentioned.

R ¹ each independently represent a hydrogen atom or an organic group. As an organic group, the organic group specified in the substituent T mentioned later is mentioned. The carbon number of the organic group is preferably 1-18, more preferably 1-12, and still more preferably 1-6. Among them, R ¹ is an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and further preferably having 1 to 3 carbon atoms). R ¹ may have a substituent T as long as the effects of the present invention are exhibited.

When n2 is 2 and R ¹ is 2, both of them will not be hydrogen atoms. n1 and n2 are 1 or 2, and n1+n2 is 3. n3 is 0 or 1. Wherein, when n3 is 1, X is not a single bond. When n1 is 2, the groups in the two [ ] may be the same or different from each other. When n2 is 2, the two R ¹ may be the same as or different from each other.

When n2 is 2, two R ¹ may be connected to each other to form a ring structure. As the formed cyclic structure, aliphatic hydrocarbon rings (the ones exemplified below will be referred to as ring Cf) (for example, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclopropene ring, etc.) ring, cyclobutene ring, cyclopentene ring, cyclohexene ring, etc.), aromatic hydrocarbon ring (the ones exemplified below will be referred to as ring Cr) (benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc.), containing Nitrogen heterocyclic rings (the ones exemplified below are referred to as ring Cn) (for example, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrroline ring, pyrrolidine ring, imidazole ring, pyrazolidine ring, piperidine ring, piperone ring, peroline ring, etc.), acid-containing heterocycle (the following examples are referred to as ring Co) (furan ring, pyran ring, oxirane ring, oxetane ring, tetrahydrofuran ring, tetrahydrofuran ring, tetrahydrofuran ring, etc. Hydropyran ring, Erkoukoushan ring, etc.), sulfur-containing heterocycle (the ones exemplified below are referred to as ring Cs) (thiophene ring, thioethane ring, thiotane ring, tetrahydrothiophene ring, Tetrahydrothiopyran ring, etc.), etc. These rings are collectively referred to as ring Cy.

At least one of R ¹ has a polymerizable group. As for the polymerizable group, the example of the above-mentioned Ps can be mentioned, and the example of the above-mentioned linking group Zp can be mentioned as the form of its connection.

式（N1-1）中，X¹ 為2價的連結基，作為其較佳的範圍，可舉出上述X的例子。在發揮本發明的效果之範圍內，X¹ 亦可以適當地具有取代基T。 R¹¹ 及R¹² 分別獨立地表示氫原子或有機基團。作為R¹¹ 及R¹² 的有機基團，分別獨立地可舉出後述之取代基T中規定之有機基團。有機基團的碳數為1～18為較佳，1～12為更佳，1～6為進一步較佳。尤其，R¹¹ 及R¹² 分別獨立地表示烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）為較佳。其中，R¹¹ 及R¹² 該兩者不會都是氫原子。在發揮本發明的效果之範圍內，R¹¹ 及R¹² 亦可以具有取代基T。 R¹¹ 與R¹² 可以彼此連結而形成環狀結構。作為所形成之環，可舉出環Cy的例子。 R¹¹ 及R¹² 中的至少一個具有聚合性基。關於聚合性基，可舉出上述Ps的例，作為其連結的樣態，可舉出上述連接基Zp的例子。It is preferable that the above formula (N1) is any one of the following formula (N1-1), formula (N1-2) and formula (N1-3). [chemical formula 10]

In the formula (N1-1), X ¹ is a divalent linking group, and examples of the above-mentioned X can be mentioned as its preferable range. ^X1 may have a substituent T as appropriate within the range in which the effect of the present invention is exhibited. R ¹¹ and R ¹² each independently represent a hydrogen atom or an organic group. Examples of the organic groups for R ¹¹ and R ¹² independently include organic groups specified in the substituent T described later. The carbon number of the organic group is preferably 1-18, more preferably 1-12, and still more preferably 1-6. In particular, R ¹¹ and R ¹² each independently represent an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and still more preferably having 1 to 3 carbon atoms). Wherein, both R ¹¹ and R ¹² will not be hydrogen atoms. R ¹¹ and R ¹² may have a substituent T as long as the effects of the present invention are exhibited. R ¹¹ and R ¹² may be connected to each other to form a ring structure. As the formed ring, an example of ring Cy can be given. At least one of R ¹¹ and R ¹² has a polymerizable group. As for the polymerizable group, the example of the above-mentioned Ps can be mentioned, and the example of the above-mentioned linking group Zp can be mentioned as the form of its connection.

In the formula (N1-2), X ² is a divalent linking group, and examples of the above-mentioned X can be mentioned as its preferable range. ^X2 may also have a substituent T as appropriate within the range in which the effect of the present invention is exhibited. R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an organic group. Examples of organic groups for R ¹³ and R ¹⁴ each independently include organic groups specified in the substituent T described later. The carbon number of the organic group is preferably 1-18, more preferably 1-12, and still more preferably 1-6. In particular, R ¹³ and R ¹⁴ are each independently an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and still more preferably having 1 to 3 carbon atoms). Wherein, both R ¹³ and R ¹⁴ will not be hydrogen atoms. R ¹³ and R ¹⁴ may have a substituent T as long as the effect of the present invention is exhibited. R ¹³ and R ¹⁴ may be connected to each other to form a ring structure. As the formed ring, an example of ring Cy can be given. At least one of R ¹³ and R ¹⁴ has a polymerizable group. As for the polymerizable group, the example of the above-mentioned Ps can be mentioned, and the example of the above-mentioned linking group Zp can be mentioned as the form of its connection.

In the formula (N1-3), X ³ is a linking group with a valence of 2+m4, wherein the aromatic hydrocarbon group (preferably 6-22 carbons, more preferably 6-18, more preferably 6-10) is Preferably, as the ring structure, an example of the aromatic hydrocarbon ring Ary described later can be given. ^X3 may also have a substituent T as appropriate within the range in which the effect of the present invention is exhibited. Y ¹ is a group represented by -(CO) _m3 -OH, where m3 is 0 or 1. R ¹⁵ to R ¹⁸ each independently represent a hydrogen atom or an organic group. Examples of the organic groups for R ¹⁵ to R ¹⁸ independently include organic groups specified in the substituent T described later. The carbon number of the organic group is preferably 1-18, more preferably 1-12, and still more preferably 1-6. In particular, R ¹⁵ to R ¹⁸ are each independently an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and still more preferably having 1 to 3 carbon atoms). m4 is an integer of 0-12, preferably an integer of 0-8, more preferably an integer of 0-4. Both R ¹⁵ and R ¹⁶ may not be hydrogen atoms. R ¹⁵ and R ¹⁶ may be connected to each other to form a ring. As the formed ring, an example of ring Cy can be given. At least one of R ¹⁵ and R ¹⁶ has a polymerizable group. As for the polymerizable group, the example of the above-mentioned Ps can be mentioned, and the example of the above-mentioned linking group Zp can be mentioned as the form of its connection. R ¹⁵ and R ¹⁶ may have a substituent T as long as the effect of the present invention is exhibited. Both R ¹⁷ and R ¹⁸ may not be hydrogen atoms. R ¹⁷ and R ¹⁸ may be connected to each other to form a ring. As the formed ring, an example of ring Cy can be given. At least one of R ¹⁷ and R ¹⁸ has a polymerizable group. As for the polymerizable group, the example of the above-mentioned Ps can be mentioned, and the example of the above-mentioned linking group Zp can be mentioned as the form of its connection. R ¹⁷ and R ¹⁸ may have a substituent T as long as the effect of the present invention is exhibited. When X ³ is a linking group composed of an aromatic ring, a benzene ring is preferable, and in this case, for example, an aspect in which two carboxyl groups are substituted for Y ¹ can be mentioned. When expressed concretely, the following formula (N1-3a) can be mentioned.

式中，R¹⁵ ～R¹⁸ 分別獨立地表示氫原子或有機基團。R¹⁵ ～R¹⁸ 的較佳的樣態的含義與先前以式（N1-3）定義的相同。R¹⁵ 與R¹⁶ 、R¹⁷ 與R¹⁸ 各兩者不會都是氫原子，可以形成環Cy。R¹⁵ 及R¹⁶ 中的至少任一個又R¹⁷ 及R¹⁸ 中的至少任一個具有聚合性基Ps，聚合性基亦可以經由連接基Zp導入到母結構。[chemical formula 11]

In the formula, R ¹⁵ to R ¹⁸ each independently represent a hydrogen atom or an organic group. Desirable aspects of R ¹⁵ to R ¹⁸ have the same meanings as defined above in the formula (N1-3). Both of R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ may not be hydrogen atoms, and may form a ring Cy. At least one of R ¹⁵ and R ¹⁶ and at least one of R ¹⁷ and R ¹⁸ has a polymerizable group Ps, and the polymerizable group can also be introduced into the parent structure via the linker Zp.

