TW202024787A - Photosensitive resin composition, cured product, layered product, production method for cured product, and semiconductor device - Google Patents

Abstract

Provided are: a photosensitive resin composition capable of providing a film having excellent storage stability and excellent elongation at break; and a cured product, layered product, and cured product production method using the photosensitive resin composition; and a semiconductor device. This photosensitive resin composition contains a thermal base generator and a polyimide precursor. The thermal base generator generates a base at 200 DEG C or lower and has a polymerizable group at a site where a base is to be generated.

Description

Photosensitive resin composition, cured film, laminate, cured film manufacturing method, semiconductor device

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

Cyclized and hardened resins such as polyimide resins and polybenzoxazole resins are excellent in heat resistance and insulating properties, and therefore are used in various applications (for example, refer to 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, the use as a raw material of an insulating film or a sealing material or a protective film of an insulating film can be cited. In addition, it is also used as a base film or cap layer for flexible substrates. 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. With this, it is possible to achieve excellent operability, and to be applied to a substrate or the like in various forms and processed when manufacturing each product as described above. After that, it is set to a structure formed by cyclizing polyimide and other precursors, and it can form a hardened product. In addition to the high performance possessed by polyimide resins, from the viewpoint of excellent manufacturing adaptability, more and more industrial applications are expected.

Try to apply 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 Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2015-108053 [Patent Document 2] JP 2014-201695 A [Patent Document 3] JP 2006-282880 A [Non-Patent Literature]

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

As described in the above-mentioned patent documents, etc., the polyimide precursor or polybenzoxazole precursor (hereinafter, sometimes collectively referred to as "polymer precursor") is cyclized (ring closed) as described above Thereby, the resin composition can be cured. The polymer precursor is cyclized by heating, but if an alkali is present at this time, the polymer precursor becomes a catalyst to promote cyclization and quickly harden. Therefore, it is considered to include a thermal base generator that generates an alkali during heating to promote the cyclization reaction of the polymer precursor. Regarding this kind of hot alkali generator, it is also required that no alkali is released before heating so as to avoid hardening due to unintentional cyclization and to achieve stability during storage. In addition, among the conventional hot alkali generators, the molecules generated as alkalis are relatively small and volatile. Therefore, in an environment heated to a predetermined temperature, the alkali sometimes volatilizes from the system. If the base volatilizes from the composition, the effect of using the base to cyclize the polymer precursor cannot be expected, resulting in the deterioration of the elongation at break of the resulting film.

In view of the technical problems in these photosensitive resin compositions, the object of the present invention is to provide a photosensitive resin composition capable of achieving sufficient curing properties by heating for photosensitive resin compositions containing polymer precursors and A cured film, a laminate, a cured film manufacturing method and a semiconductor device using the photosensitive resin composition. In particular, its object is to provide a photosensitive resin composition that is excellent in storage stability and also excellent in elongation at break when used as a cured film, and a cured film, laminate, and cured film using the photosensitive resin composition And semiconductor devices.

As a result of research conducted by the present inventors, they studied to impart a polymerizable group to the generated base. That is, the polymerizable group is introduced into the thermal base generator to form a structure in which the decomposed base has the polymerizable group. The generated base is polymerized with other molecules via the polymerizable group, whereby the base exists in the system while maintaining its activity and in a state that is higher than that of a conventional polymer. Thereby, it was found that the volatilization of the alkali can be suppressed, and the cyclization of the polymer precursor during heat curing can be effectively promoted. Specifically, the above-mentioned problem was solved by the following method.

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 alkali generator generates a base at 200°C or less, and has a polymerizable group at the site of the generated salt. <2> The photosensitive resin composition according to <1>, wherein the thermal alkali 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 each 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 [] may be the same or different from each other, when n2 is 2, the two R ¹ may be the same or different from each other, and 2 R ¹ May be linked to each other to form a cyclic structure, and at least one of R ¹ 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 R ² may be the same or different from each other, the two R ² may be connected to each other to form a cyclic structure, and at least one of R ² has a polymerizable group; [Chemical formula 3]

In formula (N3), R ⁴ represents an n8-valent organic group, R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, R ⁷ to R ⁹ each independently represent a hydrocarbon group, A represents an m-valent acid anion, m It is an integer from 1 to 4, n7 represents an integer from 1 to 12, n8 and n9 represent an integer from 1 to 12, and n8=n9, R ⁵ and R ⁶ may be connected to form a cyclic structure, R ⁷ to R ⁹ Two or more may be connected separately to form a cyclic 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 contained in the site to be the base produced is an epoxy group, an oxetane group, and an ethylenic A saturated group or a group represented by the following formula (Z); [Chemical formula 4]

In formula (Z), Rc represents an oxygen atom, nitrogen atom or (n+2) valence aromatic group, Ra and Rb each 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, and when Rc is a nitrogen atom, n is 1, and * represents a bonding 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 each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent hydrogen Atom or monovalent organic group. <6> The photosensitive resin composition according to <5>, in which at least one of R ¹¹³ and R ¹¹⁴ in the above formula (1) contains a radical polymerizable group. <7> The photosensitive resin composition according to any one of <1> to <6>, which is used for formation of an interlayer insulating film for a rewiring layer. <8> A cured film obtained by curing the photosensitive resin composition described in any one of <1> to <7>. <9> A laminated body having two or more layers and seven or less layers of the cured film described in <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 as described in <10>, which includes a heating step of heating the film at 80 to 450°C. <12> The method for producing a cured film as described in <10> or <11>, which has an exposure step of exposing the film and a development step of developing the film. <13> A semiconductor device having the cured film described in <8> or the laminated body described in <9>. [Invention Effect]

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

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

The description of the constituent elements of the present invention described below may be performed based on representative embodiments of the present invention, but the present invention is not limited to these embodiments. Regarding the label of the group (atomic group) in this specification, the label system that does not describe substituted and unsubstituted includes both those that do not have a substituent and those that have a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl), but also substituted alkyl (substituted alkyl). In addition, when it is called an alkyl group, it may be chained or cyclic, and when it is chained, it may be linear or branched. The meanings of these are the same for alkenyl, alkylene, and alkenylene. As long as "exposure" in this specification is not particularly limited, in addition to exposure with light, drawing with particle beams such as electron beams and ion beams is also included in exposure. In addition, as the light used for exposure, there are usually actinic rays or radiations such as extreme ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, electron beams, etc. represented by the bright-ray spectrum of mercury lamps and excimer lasers. In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic" and "methacrylic". Both or either, "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, the term "step" is not only an independent step, but even if it cannot be clearly distinguished from other steps, if the desired effect of the step can be achieved, it is included in this term. Unless otherwise specified, the physical property values in the present invention are values at a temperature of 23° C. and an air pressure of 101,325 Pa. In this specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are based on gel permeation chromatography (GPC measurement) and are defined as styrene conversion values. In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). As long as there is no special description, the eluent will be measured with THF (tetrahydrofuran). In addition, as long as there is no special description, the detection is to use a UV ray (ultraviolet) wavelength 254 nm detector.

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 including a thermal base generator having a polymerizable group (hereinafter, sometimes It is called "specific thermal base generator"), polymer precursor, photopolymerization initiator and polymerizable compound. Hereinafter, the present invention will be described in detail according to preferred embodiments.

＜Specific hot alkali generator＞ The specific thermal base generator generates a base at 200°C or lower and has a polymerizable group at the site of the salt to be generated. The generation of a base at 200°C or lower means that the compound becomes a compound with a larger pKa of the conjugate acid than the original compound by isomerization or decomposition at a temperature of 200°C or lower. The temperature at which the above-mentioned specific hot alkali generator generates alkali (hot alkali generation temperature) is preferably 180°C or less, and may also be 150°C or less. As the lower limit of the hot alkali generation temperature, 50°C or higher is preferred, 60°C or higher is more preferred, 70°C or higher is more preferred, and 80°C or higher is even more preferred. It is preferable to set the temperature of the alkali that generates the hot alkali generator to be less than the above-mentioned upper limit because it can generate alkali with low energy consumption and harden the resin compared to those generated at higher temperatures. On the other hand, it is preferable to set the temperature at which the alkali is generated to be equal to or higher than the above-mentioned lower limit, so as to decompose compounds during storage at room temperature and the like to generate alkali, thereby suppressing or preventing hardening of the resin. In addition, it is preferable that the specific thermal alkali generator generates alkali within the above-mentioned temperature range in the heating step described later. In addition, the specific thermal alkali generator is preferably a compound that generates alkali below the heat-resistant temperature of the cured film.

As an embodiment of the present invention, two or more specific thermal alkali generators having different alkali generation temperatures can also be blended. With this configuration, for example, the base is generated in stages, 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 base produced. The number of polymerizable groups possessed by the specific thermal base generator 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 more preferably 3 or less. The lower limit is not particularly limited, and may be 1 or more. Examples of the polymerizable group include those undergoing radical polymerization, those undergoing addition polymerization, and those undergoing polycondensation. Those undergoing radical polymerization and addition polymerization are preferred, and those undergoing radical polymerization are more preferred. Examples of the polymerizable group include an epoxy group (including a glycidyl group), an oxetane 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)acrylic acid, (methyl) ) Allyloxy, (meth)acrylic amino, etc., among which vinyl, vinylphenyl, (meth)acrylic, (meth)acrylic, (meth)acrylic An amino group is preferred. The amine group of the (meth)acryloylamino group is not limited to -NH-, and may be -NR ^N- (R ^N is an alkyl, alkenyl, aryl, arylalkyl or heterocyclic group, specifically In other words, it is selected from the structure of the alkyl group described in the substituent T described later). ^RN may be connected to the linker to which the polymerizable group is connected or the parent structure of the thermal base generator to form a ring. As the ring to be formed, an example of the ring Cn described later can be given. In this specification, the ethylenically unsaturated group exemplified here is referred to as Et, and the polymerizable group containing the ethylenically unsaturated group is referred to as 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 the formula (Z), Rc represents an oxygen atom, a nitrogen atom, or a (n+2)-valent aromatic group. 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. When Rc is a benzene ring, for example, n is an integer of 0-4. * Indicates a bonding key. Examples of the (n+2)-valent aromatic group include an aromatic hydrocarbon group (a carbon number of 6-22 is preferred, 6-18 is more preferred, and 6-10 is even more preferred) or aromatic heterocyclic group ( The carbon number is preferably from 1 to 24, more preferably from 1 to 12, and even more preferably from 1 to 6), more specifically, a group including the aromatic hydrocarbon ring Ary and the aromatic heterocyclic ring Aro described later . When Ra and Rb are organic groups, examples of the organic groups include independently alkyl groups (1 to 12 carbon atoms are preferred, 1 to 6 are more preferred, and 1 to 3 are further preferred), Alkenyl (2 to 12 carbons is preferred, 2 to 6 is more preferred, 2 to 3 is more preferred), aryls (6 to 22 are preferred, 6 to 18 is more preferred, 6 to 10 Is further preferred), arylalkyl (carbon number 7-23 is preferred, 7-19 is more preferred, 7-11 is further preferred). Among them, the alkyl group is preferred, and specifically, the example of Alk described later can be given.

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 ¹ in the formula is an organic group. Examples of organic groups include alkyl groups (1 to 12 carbon atoms are preferable, 1 to 6 are more preferable, and 1 to 3 are more preferable), alkenyl groups (2 to 12 carbons are preferable, 2-6 is more preferable, 2-3 is more preferable), aryl (carbon number 6-22 is preferable, 6-18 is more preferable, 6-10 is more preferable), arylalkyl (carbon The number is preferably from 7 to 23, more preferably from 7 to 19, and even more preferably from 7 to 11). Among them, the alkyl group is preferred, and specifically, the example of Alk described later can be given. Rb ¹ is a hydrogen atom or a methyl group. nb is an integer of 1-5. na is an integer that becomes 5-nb. * Is a bonding key. Ar ¹ can be exemplified by an aromatic hydrocarbon group (with 6 to 22 carbons, more preferably 6 to 18, and even more preferably 6 to 10) or aromatic heterocyclic groups (with 1 to 24 carbons, 1 -12 is more preferable, and 1 to 6 are more preferable). More specifically, a group including the aromatic hydrocarbon ring Ary and the aromatic heterocyclic ring Aro described later can be mentioned. Among them, Ar ¹ is preferably a phenyl group.