Hereinafter, although the compound which forms the specific thermal base generator represented by formula (N1) is illustrated, this invention is not limitedly interpreted by this.

[chemical formula 12]

式（N2）中，R² 表示氫原子或有機基團。作為R² 的有機基團，可舉出後述之取代基T中規定之有機基團。有機基團的碳數為1以上為較佳。作為上限，30以下為較佳，18以下為更佳，14以下為進一步較佳。尤其，R² 為烷基（碳數1～12為較佳，1～6為更佳，1～3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）或芳基烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳）為較佳。在發揮本發明的效果之範圍內，R² 亦可以具有取代基T。<<Formula (N2)>> It is also preferable that the specific heat base generator has a structure represented by the following formula (N2). [chemical formula 13]

In formula (N2), R ² represents a hydrogen atom or an organic group. Examples of the organic group for R ² include organic groups specified in the substituent T described later. The carbon number of the organic group is preferably 1 or more. As an upper limit, 30 or less is preferable, 18 or less is more preferable, and 14 or less is still more preferable. In particular, R ^is alkyl (preferably 1-12 carbons, more preferably 1-6, further preferably 1-3), aryl (preferably 6-22 carbons, more preferably 6-18 Preferably, 6-10 is more preferred) or arylalkyl (with 7-23 carbons is preferred, 7-19 is more preferred, 7-11 is further preferred) is preferred. R ² may have a substituent T as long as the effect of the present invention is exhibited.

^R3 is an organic group, alkyl (preferably 1-24 carbons, more preferably 2-18, further preferably 3-14), aryl (preferably 6-30 carbons, 6-24 is more preferred, 6-18 is further preferred), arylalkyl (7-31 carbons is preferred, 7-25 is more preferred, 7-19 is further preferred) or a heterocyclic group-containing group (1 to 30 carbons is preferred, 2 to 24 is more preferred, and 3 to 18 is further preferred; the heterocyclic group is preferably a 5-membered ring, a 6-membered ring or a combination thereof; as a specific heterocyclic group Examples include examples of the substituent T described later) are preferable. R ³ may have a substituent T as long as the effect of the present invention is exhibited.

n4 and n5 are 1 or 2, and n4+n5 is 3. When n5 is 2, R ² cannot both be hydrogen atoms. When n4 is 2, the groups in ( ) may be the same or different from each other. When n5 is 2, two R ² may be the same or different from each other. Two R ² may be connected to each other to form a ring structure, and the ring Cy is exemplified as the formed ring. At least one of R ² has a polymerizable group. The type of the polymerizable group is exemplified by the polymerizable group Ps, and the link to the parent structure is exemplified by the linker Zp.

The above formula (N2) is preferably represented by the following formula (N2-1) or formula (N2-2). [chemical formula 14]

In formula (N2-1), R ²¹ and R ²² each independently represent a hydrogen atom or an organic group. Wherein, both R ²¹ and R ²² will not be hydrogen atoms. When R ²¹ and R ²² are organic groups, examples of the organic groups include organic groups of the substituent T described later. Among them, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and still more preferably having 1 to 3 carbon atoms) is preferred. R ²¹ and R ²² may have a substituent T as long as the effect of the present invention is exhibited. At least one of ^R21 and ^R22 has a polymerizable group. Examples of the polymerizable group include the aforementioned polymerizable group Ps, and examples of the connection to the R ²¹ and R ²² sides include connection via the linker Zp. R ²¹ and R ²² may be connected to each other to form a ring. As the formed ring, an example of ring Cy can be given. R ³¹ is an organic group, preferably an alkyl group. At this time, the alkyl group is preferably 1 to 24 carbons, more preferably 1 to 18, and even more preferably 1 to 12, especially tertiary alkyls (for example, tertiary butyl, 1,1-di methylpropyl, adamantyl) are preferred. R ³¹ may have a substituent T as long as the effect of the present invention is exhibited.

In formula (N2-2), R ²³ and R ²⁴ each independently represent a hydrogen atom or an organic group. Wherein, both R ²³ and R ²⁴ will not be hydrogen atoms. When R ²³ and R ²⁴ are organic groups, examples of the organic groups include organic groups of the substituent T described later. Among them, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and still more preferably having 1 to 3 carbon atoms) is preferred. R ²³ and R ²⁴ may also have a substituent T within the range of exerting the effect of the present invention. At least one of ^R23 and ^R24 has a polymerizable group. Examples of the synthetic group include the aforementioned polymerizable group Ps, and examples of the connection to the R ²³ and R ²⁴ sides include the connection via the linker Zp. R ²³ and R ²⁴ may be connected to each other to form a ring. As the formed ring, an example of ring Cy can be given. L ¹ is a single bond or a linking group, especially a linking group is preferred. When ^L1 is a linking group, examples of the linking group L described later can be given, among which alkylene (1-12 carbons is preferred, 1-6 is more preferred, 1-3 is further preferred) is preferred. good. Ar ² is an aromatic ring, an aromatic hydrocarbon ring (preferably 6-22 carbons, more preferably 6-18, and further preferably 6-14; 5-membered ring or 6-membered ring or at least any heterocyclic ring is Preferable; as a specific example, the example of Ary) or an aromatic heterocyclic ring (with 2 to 24 carbon atoms is preferred, 2 to 18 is more preferred, and 2 to 12 is further preferred; as a hetero atom, an oxygen atom, A nitrogen atom and a sulfur atom are preferable, and the number of heteroatoms is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. As a specific example, the example of Aro can be given. or thioxanthene 10,10-dioxide) is preferred. Ar ² may have a substituent T as long as the effect of the present invention is exhibited.

As the thermal base generator represented by formula (N2), the following compounds can be illustrated, but the present invention is not limitedly interpreted thereto. [chemical formula 15]

<<Formula (N3)>> It is also preferable that the specific thermal base generator has a structure represented by the following formula (N3). [chemical formula 16]

In formula (N3), R ⁴ represents an organic group with a valence of n8. Examples of the organic group include organic groups of the substituent T described later (wherein, the valence number is explained by n8). Among them, n8 valent alkane structure group (1-18 carbon number is preferred, 1-12 is more preferred, 1-6 is further preferred) or aryl structure group (carbon number 6-22 is preferred) better, 6-18 is more preferred, 6-10 is further preferred) is more preferred. R ⁴ may have a substituent T as long as the effect of the present invention is exhibited. R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group. As an organic group, hydrocarbon groups are preferred, aliphatic hydrocarbon groups (preferably 1-18 carbons, more preferably 1-12, further preferably 1-6) and aromatic hydrocarbon groups (6-22 carbons are more preferred) better, 6-18 is more preferred, 6-10 is further preferred) is more preferred, alkyl (carbon number 1-12 is preferred, 1-6 is preferred, 1-3 is further preferred) is further preferred better. It is particularly preferable that both of R ⁵ and R ⁶ are hydrogen atoms. When R ⁵ and R ⁶ are organic groups, they may have a substituent T within the range of exerting the effect of the present invention. R ⁵ and R ⁶ may be connected to each other to form a ring. Examples of the formed ring include ring Cf. R ⁷ to R ⁹ each independently represent a hydrocarbon group. Examples of the hydrocarbon groups for R ⁷ to R ⁹ each independently include hydrocarbon groups specified in the substituent T described later. The number of carbon atoms in the hydrocarbon group is preferably 1-18, more preferably 1-12, and still more preferably 1-6. In particular, R ⁷ to R ⁹ are each independently an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and still more preferably having 1 to 3 carbon atoms). The hydrocarbon groups of R ⁷ to R ⁹ may have a substituent T as long as the effect of the present invention is exerted. Two or more of R ⁷ to R ⁹ may be linked together to form a ring. The formed ring includes ring Cy, and more specifically, examples of Cn include a piperidine ring. A represents an m-valent acid anion. As a specific example of A, a group including * ^-COO- (carboxylate anion) can be exemplified (* is a bond with another site), and * ^-COO- is preferable. The formula weight of A is preferably 44 or more, more preferably 300 or less, and more preferably 200 or less. m is an integer of 1-4. n7 represents the integer of 1-12. n8 and n9 represent the integer of 1-12. Among them, n8=n9. At least one of R ⁷ to R ⁹ has a polymerizable group. The type of the polymerizable group is exemplified by the aforementioned polymerizable group Ps, and the form of its connection is exemplified by the linking group Zp.