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

<<Linker>> In the specific thermal base generator, the polymerizable group can be introduced into the compound via the linker. The structure in which the polymerizable group is introduced with or without the linking group can be represented by the following formula (Zp), for example. In addition, in the present specification, when it is referred to as "having a polymerizable group", "including a polymerizable group", etc., it includes the state where the polymerizable group is introduced into the parent structure by the linking group as described above. *-Zp-Ps formula (Zp) * indicates the bonding position with the parent structure of the hot alkali generator. The meaning of Ps is the same as the above-mentioned polymerizable group Ps. Zp is a single bond or a linking group (hereinafter, to include a single bond, it is sometimes called a linking group Zp or Zp for short). The structure of the linking group Zp is not particularly limited as long as it can connect the polymerizable group to the parent structure of the base generator. Therefore, as long as it is not too long or too large, it can be a linking base of any structure. For example, when the 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 site serving as the linking group or the reactivity with the parent structure or the polymerizable group. The length of the linking chain of Zp is also not particularly limited, but considering the structure of the actual linking group, 0-24 is preferred, 0-12 is more preferred, and 0-6 is further preferred (0 means single bond ). When Zp is a linking group, it is preferable that the carbon atom and the hydrogen atom include a hetero atom (at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom) 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. The hydrogen atoms may be determined according to the number of carbon atoms and the like. The number of heteroatoms is preferably 0-12 independently of oxygen atoms, nitrogen atoms, sulfur atoms, etc., more preferably 0-6, and still more preferably 0-3. As the types of specific linking groups are wide, examples of linking groups L described later can be given. Among them, Zp is an alkylene group (the carbon number is preferably from 1 to 12, the carbon number is more preferably from 1 to 6, and the 1-3 is even more preferred), and the arylene group (the carbon number is preferably from 6 to 22, and from 6 to 18 is More preferably, 6 to 10 are further preferred), an oxygen atom (oxy group), a carbonyl group, -NH-, -NR ^N -, and groups formed by combining these are preferred. ^RN may be connected to other parts to form a ring structure. Specifically, as the cyclic structure formed, the following examples of the ring Cn can be given.

It is more preferable that the linking group Zp is a linking group 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 hot alkali generator. ** is the bond position with Ps. R ^M is a hydrogen atom or a group defined by R ^N above. R ^M may be connected to the methylene group in the parentheses of nz in the following formulas z5 to z8 to form a cyclic structure. Specifically, examples of the following ring Cn can be given, and more specifically, a piperidine ring can be given. [Chemical formula 8]

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

<<Formula (N1)>> The specific thermal base generator preferably has a structure represented by the following formula (N1). [Chemical formula 9]

In the formula (N1), X is a single bond or a divalent linking group. As the bivalent linking group, examples of linking group L described later can be given. Among them, the hydrocarbon group is preferred, and the alkylene group, alkenylene group, arylene group or a combination thereof is 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. The link chain length when X is a divalent linking group is preferably 1-12, more preferably 1-8, and still more preferably 1-6. Specifically, ethylene group, propylene group, butyl group, ethylene group, phenyl group, phenylene group, phenylene group, and methylene phenylene group can be mentioned. In the range where the effect of the present invention is exerted, X may have a substituent T as appropriate. For example, the aspect in which a predetermined linking group has a hydroxyl group or a carboxyl group, etc. are mentioned.

R ¹ each independently represents a hydrogen atom or an organic group. As an organic group, the organic group specified in the substituent T mentioned later can be 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 (the carbon number is preferably 1 to 12, more preferably 1 to 6, and more preferably 1 to 3). R ¹ may have a substituent T within the range of exerting the effect of the present invention.

When n2 is 2 and R ¹ is 2, both of them are not 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, two R ¹ may be the same or different from each other.

When n2 is 2, two R ¹ may be connected to each other to form a ring structure. Examples of the formed cyclic structure include aliphatic hydrocarbon rings (the ones exemplified below are referred to as ring Cf) (for example, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclopropene ring Ring, cyclobutene ring, cyclopentene ring, cyclohexene ring, etc.), aromatic hydrocarbon ring (the exemplified below is called ring Cr) (benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc.), Nitrogen heterocycles (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, pyrazole ring, piperidine ring, Piper 𠯤 ring, oromoline ring, etc.), acid-containing heterocyclic ring (the following examples are called ring Co) (furan ring, piperan ring, oxirane ring, oxetane ring, tetrahydrofuran ring, tetrahydrofuran Hydropiperan ring, two mouth ring mountain ring, etc.), sulfur-containing heterocyclic ring (the following examples are referred to as ring Cs) (thiophene ring, sulfide ring, thiocyclobutane ring, tetrahydrothiophene ring, Tetrahydrothiopyran ring, etc.) and so on. These rings are collectively referred to as the ring Cy.

At least one of R ¹ has a polymerizable group. As for the polymerizable group, examples of the above-mentioned Ps can be given, and examples of the linking group Zp mentioned above can be given as an aspect 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。The above formula (N1) is preferably any one of the following formula (N1-1), formula (N1-2), and formula (N1-3). [Chemical formula 10]

In formula (N1-1), X ¹ is a divalent linking group, and examples of the above-mentioned X can be given as a preferable range. In the range where the effect of the present invention is exerted, X ¹ may have a substituent T as appropriate. R ¹¹ and R ¹² each independently represent a hydrogen atom or an organic group. As the organic group of R ¹¹ and R ¹² , each independently includes the organic group 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 (the carbon number is preferably from 1 to 12, preferably from 1 to 6 and more preferably from 1 to 3). However, both of R ¹¹ and R ¹² are not hydrogen atoms. R ¹¹ and R ¹² may have a substituent T within the range of exerting the effect of the present invention. R ¹¹ and R ¹² may be connected to each other to form a ring structure. As the formed ring, an example of the ring Cy can be given. At least one of R ¹¹ and R ¹² has a polymerizable group. As for the polymerizable group, examples of the above-mentioned Ps can be given, and examples of the linking group Zp mentioned above can be given as an aspect of its connection.

In the formula (N1-2), X ² is a divalent linking group, and examples of the above-mentioned X can be given as a preferable range. In the range where the effect of the present invention is exerted, X ² may have a substituent T as appropriate. R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an organic group. As the organic group for R ¹³ and R ¹⁴ , each independently includes the 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 (the carbon number is preferably from 1 to 12, preferably from 1 to 6 and more preferably from 1 to 3). However, both of R ¹³ and R ¹⁴ are not hydrogen atoms. R ¹³ and R ¹⁴ may have a substituent T within the range of exerting the effect of the present invention. R ¹³ and R ¹⁴ may be connected to each other to form a ring structure. As the formed ring, an example of the ring Cy can be given. At least one of R ¹³ and R ¹⁴ has a polymerizable group. As for the polymerizable group, examples of the above-mentioned Ps can be given, and examples of the linking group Zp mentioned above can be given as an aspect of its connection.