It is preferable that the above formula (N3) is the following formula (N3-1), formula (N3-2) or formula (N3-3). [chemical formula 17]

In formula (N3-1), R ⁴¹ represents an organic group. Examples of the organic group of R ⁴¹ include organic groups of the substituent T described later. Among them, alkyl (preferably 1-18 carbons, more preferably 1-12, further preferably 1-6) or aryl (preferably 6-22 carbons, more preferably 6-18, 6 ~10 is further preferred) is preferred. R ⁴¹ may have a substituent T or a polymerizable group Ps via a linker Zp (including a single bond) within the range of exerting the effect of the present invention. R ⁷¹ , R ⁸¹ and R ⁹¹ each independently represent a hydrocarbon group. Examples of the hydrocarbon groups for R ⁷¹ , R ⁸¹ and R ⁹¹ each independently include hydrocarbon groups specified in the substituent T described later. The number of carbon atoms in the hydrocarbon group is preferably 1-18, more preferably 1-12, and still more preferably 1-6. In particular, R ⁷¹ , R ⁸¹ and R ⁹¹ are each independently an alkyl group (preferably having 1-12 carbon atoms, more preferably having 1-6 carbon atoms, and still more preferably having 1-3 carbon atoms). R ⁷¹ , R ⁸¹ , and R ⁹¹ may have a substituent T as long as the effect of the present invention is exhibited. Two or more of R ⁷¹ , R ⁸¹ and R ⁹¹ may be linked together to form a ring. The formed ring includes ring Cy, and more specifically, examples of Cn include a piperidine ring. At least one of R ⁷¹ , R ⁸¹ and R ⁹¹ has a polymerizable group. The type of the polymerizable group is exemplified by the aforementioned polymerizable group Ps, and the form of its connection is exemplified by the linking group Zp. A is an acid anion, and the preferred range is the same as that of formula (N3).

In formula (N3-2), R ⁴² represents an organic group. Examples of the organic group of R ⁴² include organic groups of the substituent T described later. Among them, alkyl (preferably 1-18 carbons, more preferably 1-12, further preferably 1-6) or aryl (preferably 6-22 carbons, more preferably 6-18, 6 ~10 is further preferred) is preferred. R ⁴² may have a substituent T or a polymerizable group Ps via a linker Zp (including a single bond) within the range of exerting the effect of the present invention. R ⁸² represents a hydrocarbon group. Examples of the hydrocarbon group include those specified in the substituent T described later. The number of carbon atoms in the hydrocarbon group is preferably 1-18, more preferably 1-12, and still more preferably 1-6. In particular, R ⁸² is preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and further preferably having 1 to 3 carbon atoms). R ⁸² may also have a substituent T within the range of exerting the effect of the present invention. m1 is an integer of 0-10. R ⁹² represents a substituent. Examples of substituents for R ⁹² include substituent T described later. When there are two or more ^R92s , they may be connected to each other to form a ring. As the formed ring, an example of ring Cy can be given. At least one of R ⁸² and R ⁹² and the piperidine ring has a polymerizable group. The type of the polymerizable group is exemplified by the aforementioned polymerizable group Ps, and the form of its connection is exemplified by the linking group Zp. A is an acid anion, and the preferred range is the same as that of formula (N3).

In the formula (N3-3), R ⁴³ represents an organic group, and an example of the organic group of the linking group L can be given. Among them, alkylene group (preferably 1-24 carbons, more preferably 1-12, further preferably 1-6), (oligo)alkylene group (the carbon number of the alkylene group in one constituent unit is The number is preferably 1-12, more preferably 1-6, and further preferably 1-3; the number of repetitions is preferably 1-50, more preferably 1-40, and further preferably 1-30; Oxygen atom can be increased or decreased according to the type of element to be connected), aryl group (6-22 carbon number is preferred, 6-18 is more preferred, 6-10 is further preferred), the base of these combinations Group is better. R ⁴³ may have a substituent T or a polymerizable group Ps via a linker Zp (including a single bond) within the range of exerting the effect of the present invention. R ⁷³ , R ⁸³ , R ⁹³ , R ⁷⁴ , R ⁸⁴ and R ⁹⁴ each independently represent a hydrocarbon group. Examples of the hydrocarbon group independently include hydrocarbon groups specified in the substituent T described later. The number of carbon atoms in the hydrocarbon group is preferably 1-18, more preferably 1-12, and still more preferably 1-6. In particular, R ⁷³ , R ⁸³ , R ⁹³ , R ⁷⁴ , R ⁸⁴ and R ⁹⁴ are each independently an alkyl group (preferably 1-12 carbons, more preferably 1-6 carbons, still more preferably 1-3 carbons) is better. R ⁷³ , R ⁸³ , R ⁹³ , R ⁷⁴ , R ⁸⁴ , and R ⁹⁴ may have a substituent T as long as the effect of the present invention is exhibited. Two or more of R ⁷³ , R ⁸³ , and R ⁹³ may be linked together to form a ring. The formed ring includes ring Cy, and more specifically, examples of Cn include a piperidine ring. Two or more of R ⁷⁴ , R ⁸⁴ , and R ⁹⁴ may be linked together to form a ring. The formed ring includes ring Cy, and more specifically, examples of Cn include a piperidine ring. At least one of R ⁷³ , R ⁸³ and R ⁹³ has a polymerizable group. The type of the polymerizable group is exemplified by the aforementioned polymerizable group Ps, and the form of its connection is exemplified by the linking group Zp. At least one of R ⁷⁴ , R ⁸⁴ and R ⁹⁴ has a polymerizable group. The type of the polymerizable group is exemplified by the aforementioned polymerizable group Ps, and the form of its connection is exemplified by the linking group Zp. A is an acid anion, and the preferred range is the same as that of formula (N3).

As the thermal base generator represented by the formula (N3), the following compounds can be exemplified, but the present invention is not limitedly interpreted thereto. [chemical formula 18]

Among the formulas (N1) to (N3), the heat base generator of the formula (N1) or the formula (N2) is more preferable. In the thermal base generator in the form of salt included in the formula (N3), the basic ammonium ion can promote the cyclization of the polymer precursor. From the viewpoint of further improving storage stability without such an action, the specific thermal base generator that does not take the form of a salt is preferable.

The manufacturing method of the specific thermal base generator may be a conventional method. For example, a thermal base generator having a structure represented by formula (N1) can be synthesized by adding an amine to the corresponding lactone or cyclic acid anhydride. A thermal base generator having a structure represented by formula (N2) can be synthesized by reacting an acid chloride or an acid anhydride with a corresponding amine. The thermal base generator having a structure represented by formula (N3) can be synthesized by the method described in International Publication No. WO2015/199219 pamphlet.

In the specific thermal base generator, the pKa of the conjugate acid of the part protonated on the nitrogen atom (hereinafter, sometimes simply referred to as "the pKa of the conjugate acid of the specific thermal base generator") is preferably 4 or less, 2 or less is more preferable, 1 or less is still more preferable, and 0.4 or less is still more preferable. The lower limit of the above-mentioned pKa is actually -5 or more. By setting the pKa of the conjugate acid of the specific thermal base generator to be equal to or less than the above-mentioned upper limit, it is preferable that the cyclization reaction of the polymer precursor is not hindered. The pKa described in the present specification means that the equilibrium constant Ka is represented by a negative common logarithm pKa in consideration of the dissociation reaction of releasing hydrogen ions from oxygen. The lower the pKa, the stronger the acid. Unless otherwise stated, pKa is set to the calculated value based on ACD/ChemSketch. Alternatively, you can refer to the values described in "Revised 5th Edition: Chemistry Handbook - Basics" edited by the Chemical Society of Japan. Regarding the pKa of the conjugate acid of the specific thermal base generator, the increase in pKa based on the same heating (ΔpKa) (difference in pKa before and after heating) is preferably 2 or more, more preferably 5 or more, and still more preferably 8 or more .

Hereinafter, the pKa of the conjugate acid of some exemplified compounds of the specific heat base generator is given.

[Table 1] No. pKa Ba-1 9.07 Ba-2 7.68 Ba-3 6.83 Ba-4 9.53 Ba-5 9.02 Ba-6 9.77 Ba-7 10 Ba-8 11.13 Ba-9 7.72 Ba-10 10.18 Ba-11 7.22 Ba-12 10.77 Ba-13 3.74 Bb-1 7.21 Bb-2 6.48 Bb-3 7.69 Bb-4 9.63 Bb-5 9.61 Bb-6 7.64 Bb-7 3.63 Bc-1 9.67 Bc-2 8.88 Bc-3 8.01 Bc-4 9.77 Bc-5 8.82 Bc-6 7.08

The molecular weight of the specific thermal base generator is not particularly limited, but is preferably 2,000 or less, more preferably 1,000 or less, and still more preferably 500 or less. In order to suppress volatilization of the generated base, it is conceivable to use a high molecular weight base or thermal base generating agent. However, polymer additives may cause problems of solubility in the composition or compatibility with polymer precursors. On the other hand, the specific thermal base generator of the present invention can immobilize the base through the polymerizable group in the system, so it is not necessary to make the thermal base generator high molecular weight, and it is preferable in that it can solve the problem of solubility. Moreover, it is also preferable at the point which can increase the quantity (number of moles) of the base to generate|occur|produce per compounding quantity by using it as a thermal base generator of a low molecular weight. The lower limit of the molecular weight of the specific thermal base generator is not particularly limited, but is actually 80 or more.

The content of the specific thermal base generator in the photosensitive resin composition is preferably at least 0.0025% by mass, more preferably at least 0.01% by mass, and still more preferably at least 0.02% by mass. The upper limit is, for example, preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and may be 3% by mass or less. With respect to 100 parts by mass of the polymer precursor, it is preferably at least 0.01 part by mass, more preferably at least 0.05 part by mass, and still more preferably at least 0.1 part by mass. As an upper limit, for example, 20 mass parts or less is preferable, 10 mass parts or less is more preferable, 7.5 mass parts or less is still more preferable, and 5.0 mass parts or less may be sufficient. By making content of a specific thermal base generator more than the said lower limit, it is preferable at the point which can ensure favorable storage stability. On the other hand, it is preferable at the point which can ensure the corrosion resistance of metal by being below the said upper limit. In addition, as described above, the base generated in the specific thermal base generator has a polymerizable group and is polymerized, so its volatilization can be effectively suppressed. Thereby, a base is more likely to exist in a composition, and a more effective cyclization promotion action can be expected. As a result, the addition amount of the thermal base generator can be suppressed, the side effects caused by adding it can be reduced, and the physical properties of the photosensitive resin composition or the performance of its cured film can be improved. The specific heat base generating agent may use 1 type or may use plural types. When using plural types, the total amount is within the range prescribed above. When the composition of the present invention contains two or more base generators, it is preferable that 80 mass % or more (further 90 mass % or more, especially 95 mass % or more) of the specific thermal base generator contained in the composition is better. In addition, the coordination compound in which the base is immobilized via a polymerizable group is not particularly limited. For example, the state in which the generated bases are bonded to each other or polymerized can be mentioned. Moreover, it can also polymerize with a polymeric compound. In addition, when the polymer precursor has a polymerizable group, it can also be polymerized with the polymerizable group. In addition, it is also possible to perform such polymerization in a complex manner.

Examples of the substituent T include alkyl (preferably having 1 to 24 carbons, more preferably 1 to 12, and still more preferably 1 to 6), arylalkyl (preferably having 7 to 21 carbons, 7-15 is more preferable, 7-11 is further preferable), alkenyl (carbon number 2-24 is preferable, 2-12 is more preferable, 2-6 is further preferable), alkynyl (carbon number 2 ～24 is preferred, 2～12 is more preferred, 2～6 is further preferred), organic amino group (-NR ^N ₂ ) (carbon number 1～24 is preferred, 1～12 is preferred, 1～ 6 is further preferred), aryl (preferably 6-22 carbons, more preferably 6-18, further preferred 6-10), arylalkyl (preferably 7-23 carbons, 7 ～19 is more preferred, 7～11 is further preferred), alkoxy group (carbon number 1～12 is preferred, 1～6 is more preferred, 1～3 is further preferred), aryloxy group (carbon number 6-22 is preferable, 6-18 is more preferable, 6-10 is more preferable), acyl group (carbon number 2-12 is preferable, 2-6 is more preferable, 2-3 is still more preferable) , acyloxy (preferably 2-12 carbons, more preferably 2-6, further preferably 2-3), aryloxy (preferably 7-23 carbons, more preferably 7-19, 7-11 is more preferred), aryloxy group (7-23 carbons is preferred, 7-19 is more preferred, 7-11 is further preferred), carbamoyl group (1-12 carbons is preferred, 1-6 is more preferred, 1-3 is further preferred), sulfamoyl group (carbon number 0-12 is preferred, 0-6 is more preferred, 0-3 is further preferred), Alkylsulfonyl (preferably 1-12 carbons, more preferably 1-6, further preferably 1-3), arylsulfonyl (preferably 6-22 carbons, 6-18 More preferably, 6-10 is further preferred), heterocyclic group (including at least one of oxygen atom, nitrogen atom and sulfur atom; carbon number 1-30 is preferred, 2-24 is more preferred, 3-18 is Further preferred; comprising a 5-membered ring or a 6-membered ring is preferred), (meth)acryl, (meth)acryloxy, imino (=NR ^N ), alkylene (=C( R ^N ) ₂ ), organic groups such as carboxyl groups. In addition, the substituent T includes hydroxyl group, amino group (NH ₂ ), sulfanyl group, sulfonic acid group, sulfonyloxy group, phosphonyl group, phosphonyloxy group, halogen atom (such as fluorine atom, chlorine atom, bromine atom) , iodine atom), oxo group (=O) and other groups composed of inorganic elements. R ^N is an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or a heterocyclic group, specifically, it is selected from the alkyl groups described in the substituent T described later, and the like. The alkyl moiety and alkenyl moiety contained in each substituent may be chain or cyclic, and may be linear or branched. When the said substituent T is a group which can obtain a substituent, it may have a substituent T further. For example, it may be a hydroxyalkyl group in which a hydroxyl group is substituted on the alkyl group.

Examples of the linking group L include alkylene (preferably having 1 to 24 carbons, more preferably 1 to 12, and still more preferably 1 to 6), alkenylene (preferably having 2 to 12 carbons, 2 to 6 are more preferred, 2 to 3 are further preferred), alkynylene (2 to 12 carbons are preferred, 2 to 6 are more preferred, 2 to 3 are further preferred), (oligo)alkane Oxygen group (the carbon number of the alkylene group in one constituent unit is preferably 1-12, more preferably 1-6, further preferably 1-3; preferably 1-50 repetitions, 1-50 40 is more preferred, 1-30 is further preferred; the direction of the alkylene group has nothing to do with the direction of the oxygen compound; the terminal oxygen atom can also increase or decrease according to the element connected), the arylene group (carbon number 6-22 is more preferred, 6 to 18 is more preferred, and 6 to 10 is further preferred), oxygen atom, sulfur atom, sulfonyl group, carbonyl, thiocarbonyl, -NH-, -NR ^N - and the linking group of these combinations . An alkylene group, an alkenylene group, and an alkylene group may have the substituent T mentioned above. For example, an alkylene group may have a hydroxyl group. The linking chain length of the linker L is preferably 1-24, more preferably 1-12, and still more preferably 1-6. Linkage chain length refers to the number of atoms that lie on the shortest path in the group of atoms associated with the link. For example, -CH ₂ -(C=O)-O- becomes 3. In addition, the alkylene group, alkenylene group, and (oligo)alkyleneoxy group defined by the linking group L may be chain or cyclic, and may be linear or branched. The atoms constituting the linking group L preferably include carbon atoms, hydrogen atoms, and optionally heteroatoms (at least one selected from oxygen atoms, nitrogen atoms, and sulfur atoms, etc.). The number of carbon atoms in the linking group is preferably 1-24, more preferably 1-12, and still more preferably 1-6. Hydrogen atoms may be determined according to the number of carbon atoms or the like. The number of heteroatoms is preferably 0 to 12 independently of oxygen atoms, nitrogen atoms, and sulfur atoms, more preferably 0 to 6, and still more preferably 0 to 3.

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

式（1）中，A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹¹ 表示2價的有機基團，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> As a polyimide precursor, it is preferable to contain the structural unit represented by following formula (1). By setting it as such a structure, the composition more excellent in film strength can be obtained. [chemical formula 19]

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 >> R ¹¹¹ represents a divalent organic group. Examples of divalent organic groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or combinations thereof, and straight-chain groups having 2 to 20 carbon atoms. Aliphatic groups, branched aliphatic groups with 3 to 20 carbons, cyclic aliphatic groups with 3 to 20 carbons, aromatic groups with 6 to 20 carbons, or combinations thereof are preferred. An aromatic group having 6 to 20 carbon atoms is more preferable. Examples of the aromatic group include the following AR-1 to AR-10.

[chemical formula 20]

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

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. Diamine may use only 1 type, and may use 2 or more types. 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 a diamine, specifically, the compound described in paragraph 0032 of International Publication No. WO2015/199220 pamphlet can be referred, and it is incorporated in this specification by citing it.