In the formula (N1-3), X ³ is a 2+m4 linking group, among which, an aromatic hydrocarbon group (the carbon number is preferably 6-22, 6-18 is more preferably, 6-10 is more preferably) is Preferably, in terms of the ring structure, an example of the aromatic hydrocarbon ring Ary described later can be given. In the range where the effect of the present invention is exerted, X ³ may have a substituent T as appropriate. Y ¹ is a group represented by -(CO) _m3 -OH, and m3 is 0 or 1. R ¹⁵ to R ¹⁸ each independently represent a hydrogen atom or an organic group. As the organic group of R ¹⁵ to R ¹⁸ , each independently includes the organic group 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 (the carbon number is preferably from 1 to 12, from 1 to 6 is more preferably, and from 1 to 3 is more preferably) is preferably. m4 is an integer of 0-12, preferably an integer of 0-8, and more preferably an integer of 0-4. Both R ¹⁵ and R ¹⁶ are not hydrogen atoms. R ¹⁵ and R ¹⁶ may be connected to each other to form a ring. As the formed ring, an example of the ring Cy can be given. At least one of R ¹⁵ and R ¹⁶ has a polymerizable group. As for the polymerizable group, examples of the above-mentioned Ps can be given, and examples of the linking group Zp mentioned above can be given as an aspect of its connection. R ¹⁵ and R ¹⁶ may have a substituent T within the range of exerting the effect of the present invention. Both R ¹⁷ and R ¹⁸ are not hydrogen atoms. R ¹⁷ and R ¹⁸ may be connected to each other to form a ring. As the formed ring, an example of the ring Cy can be given. At least one of R ¹⁷ and R ¹⁸ has a polymerizable group. As for the polymerizable group, examples of the above-mentioned Ps can be given, and examples of the linking group Zp mentioned above can be given as an aspect of its connection. R ¹⁷ and R ¹⁸ may have a substituent T within the range of exerting the effect of the present invention. When X ³ is a linking group constituted by an aromatic ring, a benzene ring is preferred. In this case, for example, the aspect in which two carboxyl groups are substituted as Y ¹ can be mentioned. If it expresses specifically, the following formula (N1-3a) is 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. The meanings of the preferable aspects of R ¹⁵ to R ¹⁸ are the same as those previously defined by formula (N1-3). R ¹⁵ and R ¹⁶ , and R ¹⁷ and R ¹⁸ are not hydrogen atoms, and may form a ring Cy. At least any one of R ¹⁵ and R ¹⁶ and at least one of R ¹⁷ and R ¹⁸ have a polymerizable group Ps, and the polymerizable group may be introduced into the parent structure via a linking group Zp.

Hereinafter, the compound forming the specific thermal base generator represented by formula (N1) is exemplified, but the present 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 thermal base generator has a structure represented by the following formula (N2). [Chemical formula 13]

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

R ³ is an organic group, an alkyl group (the carbon number is preferably 1-24, 2-18 is more preferable, and 3-14 is more preferable), an aryl group (the carbon number is preferably 6-30, 6-24 More preferably, 6-18 is further preferred), arylalkyl (the carbon number is preferably 7 to 31, 7-25 is more preferred, 7-19 is further preferred), or a heterocyclic group-containing group (The carbon number is preferably 1-30, 2-24 is more preferable, 3-18 is more preferable; the heterocyclic group is preferably a 5-membered ring, a 6-membered ring or a combination of these; Examples include the examples of the substituent T described later). R ³ may have a substituent T within the range of exerting the effect of the present invention.

n4 and n5 are 1 or 2, and n4+n5 is 3. When n5 is 2, R ² will not be both 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 cyclic structure, and examples of the ring formed include the ring Cy. At least one of R ² has a polymerizable group. As the type of the polymerizable group, an example of the polymerizable group Ps can be given, and the connection with the parent structure can be an example of the linking group 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. However, both R ²¹ and R ²² are not 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 (the carbon number is preferably from 1 to 12, from 1 to 6 is more preferred, and from 1 to 3 is even more preferred) is preferred. R ²¹ and R ²² may have a substituent T within the range of exerting the effect of the present invention. At least one of R ²¹ and R ²² has a polymerizable group. Examples of the polymerizable group include the above-mentioned polymerizable group Ps, and the connection to the R ²¹ and R ²² side includes the connection via the linking group Zp. R ²¹ and R ²² may be connected to each other to form a ring. As the formed ring, an example of the ring Cy can be given. R ³¹ is an organic group, and an alkyl group is preferred. In this case, the alkyl group has preferably 1-24 carbon atoms, more preferably 1-18, and even more preferably 1-12, especially tertiary alkyl (for example, tertiary butyl, 1,1-di Methylpropyl, adamantyl) are preferred. R ³¹ may have a substituent T within the range of exerting the effect of the present invention.

In the formula (N2-2), R ²³ and R ²⁴ each independently represent a hydrogen atom or an organic group. However, both R ²³ and R ²⁴ are not 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 (the carbon number is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3) is preferred. R ²³ and R ²⁴ may have a substituent T within the range of exerting the effect of the present invention. At least one of R ²³ and R ²⁴ has a polymerizable group. Examples of the binding group include the above-mentioned polymerizable group Ps, and the connection to the side of R ²³ and R ²⁴ includes connection through the linking group Zp. R ²³ and R ²⁴ may be connected to each other to form a ring. As the formed ring, an example of the ring Cy can be given. L ¹ is a single bond or a linking group, and a linking group is particularly preferred. When L ¹ is a linking group, examples of the linking group L described later can be given, among which the alkylene group (the carbon number is preferably 1-12, more preferably 1-6, and more preferably 1-3) is more good. Ar ² is an aromatic ring, an aromatic hydrocarbon ring (the carbon number is 6-22 is preferred, 6-18 is more preferred, 6-14 is more preferred; 5-membered ring or 6-membered ring or at least any heterocyclic ring is Preferred; as specific examples can be given Ary's example) or aromatic heterocyclic ring (carbon number 2-24 is preferred, 2-18 is more preferred, 2-12 is further preferred; as the heteroatom, oxygen atom, Nitrogen and sulfur atoms are preferred, 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, Aro can be cited Or thioxanthene (10,10-dioxide) is preferred. Ar ² may have a substituent T within the range of exerting the effect of the present invention.