From the viewpoint of the flexibility of the obtained cured film, R ¹¹¹ is preferably represented by -Ar ⁰ -L ⁰ -Ar ⁰ -. However, Ar ⁰ are each independently an aromatic group, an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and particularly preferably having 6 to 10 carbon atoms), and more preferably a phenylene group. L ⁰ represents a single bond, an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO- and groups selected from combinations thereof. The definition of the preferable range is the same as that of A above.

R⁵⁰ ～R⁵⁷ 分別獨立地為氫原子、氟原子或1價的有機基團，R⁵⁰ ～R⁵⁷ 中的至少一個為氟原子、甲基、氟甲基、二氟甲基或三氟甲基。 作為R⁵⁰ ～R⁵⁷ 的1價的有機基團時，可舉出碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式22]

R⁵⁸ 及R⁵⁹ 分別獨立地為氟原子、氟甲基、二氟甲基或三氟甲基。 作為賦予式（51）或（61）的結構之二胺化合物，可舉出二甲基-4,4’-二胺基聯苯、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。可以使用該等中的一種，亦可以組合使用2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 21]

R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, methyl, fluoromethyl, difluoromethyl or trifluoromethyl base. As the monovalent organic group of R ⁵⁰ to R ⁵⁷ , unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), unsubstituted alkyl groups having 1 to 10 carbons (preferably C1-6) fluorinated alkyl group, etc. [chemical formula 22]

R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group. Examples of the diamine compound giving the structure of formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4, 4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. One of these can be used, or two or more can be used in combination

R¹¹² 的定義與A相同，較佳範圍亦相同。<<R ¹¹⁵ >> R ¹¹⁵ in the formula (1) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group including an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. [chemical formula 23]

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 相同。As for the tetravalent organic group represented by R ¹¹⁵ in formula (1), specifically, a tetracarboxylic acid residue remaining after removing an acid dianhydride group from tetracarboxylic dianhydride, etc. are mentioned. Only 1 type may be used for tetracarboxylic dianhydride, and 2 or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7). [chemical formula 24]

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

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

<<R ¹¹³ and R ¹¹⁴ >> In formula (1), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R ¹¹³ and R ¹¹⁴ is a repeating unit containing a radical polymerizable group, and it is more preferable that both of them contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example includes a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth)acryl group, a group represented by the following formula (III), and the like.

[chemical formula 25]

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

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

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and an alkyl group substituted with an aromatic group is more preferable. The carbon number of the alkyl group is preferably 1 to 30 (3 or more when cyclic). The alkyl group may be any of linear, branched and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, Alkyl, octadecyl, isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, camphenyl, camphenyl (camphenyl), decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, camphenyl Diacyl, dicyclohexyl and pinenyl. Also, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable. In this specification, the alkyl group specified here is called "Alk".

The aromatic group is specifically a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure of the constituent group includes a benzene ring (the above formulas AR-1, AR-2, AR-3), Naphthalene ring, biphenyl ring (such as the above formula AR-5, AR-6, AR-7), bisphenyl ring (such as the above formula AR-8, AR-9, AR-10), fenhe ring, pentacyclopentadiene ring Diene, indene ring, azulene ring, heptene ring, indenene ring, perylene ring, condensed pentaphenyl ring, acenaphthene ring, phenanthrene ring, anthracene ring, condensed tetraphenyl ring, chrysene ring, biterphenyl (triphenylene) ring, etc.) (in this specification, the aromatic hydrocarbon group specified here is referred to as "Ary") or a substituted or unsubstituted aromatic heterocyclic group (the ring structure as the constituent group is ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrimidine ring, pyrimidine ring, clam ring, indole ring, indole ring, benzofuran ring , benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthrene pyridine ring, acridine ring, phenanthroline ring, thienium ring, chromene ring, dibenzopyran ring, phenanthiazine ring, phenanthiazine ring or phenanthazine ring) (in this specification, it will be specified here The aromatic heterocycle is called "Aro").

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

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

A¹¹ 及A¹² 表示氧原子或NH，R¹¹¹ 及R¹¹² 分別獨立地表示2價的有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價的有機基團，R¹¹³ 及R¹¹⁴ 中的至少一者為包含自由基聚合性基團之基團為較佳，自由基聚合性基團為更較佳。The structural unit represented by formula (1) is preferably a structural unit represented by formula (1-A) or formula (1-B). [chemical formula 26]

A ¹¹ and A ¹² represent an oxygen atom or NH, R ¹¹¹ and R ¹¹² independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or a monovalent organic group, R ¹¹³ and R It is preferable that at least one of ¹¹⁴ is a group containing a radical polymerizable group, and it is more preferable that it is a radical polymerizable group.

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

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

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

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

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

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

R¹²¹ 表示2價的有機基團，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> It is preferable that a polybenzoxazole precursor contains the structural unit represented by following formula (2). [chemical formula 27]

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, the definition is the same as that of R ¹¹⁵ in the above formula (1), and the preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group, and their definitions are the same as those of R ¹¹³ and R ¹¹⁴ in the above formula (1), and their preferred ranges are also the same.

In addition to the constituent units of the above formula (2), the polybenzoxazole precursor may also contain other types of repeating structural units.

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

The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably at least 20% by mass, more preferably at least 30% by mass, and still more preferably at least 40% by mass, based on the total solid content of the composition. It is more preferably 50 mass % or more, 60 mass % or more is still more preferable, and 70 mass % or more is still more preferable. In addition, the content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and still more preferably 98% by mass or less with respect to the total solid content of the composition. Preferably, 95% by mass or less is still more preferable. The photosensitive resin composition of the present invention may contain only one type of polymer precursor, or may contain two or more types. When containing 2 or more types, it is preferable that a total amount becomes the said range.

＜Polymerization initiator＞ The photosensitive resin composition of this invention contains a photoinitiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. In addition, a thermal polymerization initiator (preferably a thermal radical polymerization initiator) may be used in combination as a means to accelerate the polymerization of the base generated by the thermal base generator.

＜＜Photopolymerization Initiator＞＞ It does not specifically limit as a photoinitiator, It can select suitably from well-known photoinitiator. For example, a photoradical polymerization initiator having photosensitivity to rays from an ultraviolet region to a visible region is preferable. Also, it can be an active agent that interacts with a photoexcited sensitizer to generate active free radicals. The photopolymerization initiator preferably 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.

Since the photosensitive resin composition according to the preferred embodiment of the present invention contains a specific thermal base generator and a photopolymerization initiator, the following actions can be expected. By applying a photosensitive resin composition to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer and then heating, the precursor of a heterocyclic ring-containing polymer can be cyclized and the composition can be cured (primary curing). In this heat hardening, the specific thermal base generator of this invention is useful. Next, light is irradiated to the cured photosensitive resin composition layer. Thereby, (secondary hardening) hardening due to radicals generated by the action of the photopolymerization initiator described above occurs. In this case, when the polymer precursor has a polymerizable group, the polymerizable group or the polymerizable compound polymerizes to perform photocuring. As a result, the solubility in the light irradiation part can be reduced. There is an advantage that regions with different solubility can be easily produced by utilizing this action. Specifically, the photosensitive resin composition layer is exposed through a photomask having a pattern that shields only the electrode portion. Thereby, depending on the pattern of the electrodes, regions having different solubility can be produced.

As the photopolymerization initiator, any known compound can be used arbitrarily. For example, descriptions in paragraphs 0107 to 119 of International Publication No. WO2015/199220 pamphlet can be referred to, and incorporated in this specification by citing them.

In the photosensitive resin composition of the present invention, it is preferable to use an oxime compound (oxime-based photopolymerization initiator) as a photopolymerization initiator. The oxime-based photopolymerization initiator has a linking group >C=N-O-C(=O)- in the molecule. Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04, IRGACURE OXE 369 (above, manufactured by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, Japan Special The photoradical polymerization initiator 2 described in the publication No. 2012-014052). In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKAARKLS NCI-831 and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. Moreover, DFI-091 (made by DAITO CHEMIX Co., Ltd.) can be used.

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

＜＜Thermal polymerization initiator＞＞ A thermal polymerization initiator can also be used in the present invention. A thermal polymerization initiator is a compound that generates free radicals by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound. By adding a thermal polymerization initiator, the cyclization of the polymer precursor can proceed, and the polymerization reaction of the polymer precursor can proceed, so higher heat resistance can be realized. Specific examples of the thermal polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

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

＜Polymerizable compound＞ The photosensitive resin composition of the present invention contains a polymerizable compound, preferably a radical polymerizable compound. Examples of the polymerizable group include the above-mentioned polymerizable group Ps, and among them, groups having ethylenically unsaturated bonds such as vinyl, allyl, vinylphenyl, (meth)acryl, etc. Example of Et. The polymerizable group contained in the polymerizable compound is particularly preferably a (meth)acryl group.