As the thermal base generator represented by the formula (N2), the following compounds can be exemplified, but the present invention is not limitedly interpreted by this. [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 the formula (N3), R ⁴ represents an n8-valent organic group. Examples of the organic group include the organic group of the substituent T described later (wherein, the valence is interpreted as n8). Among them, the n8-valent alkane structure group (the carbon number is preferably 1-18, 1-12 is more preferably, and the 1-6 is more preferable) or the aryl structure group (the carbon number is 6-22 is more Preferably, 6-18 is more preferable, 6-10 is further preferable) is more preferable. R ⁴ may have a substituent T within the range of exerting the effect of the present invention. R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group. As the organic group, the hydrocarbon group is preferred, the aliphatic hydrocarbon group (the carbon number is preferably from 1 to 18, the more preferred is from 1 to 12, and the more preferred is from 1 to 6) and the aromatic hydrocarbon group (the carbon number is from 6 to 22 is more preferred). Preferably, 6-18 is more preferable, 6-10 is more preferable) is more preferable, and alkyl group (the carbon number is 1-12 is preferable, 1-6 is more preferable, and 1-3 is more preferable) is further 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 where the effects of the present invention are exhibited. R ⁵ and R ⁶ may be connected to each other to form a ring. As the ring formed, an example of the ring Cf can be given. R ⁷ to R ⁹ each independently represent a hydrocarbon group. As the hydrocarbon group of R ⁷ to R ⁹ , the hydrocarbon groups defined in the substituent T described later can be individually exemplified. The carbon number of 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 (the carbon number is preferably 1 to 12, more preferably 1 to 6, and more preferably 1 to 3). The hydrocarbon group of R ⁷ to R ⁹ may have a substituent T within the range of exerting the effect of the present invention. R ⁷ to R ⁹ may each connect two or more to form a ring. Examples of the ring formed include ring Cy, and more specifically, examples of Cn. Among them, a piperidine ring can be cited. A represents an m-valent acid anion. Specific examples of A can be exemplified comprise * -COO ^- (carboxylate anion) of the group (* is a bonding site with the other key), * ^- COO - are preferred. 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 an 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 can be exemplified by the above-mentioned polymerizable group Ps, and the form of the connection can be exemplified by the linking group Zp.

The above formula (N3) is preferably the following formula (N3-1), formula (N3-2) or formula (N3-3). [Chemical formula 17]

In the 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, the alkyl group (the carbon number is preferably 1 to 18, the more preferable is 1 to 12, and the more preferable is 1 to 6) or the aryl group (the carbon number is 6 to 22 is preferable, and the 6 to 18 is more preferable, and 6 ~10 is further preferred) is preferred. In the range where the effect of the present invention is exerted, R ⁴¹ may have a substituent T or a polymerizable group Ps via the linking group Zp (including a single bond). R ⁷¹ , R ⁸¹ and R ⁹¹ each independently represent a hydrocarbon group. As the hydrocarbon group of R ⁷¹ , R ^81, and R ⁹¹ , each independently includes the hydrocarbon group specified in the substituent T described later. The carbon number of 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 (the carbon number is preferably from 1 to 12, from 1 to 6 is more preferred, and from 1 to 3 is further preferred). R ⁷¹ , R ^81, and R ⁹¹ may have a substituent T within the range of exerting the effect of the present invention. Two or more of R ⁷¹ , R ⁸¹ and R ⁹¹ may be connected to each other to form a ring. Examples of the ring formed include ring Cy, and more specifically, examples of Cn. Among them, a piperidine ring can be cited. At least one of R ⁷¹ , R ⁸¹ and R ⁹¹ has a polymerizable group. The type of the polymerizable group can be exemplified by the above-mentioned polymerizable group Ps, and the form of the connection can be 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 (N3-2), 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, the alkyl group (the carbon number is preferably 1 to 18, the more preferable is 1 to 12, and the more preferable is 1 to 6) or the aryl group (the carbon number is 6 to 22 is preferable, and the 6 to 18 is more preferable, and 6 ~10 is further preferred) is preferred. As long as the effect of the present invention is exerted, R ⁴² may have a substituent T or a polymerizable group Ps via the linking group Zp (including a single bond). R ⁸² represents a hydrocarbon group. As this hydrocarbon group, the hydrocarbon group specified in the substituent T mentioned later can be mentioned. The carbon number of 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 (the carbon number is preferably 1 to 12, more preferably 1 to 6, and more preferably 1 to 3). R ⁸² may have a substituent T within the range of exerting the effects of the present invention. m1 is an integer of 0-10. R ⁹² represents a substituent. As the substituent of R ⁹² , examples of the substituent T described later can be given. When R ⁹² has two or more, they may be connected to each other to form a ring. As the formed ring, an example of the 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 can be exemplified by the above-mentioned polymerizable group Ps, and the form of the connection can be 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 examples of the organic group of the linking group L can be given. Among them, alkylene (the carbon number is preferably 1-24, more preferably 1-12, and even more preferably 1-6), (oligo)alkyleneoxy (the carbon of the alkylene in one structural unit The number is preferably from 1 to 12, more preferably from 1 to 6, and more preferably from 1 to 3; the number of repetitions is preferably from 1 to 50, more preferably from 1 to 40, and more preferably from 1 to 30; The oxygen atom of is increased or decreased according to the type of element to be connected), aryl group (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), the base of these combinations Group is better. As long as the effect of the present invention is exerted, R ⁴³ may have a substituent T or a polymerizable group Ps via the linking group Zp (including a single bond). R ⁷³ , R ⁸³ , R ⁹³ , R ⁷⁴ , R ⁸⁴ and R ⁹⁴ each independently represent a hydrocarbon group. As the hydrocarbyl group, the hydrocarbyl group specified in the substituent T described later can be individually exemplified. The carbon number of 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 (the carbon number is preferably from 1 to 12, from 1 to 6 is more preferred, and from 1 to 3 is further preferred) For better. R ⁷³ , R ⁸³ , R ⁹³ , R ⁷⁴ , R ^84, and R ⁹⁴ may have a substituent T within the range of exerting the effects of the present invention. Two or more of R ⁷³ , R ⁸³ , and R ⁹³ may each be connected to form a ring. Examples of the ring formed include ring Cy, and more specifically, examples of Cn. Among them, a piperidine ring can be cited. Two or more of R ⁷⁴ , R ⁸⁴ , and R ⁹⁴ may be connected to each other to form a ring. Examples of the ring formed include ring Cy, and more specifically, examples of Cn. Among them, a piperidine ring can be cited. At least one of R ⁷³ , R ⁸³ and R ⁹³ has a polymerizable group. The type of the polymerizable group can be exemplified by the above-mentioned polymerizable group Ps, and the form of the connection can be 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 can be exemplified by the above-mentioned polymerizable group Ps, and the form of the connection can be 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 by this. [Chemical formula 18]

Among formulas (N1) to (N3), the hot alkali generator of formula (N1) or formula (N2) is more preferred. In the salt form of the thermal base generator contained in the formula (N3), basic ammonium ions can promote the cyclization of the polymer precursor. From the viewpoint of further improving storage stability without this effect, a specific thermal base generator that does not adopt a salt form is preferable.

The manufacturing method of the specific hot alkali 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 anhydride. The thermal base generator having the structure represented by formula (N2) can be synthesized by reacting acid chloride or acid anhydride with the corresponding amine. The thermal base generator having the structure represented by formula (N3) can be synthesized by the method described in the pamphlet of International Publication No. WO2015/199219.

In the specific thermal base generator, it is preferable that the pKa of the conjugate acid of the part protonated on its nitrogen atom (hereinafter sometimes referred to as "pKa of the conjugate acid of the specific thermal base generator") is 4 or less. 2 or less is more preferable, 1 or less is more preferable, 0.4 or less is even more preferable. The lower limit of the 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 lower than the above upper limit, it is preferable in that it does not hinder the cyclization reaction of the polymer precursor. The pKa mentioned in this specification means that the equilibrium constant Ka is expressed by the negative common logarithm pKa in consideration of the dissociation reaction of hydrogen ion release from oxygen. It means that the smaller the pKa, the stronger the acid. Unless otherwise specified, the pKa is set to a calculated value based on ACD/ChemSketch. Alternatively, you can refer to the values recorded in the "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 rise (ΔpKa) of the same pKa based on heating (the difference in pKa before and after heating) is preferably 2 or more, more preferably 5 or more, and even more preferably 8 or more .

Hereinafter, with regard to a part of the exemplified compounds of the specific thermal base generator, the pKa of its conjugate acid 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 more preferably 500 or less. In order to suppress the volatilization of the alkali produced, it is considered that the alkali or the thermal alkali generator is a high molecular weight one. However, polymer additives sometimes cause problems with solubility in the composition or compatibility with polymer precursors. In contrast, the specific thermal base generator of the present invention can immobilize a base via a polymerizable group in the system. Therefore, there is no need to make the thermal base generator a high molecular weight, and it is preferable in that it can solve the problem of solubility. In addition, it is also preferable in terms of being able to increase the amount (number of moles) of alkali generated per blending amount by using a low molecular weight thermal alkali generator. The lower limit of the molecular weight of the specific thermal base generator is not particularly limited, but is actually 80 or more.

The specific thermal base generator is preferably 0.0025% by mass or more in the photosensitive resin composition, more preferably 0.01% by mass or more, and even more preferably 0.02% by mass or more. As an upper limit, for example, 20 mass% or less is preferable, 10 mass% or less is more preferable, 5 mass% or less is more preferable, and it may be 3 mass% or less. With respect to 100 parts by mass of the polymer precursor, 0.01 parts by mass or more is preferable, 0.05 parts by mass or more is more preferable, and 0.1 parts by mass or more is more preferable. As an upper limit, for example, 20 parts by mass or less is preferable, 10 parts by mass or less is more preferable, 7.5 parts by mass or less is more preferable, and it may be 5.0 parts by mass or less. By setting the content of the specific thermal base generator to be equal to or greater than the above lower limit, it is preferable to ensure good storage stability. On the other hand, by setting it as the upper limit or less, it is preferable to ensure the corrosion resistance of a metal. In addition, as described above, the base produced in the specific thermal base generator has a polymerizable group and is polymerized, so that volatilization can be effectively suppressed. Thereby, the base is more likely to be present in the composition, and a more effective cyclization promotion effect 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 the cured film can be improved. The specific thermal alkali generator may be used singly or in plural. When multiple types are used, the total amount becomes the range specified above. When the composition of the present invention contains two or more kinds of alkali generators, it is preferable that 80% by mass or more (and more than 90% by mass, especially 95% by mass or more) contained in the composition is the specific thermal alkali generator. Better. In addition, the coordination compound in which the base is fixed via the polymerizable group is not particularly limited. For example, a state in which the generated bases are bonded to each other or polymerized can be cited. In addition, it may be polymerized with a polymerizable compound. In addition, when the polymer precursor has a polymerizable group, it may be polymerized with the polymerizable group. In addition, it can also be a state where these aggregations are carried out in a complicated manner.

As the substituent T, an alkyl group (1 to 24 carbon atoms is preferable, 1 to 12 is more preferable, and 1 to 6 is even more preferable), arylalkyl groups (7 to 21 carbon atoms are preferable, 7-15 is more preferred, 7-11 is further preferred), alkenyl (carbon number 2-24 is preferred, 2-12 is more preferred, 2-6 is further preferred), alkynyl (carbon number is 2 ~24 is preferred, 2~12 is more preferred, 2~6 is further preferred), organic amine group (-NR ^N ₂ ) (carbon number 1~24 is preferred, 1~12 is more preferred, 1~ 6 is more preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), arylalkyl (carbon number 7-23 is preferred, 7 ～19 is more preferable, 7-11 is more preferable), alkoxy (carbon number 1-12 is preferable, 1-6 is more preferable, 1-3 is more preferable), aryloxy (carbon number 6-22 is preferable, 6-18 is more preferable, 6-10 is more preferable), acyl group (the carbon number is 2-12 is preferable, 2-6 is more preferable, 2-3 is more preferable) , Acyloxy group (the carbon number is preferably 2-12, 2-6 is more preferable, and 2-3 is more preferable), aryloxy group (the carbon number is 7-23 is preferable, and 7-19 is more preferable, 7-11 is more preferred), aryloxy (carbon number 7-23 is preferred, 7-19 is more preferred, 7-11 is more preferred), carbamethanyl (carbon number 1-12 Is preferred, 1 to 6 is more preferred, and 1 to 3 is further preferred), sulfamoyl (the carbon number is 0 to 12 is preferred, 0 to 6 is more preferred, and 0 to 3 is more preferred), Alkylsulfonyl (1 to 12 carbons is preferred, 1 to 6 is more preferred, and 1 to 3 is more preferred), arylsulfonyl (6 to 22 is preferred, 6 to 18 is More preferably, 6-10 is further preferred), heterocyclic group (containing 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 More preferably; a 5-membered ring or a 6-membered ring is preferred), (meth)acryloyl group, (meth)acryloyloxy group, imino group (=NR ^N ), alkylene group (=C( R ^N ) ₂ ), carboxyl and other organic groups. In addition, the substituent T includes a hydroxyl group, an amino group (NH ₂ ), a sulfanyl group, a sulfonic acid group, a sulfonyloxy group, a phosphinyl group, a phosphinyl group, and a halogen atom (e.g., 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, and is specifically selected from the alkyl groups described in the substituent T described later, and the like. The alkyl part and the alkenyl part contained in each substituent may be chain-like or cyclic, and may be linear or branched. When the above-mentioned substituent T is a group capable of obtaining a substituent, it may further have a substituent T. For example, it may be a hydroxyalkyl group in which a hydroxyl group is substituted on the alkyl group.