The number of polymerizable groups that the polymerizable compound has may be 1 or 2 or more, but the polymerizable compound preferably has 2 or more polymerizable groups, and more preferably has 3 or more polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less.

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

From the viewpoint of developability, the photosensitive resin composition of the present invention preferably contains at least one bifunctional or higher polymerizable compound containing two or more polymerizable groups (preferably free radical polymerizable groups), including at least One or more trifunctional polymerizable compounds are more preferred. Moreover, it may be a mixture of a bifunctional polymerizable compound and a trifunctional or higher polymerizable compound. In addition, the number of functional groups of a polymeric compound means the number of polymeric groups in 1 molecule.

As specific examples of the polymerizable compound, compounds described in paragraphs 0056 to 0100 of International Publication No. WO2015/199220 pamphlet can be referred to, which are incorporated in this specification by reference.

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

Commercially available polymeric compounds include, for example, SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four ethoxylate chains, and SR-494, which is a bifunctional acrylic acid ester having four ethyleneoxy chains. SR-209, 231, and 239 manufactured by Sartomer Company, Inc. of methyl esters, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, DPCA-60 as a hexafunctional acrylate having 6 TPA-330 of trifunctional acrylate of butoxy chain, urethane oligomer UAS-10, urethane oligomer UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

The content of the polymerizable compound is preferably at least 1% by mass, more preferably at least 3% by mass, and still more preferably at least 5% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. The upper limit is preferably at most 60% by mass, more preferably at most 50% by mass, and still more preferably at most 30% by mass. From the viewpoint of pattern formation, it is preferable that there is an advantage by using a polymerizable compound more than the above-mentioned lower limit. Moreover, it is preferable that there is an advantage by using a polymeric compound below the said upper limit from a viewpoint of elongation at break. Other polymerizable compounds may be used alone or in combination of two or more. When using 2 or more types simultaneously, it is preferable that the total amount becomes the said range.

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

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

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

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

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

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

Specific examples of migration inhibitors include the following compounds. [chemical formula 28]

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0% relative to the total solid content of the photosensitive resin composition. Mass % is further more preferable. The migration inhibitor may be only 1 type, or may be 2 or more types. When there are two or more kinds of migration inhibitors, it is preferable that the total is within the above-mentioned range.

＜Polymerization inhibitor＞ It is preferable that the photosensitive resin composition of this invention contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4- Methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylidene diphenylamine Amine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, ethylene glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxy Quinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N -Nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, etc. In addition, the polymerization inhibitors described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication WO2015/125469 can also be used. When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass % relative to the total solid content of the photosensitive resin composition of the present invention, and 0.02 to 3 mass % is More preferably, 0.05 to 2.5 mass % is still more preferable. The polymerization inhibitor may be only 1 type, or may be 2 or more types. When there are two or more kinds of polymerization inhibitors, it is preferable that the total thereof is within the above-mentioned range.

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

Examples of silane coupling agents include compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, compounds described in paragraphs 0063-0071 of International Publication WO2011/080992A1, JP-A Compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, and compounds described in paragraph 0055 of International Publication WO2014/097594. Moreover, it is also preferable to use different 2 or more types of silane coupling agents as described in paragraph 0050-0058 of Unexamined-Japanese-Patent No. 2011-128358. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulae, Et represents an ethyl group. [chemical formula 29]

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

When the photosensitive resin composition of the present invention has a metal adhesion improving agent, its content is 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The range of 0.5-5 mass % is more preferable. The adhesiveness of the cured film after a curing process and a metal layer becomes favorable by making it more than the said lower limit, and the heat resistance of the cured film after a curing process, and a mechanical characteristic become favorable by being below the said upper limit. Only 1 type may be sufficient as a metal adhesiveness improving agent, and 2 or more types may be sufficient as it. When using 2 or more types, it is preferable that the total is the said range.

＜Other additives＞ The photosensitive resin composition of the present invention can add various additives, such as photohardening accelerators, sensitizing pigments, chain transfer agents, surfactants, higher fatty acid derivatives, etc. , inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. are blended. When these additives are blended, it is preferable to set the total blending amount thereof to 3% by mass or less of the solid content of the composition.

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

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

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

When the photosensitive resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention, preferably 1 to 10 parts by mass. It is more preferable that it is a mass part, and it is still more preferable that it is 1-5 mass parts. The chain transfer agent may be only 1 type, or may be 2 or more types. When there are two or more chain transfer agents, the total range thereof is preferably the above range.

<<surfactant>> Various surfactants can be added to the photosensitive resin composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. Moreover, the following surfactants are also preferable. [chemical formula 30]

When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass relative to the total solid content of the photosensitive resin composition of the present invention. quality%. Surfactant may be only 1 type, and may be 2 or more types. When there are two or more surfactants, the total range is preferably the above range.

＜＜Higher fatty acid derivatives＞＞ In order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide can be added to the photosensitive resin composition of the present invention to partially exist in the drying process after coating. the surface of the composition. When the photosensitive resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the photosensitive resin composition of the present invention. The higher fatty acid derivative may be only 1 type, or may be 2 or more types. When there are two or more higher fatty acid derivatives, the total range is preferably the above range.

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

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

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

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

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

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

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

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

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

The manufacturing method of the cured film of this invention includes the case where the photosensitive resin composition of this invention is used. Specifically, it includes at least the following (a), preferably includes (a) and (d), and more preferably includes the steps of (a) to (d). (a) Film forming step of applying a photosensitive resin composition to a substrate to form a film (b) Exposure step of exposing the film after the film forming step (c) Developing step of developing the exposed photosensitive resin composition layer (d) Heating step of heating the developed photosensitive resin composition at 80-450°C Like this embodiment, by heating after image development, the exposed resin layer can be hardened further. In this heating step, the thermal base generator of the present invention acts to obtain sufficient curability.

The manufacturing method of the laminated body of preferable embodiment of this invention includes the manufacturing method of the cured film of this invention. The manufacturing method of the laminated body of this embodiment After forming a cured film according to the manufacturing method of the above-mentioned cured film, the step of (a) or the step of (a)-(c), or the step of (a)-(d) is performed again . In particular, it is preferable to sequentially perform each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). A laminated body can be formed by laminating a cured film in this way. In the present invention, it is preferable to provide a metal layer on the upper side of the part where the cured film is provided, or between the cured films, or both. In addition, in the manufacture of the laminate, it is not necessary to repeat all the steps (a) to (d). As mentioned above, by performing at least (a), preferably (a) to (c) or (a) to ( In the step d), a laminated body of a cured film can be obtained. These will be described in detail below.

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

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

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

＜＜Development processing steps＞＞ The manufacturing method of the present invention may include a development treatment step, which is to perform development treatment on the exposed photosensitive resin composition layer. By developing, the unexposed part (non-exposed part) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, developing methods such as spin-on immersion, spraying, dipping, and ultrasonic waves can be employed. Image development is performed using a developing solution. There are no particular limitations on the developer as long as it can remove the unexposed portion (non-exposed portion). It is preferable that the developer contains an organic solvent, and it is more preferable that the developer contains more than 90% of the organic solvent. In the present invention, the developer preferably contains an organic solvent with a ClogP value of −1 to 5, more preferably an organic solvent with a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw (chemical biological diagram). As the organic solvent, those exemplified in the section of the above-mentioned <solvent> can be preferably used. In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. It is preferable that 50 mass % or more of a developer is an organic solvent, it is more preferable that 70 mass % or more is an organic solvent, and it is still more preferable that 90 mass % or more is an organic solvent. In addition, 100% by mass of the developer may be an organic solvent.