As the linking group L, an alkylene group (the carbon number is preferably 1 to 24, 1 to 12 is more preferable, and 1 to 6 is even more preferable), and an alkenylene group (the carbon number is preferably 2 to 12, 2 to 6 are more preferable, 2 to 3 are more preferable), alkynylene (the carbon number is 2 to 12 is preferable, 2 to 6 is more preferable, and 2 to 3 is more preferable), (oligo) alkane Oxy group (the number of carbon atoms of the alkylene group in one structural unit is preferably 1-12, more preferably 1-6, more preferably 1-3; repeating number is preferably 1-50, 1~ 40 is more preferred, and 1-30 is further preferred; the direction of the alkylene group and the oxy group compound has nothing to do; the terminal oxygen atom can also increase or decrease according to the element connected), the aryl group (carbon number 6-22 Is preferred, 6-18 is more preferred, 6-10 is further preferred), oxygen atom, sulfur atom, sulfonyl group, carbonyl group, thiocarbonyl group, -NH-, -NR ^N -and linking groups of these combinations . The alkylene group, alkenylene group, and alkoxy group may also have the aforementioned substituent T. For example, the alkylene group may have a hydroxyl group. The link chain length of the linking group L is preferably 1-24, more preferably 1-12, and still more preferably 1-6. The length of the link chain refers to the number of atoms in the shortest path of the atom group related to the link. For example, when it is -CH ₂ -(C=O)-O-, it becomes 3. In addition, the alkylene group, alkenylene group, and (oligo)alkylene group defined by the linking group L may be chain-like or cyclic, and may be linear or branched. As atoms constituting the linking group L, it is preferable to include a carbon atom and a hydrogen atom, and if necessary, a hetero atom (at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom). The number of carbon atoms in the linking group is preferably 1-24, more preferably 1-12, and still more preferably 1-6. The hydrogen atoms may be determined according to the number of carbon atoms and the like. The number of heteroatoms is preferably 0-12 independently of oxygen atom, nitrogen atom, and sulfur atom, more preferably 0-6, and still more preferably 0-3.

＜Polymer precursors＞ The photosensitive resin composition of the present invention includes a polymer precursor selected from polyimide precursors and polybenzoxazole precursors. As the polymer precursor, a polyimide precursor is more preferable, and a polyimine precursor containing a structural unit represented by the following formula (1) is 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。<Polyimine precursor> As a polyimine precursor, it is preferable to contain the structural unit represented by following formula (1). By using this structure, a composition with more excellent film strength can be obtained. [Chemical formula 19]

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

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

<<R ¹¹¹ >> R ¹¹¹ represents a divalent organic group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, heteroaromatic groups, or groups containing these combinations, and linear chain having 2 to 20 carbon atoms An aliphatic group, a branched aliphatic group having 3 to 20 carbons, a cyclic aliphatic group having 3 to 20 carbons, an aromatic group having 6 to 20 carbons, or a group including a combination of these are preferred. The aromatic group having 6 to 20 carbon atoms is more preferable. As an example of an aromatic group, the following AR-1-AR-10 are mentioned.

[Chemical formula 20]

In the formula, A is a single bond or is selected from aliphatic hydrocarbon groups with 1 to 10 carbons which can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -S(=O) _2- , -NHCO- and the combination of these groups are preferred, single bonds or selected from alkylene groups with 1 to 3 carbons which may be substituted by fluorine atoms, -O-, -C(=O)-, The groups in -S- and -SO ₂ -are more preferably selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -and -C(CH _{3) 2} - group of the divalent group is further preferred.

R ¹¹¹ is preferably derived from diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, the diamine includes a linear aliphatic group having 2 to 20 carbons, a branched or cyclic aliphatic group having 3 to 20 carbons, an aromatic group having 6 to 20 carbons, or a group containing these combinations Groups are preferred, and diamines containing aromatic groups with 6 to 20 carbon atoms are more preferred.

As the diamine, specifically, the compound described in paragraph 0032 of the pamphlet of International Publication No. WO2015/199220 can be referred to and incorporated into this specification by quoting.

From the viewpoint of the flexibility of the cured film obtained, R ¹¹¹ is preferably represented by -Ar ⁰ -L ⁰ -Ar ⁰ -. However, Ar ^{0 is} each independently an aromatic group, and an aromatic hydrocarbon group (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is particularly preferred) is preferred, and phenylene is more preferred. L ⁰ represents a single bond, an aliphatic hydrocarbon group of 1 to 10 carbons that can be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO- And a group selected from the combination of these. The definition of the preferred range is the same as the above A.

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, from the viewpoint of i-ray transmittance and easy availability, the divalent organic group represented by the formula (61) is more preferable. [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 , an unsubstituted alkyl group having 1 to 10 carbons (preferably 1 to 6 carbons), and 1 to 10 carbons (preferably Carbon 1-6) fluorinated alkyl group, etc. [Chemical formula 22]

R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, fluoromethyl, difluoromethyl, or trifluoromethyl. As the diamine compound imparted to the structure of the formula (51) or (61), 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 of them can be used in combination

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

The definition of R ^{112 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。Regarding the tetravalent organic group represented by R ¹¹⁵ in the formula (1), specifically, the tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride and the like can be mentioned. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (7). [Chemical formula 24]

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ is the same as defined in formula (1) is R ^115.

Specific examples of tetracarboxylic dianhydride include those selected from 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'-Diphenylmethyl Ketonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3 ,3',4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2 ,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane- 3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3, 4,9,10-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)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1, At least one of 2,3,4-benzenetetracarboxylic dianhydride and alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

<<R ¹¹³ and R ¹¹⁴ >> In formula (1), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. At least one of R ¹¹³ and R ¹¹⁴ is preferably a repeating unit containing a radical polymerizable group, and it is more preferred 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)acryloyl group, a group represented by the following formula (III), and the like.