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

＜＜Heating step＞＞ The production method of the present invention preferably includes a step of heating after the film forming step (layer forming step), drying step, or developing step. In the heating step, the cyclization reaction of the polymer precursor proceeds. In this case, the specific thermal base generator can realize favorable exposure and developability without inhibiting photosensitivity. And, by heating the resin pattern remaining after the development, the specific thermal base generator releases a base, and hardening by cyclization of the resin proceeds quickly and sufficiently. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably at least 50°C, more preferably at least 80°C, still more preferably at least 140°C, still more preferably at least 150°C, and more preferably at least 160°C. Still more preferably, 170°C or higher is still more preferably. The upper limit is preferably 500°C or lower, more preferably 450°C or lower, still more preferably 350°C or lower, still more preferably 250°C or lower, still more preferably 220°C or lower, still more preferably 200°C or lower. good. The heating is preferably carried out at a rate of temperature increase from the temperature at the start of heating to the maximum heating temperature at a rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and still more preferably 3 to 10°C/min. By setting the rate of temperature increase to 1° C./minute or more, excess volatilization of alkali can be prevented while ensuring productivity, and residual stress of the cured film can be relaxed by setting the rate of temperature increase to 12° C./minute or less. The temperature at the start of heating is preferably from 20°C to 150°C, more preferably from 20°C to 130°C, and still more preferably from 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the highest heating temperature. For example, when the photosensitive resin composition is applied to the substrate and dried, the temperature of the dried film (layer), for example, is 30 to 200°C lower than the boiling point of the solvent contained in the photosensitive resin composition. It is preferable to gradually increase the temperature in °C. The heating time (heating time at the highest heating temperature) is preferably from 10 to 360 minutes, more preferably from 20 to 300 minutes, and still more preferably from 30 to 240 minutes. In particular, when forming a multilayer laminate, it is preferable to heat at a heating temperature of 180° C. to 320° C., and more preferably to heat at 180° C. to 260° C. from the viewpoint of the adhesiveness between layers of a cured film. The reason for this is not certain, but it is considered that by setting this temperature, the acetylene groups of the polymer precursor between the layers undergo a crosslinking reaction.

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

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

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

＜＜Stacking steps＞＞ It is preferable that the manufacturing method of the present invention further includes a layering step. The lamination step means performing (a) film formation step (layer formation step), (b) exposure step, (c) development treatment step, (d) heating step on the surface of the cured film (resin layer) or metal layer in sequence a series of steps. Among them, the (d) heating step may be performed at the end or in the middle of the lamination. That is, it may be a state in which the laminated photosensitive resin composition layers are collectively cured by repeating the steps (a) to (c) a predetermined number of times and then performing the heating in (d). Also, (c) may include (e) metal layer forming step after developing step, and at this time, heating in (d) may be performed each time, or heating in (d) may be performed collectively after a predetermined number of laminations. It goes without saying that the above-mentioned drying step, heating step, and the like may be appropriately included in the lamination step. When the layering step is performed after the layering step, the surface activation treatment step may be further performed after the above-mentioned heating step, after the above-mentioned exposure step, or after the above-mentioned metal layer forming step. As the surface activation treatment, plasma treatment is exemplified. It is better to carry out the above lamination step 2 to 5 times, more preferably 3 to 5 times. For example, the resin layer structure such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably 3 or more and 7 or less layers, and is more preferably 3 or more and 5 or less layers. That is, in the present invention, it is particularly preferable to form a cured film (resin layer) of the photosensitive resin composition so as to cover the metal layer after providing the metal layer. Concretely, the state of repeating (a) film forming step, (b) exposing step, (c) developing step, (e) metal layer forming step, (d) heating step in sequence, or (a) sequentially repeating The film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step are provided at the end or in the middle. By alternately performing the lamination step of laminating the photosensitive resin composition layer (resin) and the metal layer forming step, the photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated.

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

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

<Synthesis Example 1> [Polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and benzyl alcohol (A-1: no radical polymerizable group Synthesis of polyimide precursor)] Suspend 14.06g (64.5mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours) and 14.22g (131.58mmol) of benzyl alcohol in 50mL N-methylpyrrolidone and dried over molecular sieves. The suspension was heated at 100°C for 3 hours. After a few minutes of heating a clear solution was obtained. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of SOCl ₂ were added over 10 minutes while maintaining the temperature at -10±4°C. During the addition of SOCl ₂ the viscosity was increased. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 20 minutes at -5 to 0°C. The resulting solution. Next, after allowing the reaction mixture to react at 0°C for 1 hour, 70 g of ethanol was added, followed by stirring overnight at room temperature. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at 45° C. for 3 days under reduced pressure. The weight average molecular weight of the polyimide precursor was 18,000.

A-1 [chemical formula 31]

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

A-2 [chemical formula 32]

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

A-3 [chemical formula 33]

<Synthesis Example 4> [Derived from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (ortho-toluene) and methacrylic acid- Synthesis of polyimide precursor of 2-hydroxyethyl ester (A-4: polyimide precursor with radical polymerizable group)] 20.0 g (64.5 millimoles) of 4,4'- Oxydiphthalic anhydride (stirred at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine ( 258 millimoles) and 100 g of diglyme, and stirred at 60°C for 18 hours to produce 4,4'-oxydiphthalic anhydride and methacrylic acid-2-hydroxyethyl Diesters of esters. Next, after the obtained diester was chlorinated by SOCl ₂ , it was converted into polyimide by the same method as in Synthesis Example 1 using 4,4'-diamino-2,2'-dimethylbiphenyl Precursor, and obtained polyimide precursor with the same method as Synthetic Example 1. The weight average molecular weight of the polyimide precursor was 19,000.

A-4 [chemical formula 34]

<Synthesis Example 5> [Polybenzoxazole precursor (A-5) derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-oxybenzoyl chloride Synthesis] To 100 mL of N-methyl-2-pyrrolidone, 13.92 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added and dissolved with stirring. Next, 11.21 g of 4,4'-oxodibenzoyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5°C, and stirring was continued for 60 minutes. Next, the polybenzoxazole precursor was precipitated in 6 liters of water, and the water-polybenzoxazole precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polybenzoxazole precursor was removed by filtration, stirred again in 6 liters of water for 30 minutes and filtered again. Next, the obtained polybenzoxazole precursor was dried at 45° C. for 3 days under reduced pressure. The weight average molecular weight of the polybenzoxazole precursor is 15,000.

A-5 [chemical formula 35]

Examples and Comparative Examples ＜Preparation of photosensitive resin composition＞ The components described in the following Table 2 were mixed to obtain each photosensitive resin composition. The obtained photosensitive resin composition was pressure-filtered through a filter having a pore width of 0.8 μm. Details such as the names and structures of the compounds described in the tables are shown below the tables as notes. The following evaluation test was done about each prepared photosensitive resin composition. The results are shown in Table 3.

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

<Elongation at break> The photosensitive resin composition layer was formed by applying each of the filtered photosensitive resin compositions on a silicon wafer in a layered form by a spin coating method. The silicon wafer on which the photosensitive resin composition layer was formed was dried on a heating plate at 100°C for 5 minutes, thereby forming a uniform photosensitive resin composition layer with a thickness of 20 μm on the silicon wafer. Use a stepper (Nikon NSR 2005 i9C) to expose the photosensitive resin composition layer on the silicon wafer with an exposure energy of 500mJ/ ^cm2 . The temperature of the photosensitive resin composition layer (resin layer) was raised to 180° C., and then the temperature was maintained for 3 hours. The cured resin layer was immersed in a 4.9% hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain the resin film 1 .

The elongation at break of the resin film 1 was measured using a tensile tester (TENSILON). Specifically, measured in accordance with JIS-K6251:2017 in an environment of 25°C and 65% relative humidity (RH) in the long side direction and width direction of the film at a crosshead speed of 300 mm/min, a width of 10 mm, and a sample length of 50 mm elongation at break. The elongation at break is calculated by E _b (%)=(L _b -L ₀ )/L ₀ (E _b : elongation at the time of cutting, L ₀ : the length of the test piece before the test, L _b : the test piece has been cut The length of the test piece at break time) calculation. In the evaluation, each of the elongation at break in the longitudinal direction and the width direction was measured five times, and the average value in the longitudinal direction and the width direction was used. A: Elongation at break greater than 85% B: Elongation at break greater than 80% and less than 85% C: Elongation at break greater than 75% and less than 80% D: Elongation at break greater than 70% and less than 75% E: Elongation at break Below 70%

[Table 2] polymer precursor heat base generator Photopolymerization initiator polymeric compound polymerization inhibitor migration inhibitor Metal Adhesion Improver solvent type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass Composition 1 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 Composition 2 A-1 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 Composition 3 A-2 33.6 B-2 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-2 0.126 G-1 0.63 I-1 45 I-2 15 Composition 4 A-3 33.6 B-3 0.75 C-1 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition 5 A-4 33.6 B-4 0.75 C-1 1.26 D-2 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 Composition 6 A-5 33.6 B-5 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-3 0.126 G-1 0.63 I-1 45 I-2 15 Composition 7 A-3 33.6 B-6 0.75 C-2 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-3 0.63 I-1 45 I-2 15 Composition 8 A-3 33.6 B-7 0.3 C-1 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition 9 A-3 33.6 B-7 0.75 C-1 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition 10 A-3 33.6 B-8 0.3 C-1 1.26 D-2 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition 11 A-3 33.6 B-8 0.75 C-1 1.26 D-2 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition 12 A-3 33.6 B-9 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-4 0.126 G-1 0.63 I-1 45 I-3 15 Composition 13 A-3 33.6 B-10 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition 14 A-3 33.6 B-11 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-3 0.63 I-1 45 I-2 15 Composition 15 A-3 33.6 B-12 0.75 C-1 1.26 D-2 5.88 E-3 0.084 F-1 0.126 G-1 0.63 I-1 45 I-3 15 Composition 16 A-3 33.6 B-13 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition 17 A-3 33.6 B-14 0.75 C-1 1.26 D-3 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition 18 A-3 33.6 B-15 0.3 C-1 1.26 D-1 5.88 E-3 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 Composition 19 A-3 33.6 B-16 0.75 C-3 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-3 15 Composition 20 A-3 33.6 B-17 0.75 C-1 1.26 D-3 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 Composition 21 A-3 33.6 B-18 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition 22 A-3 33.6 B-19 0.3 C-3 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition 23 A-3 33.6 B-20 0.3 C-3 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition 24 A-3 33.6 B-4/B-5 0.3/0.45 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition 25 A-3 33.6 B-2 0.75 C-1/C-3 0.86/0.40 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition c1 A-3 33.6 BX-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition c2 A-3 33.6 BX-2 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 Composition c3 A-3 33.6 BX-3 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 [table 3] No. Composition storage stability elongation at break Example 1 Composition 1 A A Example 2 Composition 2 C A Example 3 Composition 3 A A Example 4 Composition 4 A B Example 5 Composition 5 A B Example 6 Composition 6 A A Example 7 Composition 7 A B Example 8 Composition 8 A B Example 9 Composition 9 C A Example 10 Composition 10 A B Example 11 Composition 11 C A Example 12 Composition 12 A A Example 13 Composition 13 A A Example 14 Composition 14 A A Example 15 Composition 15 A A Example 16 Composition 16 A A Example 17 Composition 17 A A Example 18 Composition 18 A B Example 19 Composition 19 A A Example 20 Composition 20 A A Example 21 Composition 21 A A Example 22 Composition 22 A B Example 23 Composition 23 A A Example 24 Composition 24 A B Example 25 Composition 25 A A Comparative example 1 Composition c1 E. C Comparative example 2 Composition c2 D. D. Comparative example 3 Composition c3 B E.

(A) Polyimide precursor: each compound shown in the synthesis example above

[化學式37]

(B) Heat base generator etc. [Chemical formula 36]

[chemical formula 37]

Regarding the thermal base generator, the relationship between the example numbers in the above Examples and the numbers of the compounds illustrated in the above general description is shown in Table 4 below. [Table 4] Example No. Usually record No. Example No. Usually record No. Example No. Usually record No. B-1 Bc-1 B-8 Bc-4 B-15 Bc-6 B-2 Ba-1 B-9 Ba-5 B-16 Ba-2 B-3 Bb-1 B-10 Ba-7 B-17 Ba-4 B-4 Bb-2 B-11 Ba-9 B-18 Ba-6 B-5 Ba-3 B-12 Ba-11 B-19 Bc-3 B-6 Bb-3 B-13 Ba-8 B-20 Ba-14 B-7 Bc-2 B-14 Ba-10 - -

Compounds of Comparative Examples [Chemical Formula 38]

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

D-3：A-TMMT（Shin-Nakamura Chemical Co.,Ltd.製）(D) Polymeric compound D-1: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) D-2: SR-209 (manufactured by Sartomer Company, Inc.) [Chemical formula 39]

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

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

(F) Migration inhibitors F-1: Compound M-1 exemplified above F-2: Compound M-2 exemplified above F-3: Compound M-3 exemplified above F-4: Compound M-4 exemplified above

(G) Metal adhesion improver G-1: Compound SC-1 exemplified above G-2: Compound SC-2 exemplified above G-3: Compound SC-3 exemplified above

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

From the above results, it can be seen that in the photosensitive resin composition of the examples using the thermal base generator having a polymerizable group in the part that becomes the base to be generated, any cured film showed a good elongation at break (80% or more ) (Example 1-25). The high elongation at break of the cured film means that the thermal curing of the photosensitive resin composition has been sufficiently carried out. It is considered that the thermal alkali generators of B-1 to B-20 can effectively generate alkali at the film curing temperature, that is, 180°C. And the volatilization of the produced alkali is suppressed. In addition, it is understood that the photosensitive resin composition can also be prepared as required to be excellent in storage stability (Examples 1, 3 to 7, 9, 11 to 24), wherein the alkalinity before heating is suppressed to be low to suppress Prolonged hardening of polymer precursors. On the other hand, in the photosensitive resin composition of the comparative example using the thermal base generator that does not have a polymerizable group, it is considered that the hardening reaction of the thermosetting resin did not proceed sufficiently, and as a result, the elongation at break of the cured film was large and poor. . Moreover, about storage stability, Comparative Examples 1 and 2 were very low.

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

Also, compounds X-4 and X-5 described in the aforementioned Patent Document 3 (JP 2006-282880 A) generate bases by light irradiation, but generation of bases was not confirmed at 200° C. or lower.

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Claims (12)

A photosensitive resin composition comprising a thermal base generator selected from polyimide precursors and polybenzo

A polymer precursor, a photopolymerization initiator, and a polymerizable compound of an azole precursor, wherein the thermal base generator generates a base at a temperature below 200°C, and has a polymerizable group at the site of the generated salt, and the thermal base generator The agent has a structure represented by any one of the following formula (N1) ~ formula (N3),

In the formula (N1), X is a single bond or a divalent linking group, ^R1 independently represents a hydrogen atom or an organic group, n1 and n2 are 1 or 2, n1+n2 is 3, n3 is 0 or 1, When n3 is 1, X is not a single bond. When n1 is 2, the groups in the two [ ] can be the same or different from each other. When n2 is 2, the two R ¹ can be the same or different from each other. The two R ¹ can be connected to each other to form a ring structure, at least one of ^R1 has a polymerizable group,

In formula (N2), R ² represents a hydrogen atom or an organic group, R ³ represents an organic group, n4 and n5 are 1 or 2, n4+n5 is 3, and when n4 is 2, the groups in ( ) can be mutually The same or different, when n5 is 2, the two ^R2 can be the same or different from each other, the two ^R2 can be connected to each other to form a ring structure, at least one of ^{the R2} has a polymerizable group,

In formula (N3), R ⁴ represents an organic group with a valence of n8, R ⁵ and R ⁶ independently represent a hydrogen atom or a hydrocarbon group, R ⁷ to R ⁹ independently represent a hydrocarbon group, A represents an acid anion with a valence of m, m is an integer of 1 to 4, n7 represents an integer of 1 to 12, n8 and n9 represent an integer of 1 to 12, and n8=n9, R ⁵ and R ⁶ can be linked to form a ring structure, R ⁷ to R ⁹ Two or more of them may be linked together to form a ring structure, and at least one of R ⁷ to R ⁹ has a polymerizable group. The photosensitive resin composition as described in item 1 of the scope of the patent application, wherein the polymerizable group of the part that becomes the generated base is an epoxy group, an oxetane group, an ethylenically unsaturated group or the following: The group represented by the formula (Z),

In the formula (Z), Rc represents an oxygen atom, a nitrogen atom or an aromatic group with a valence of (n+2), Ra and Rb independently represent a hydrogen atom or an organic group, n represents an integer from 0 to 6, and Rc represents oxygen In the case of an atom, n is 0, in the case of Rc being a nitrogen atom, n is 1, and * represents a bond. The photosensitive resin composition as described in claim 1, wherein the polymer precursor includes a polyimide precursor. The photosensitive resin composition as described in claim 3, wherein the polyimide precursor has a constituent unit represented by the following formula (1),

In formula (1), ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, ^R113 and ^R114 each independently represent hydrogen Atom or monovalent organic group. The photosensitive resin composition as described in item 4 of the patent claims, wherein at least one of R ¹¹³ and R ¹¹⁴ in the formula (1) contains a radical polymerizable group. The photosensitive resin composition described in Claim 1, which is used for forming an interlayer insulating film for a rewiring layer. A cured film, which is formed by curing the photosensitive resin composition described in any one of the first to sixth claims of the patent application. A laminate having at least two to seven layers of the cured film described in Claim 7 of the scope of application and having a metal layer between the cured films. A method for producing a cured film, comprising a film forming step of applying the photosensitive resin composition described in any one of the first to sixth claims of the patent application to a substrate to form a film. The method for producing a cured film as described in Claim 9 of the patent application, which includes a heating step of heating the film at 80°C to 450°C. The method for producing a cured film as described in Claim 9 or Claim 10 of the patent claims, which includes an exposure step for exposing the film and a developing step for developing the film. A semiconductor device comprising the cured film described in Claim 7 or the laminate described in Claim 8.