[Chemical formula 25]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferred. In formula (III), R ²⁰¹ represents an alkylene having 2 to 12 carbons, -CH ₂ CH(OH)CH ₂ -or a (poly)oxyalkylene having 4 to 30 carbons (as an alkylene, carbon The number is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 to 3; the repeating number is preferably from 1 to 12, more preferably from 1 to 6 and particularly preferably from 1 to 3). In addition, (poly)alkylene oxide means alkylene oxide or polyalkylene oxide. Preferred examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, Hexamethylene, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ -are Better. Particularly preferably, R ²⁰⁰ is a methyl group, and R ²⁰¹ is an ethylene group.

As a preferable embodiment of the polyimide precursor in the present invention, the monovalent organic group of R ¹¹³ or R ¹¹⁴ may include 1, 2 or 3 acid groups, preferably one The 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 can be mentioned. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. 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 to 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 an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, it is preferable to include 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 (when it is cyclic, it is 3 or more). The alkyl group may be any of linear, branched, and cyclic. Examples of straight-chain or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl Alkyl, octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of 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, tricyclodecyl, tetracyclodecyl, and camphenyl. Diacyl, dicyclohexyl and pinenyl (pinenyl). In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferred. In this specification, the alkyl group defined herein is referred to as "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 formula AR-1, AR-2, AR-3), Naphthalene ring, biphenyl ring (such as the above formula AR-5, AR-6, AR-7), biphenyl ring (such as the above formula AR-8, AR-9, AR-10), stilbene ring, and cyclopentane Diene, indene ring, azulene ring, heptene ring, indenene ring, perylene ring, fused pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, chrysene ring, terphenylene ring (Triphenylene ring, etc.) (in this specification, the aromatic hydrocarbon group defined herein is referred to as "Ary") or substituted or unsubstituted aromatic heterocyclic group (as the cyclic structure of the constituent group, it is 茀Ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyridine ring, pyrimidine ring, takwell 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, thien ring, chromene ring, dibenzopyran ring, phenoxathi ring, phenanthrene ring or phenanthrazine ring) (in this manual, it will be specified here The aromatic heterocyclic ring is called "Aro").

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

In addition, for the purpose of improving the adhesion to the substrate, the aliphatic group having a siloxane structure and the structural unit represented by formula (1) can be copolymerized. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

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 each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each 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 a radical polymerizable group is more preferable.

A ¹¹ , A ¹² , R ¹¹¹ , R ^113, and R ¹¹⁴ have the same meaning as the preferred ranges of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1). the same. The same as R (5) in the preferred range of meaning as in formula R ^{112 112,} more preferably an oxygen atom. The bonding position of 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, and 5 are preferred.

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

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

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 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. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent, and then reacting it with a diamine. In the production method of the polyimide precursor, it is preferable to use an organic solvent when performing the reaction. The organic solvent may be one type or two or more types. The organic solvent can be appropriately set according to the raw material, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone can be exemplified.

When manufacturing the polyimide precursor, it is preferable to include a step of separating out solids. 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, thereby enabling solid precipitation.

R¹²¹ 表示2價的有機基團，R¹²² 表示4價的有機基團，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價的有機基團。<Polybenzoxazole precursor> The polybenzoxazole precursor preferably contains a structural unit represented by the following formula (2). [Chemical formula 27]

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

R ¹²¹ represents a divalent organic group. As a divalent organic group, aliphatic groups (1-24 carbons are preferred, 1-12 are more preferred, and 1-6 are particularly preferred) and aromatic groups (carbons 6-22 are preferred, 6 to 14 are more preferable, and 6 to 12 are particularly preferable) at least one group is preferable. 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. Preferably, R ^{121 is} derived from 4,4'-oxobenzyl 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 preferred range is also the same. R ¹²² is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and have the same definitions as R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferred ranges are also the same.

In addition to the structural unit of the above-mentioned formula (2), the polybenzoxazole precursor may also contain other kinds of repeating structural units.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000. The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 20% by mass or more relative to the total solid content of the composition, more preferably 30% by mass or more, and even more preferably 40% by mass or more, It is more preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably 70% by mass or more. Furthermore, the content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less relative to the total solid content of the composition, more preferably 99% by mass or less, and more preferably 98% by mass or less. Preferably, 95% by mass or less is more preferable. The photosensitive resin composition of this invention may contain only 1 type of polymer precursor, and may contain 2 or more types. When two or more types are contained, the total amount is preferably in the above-mentioned range.

＜Polymerization initiator＞ The photosensitive resin composition of the present invention contains a photopolymerization initiator. 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 an agent that promotes the polymerization of the alkali generated by the thermal alkali generator.

＜＜Photopolymerization initiator＞＞ The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, a radical photopolymerization initiator having photosensitivity to light from the ultraviolet region to the visible region is preferable. In addition, it can be an active agent that has some effect on the sensitizer excited by light and generates active free radicals. The photopolymerization initiator preferably contains at least one compound having at least about 50 molar absorption coefficient in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is better to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) and use an ethyl acetate solvent at a concentration of 0.01 g/L.

Since the photosensitive resin composition of the preferred embodiment of the present invention contains a specific thermal base generator and a photopolymerization initiator, the following effects can be expected. The photosensitive resin composition is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer and then heated, whereby the precursor of the heterocyclic ring-containing polymer can be cyclized to harden the composition (primary curing). In this heat curing, the specific thermal alkali generator of the present invention is useful. Next, light is irradiated to the cured photosensitive resin composition layer. This produces (secondary curing) curing caused by free radicals generated by the action of the aforementioned photopolymerization initiator. At this time, it may be a form in which the polymerizable group or polymerizable compound when the polymer precursor has a polymerizable group is polymerized for photocuring. As a result, the solubility in the light irradiation part can be reduced. It has the advantage that the area with different solubility can be made easily by using this function. Specifically, the photosensitive resin composition layer is exposed through a photomask having a pattern for shielding only the electrode portion. In this way, regions with different solubility can be produced according to the electrode pattern.

As the photopolymerization initiator, any known compound can be used arbitrarily. For example, it is possible to refer to the description of paragraphs 0107 to 119 of the pamphlet of International Publication No. WO2015/199220, and to quote them and incorporate them into this specification.

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

When the photopolymerization initiator is included, the content is preferably 0.1% by mass or more relative to the total solid content of the photosensitive resin composition of the present invention, more preferably 0.5% by mass or more, and more preferably 1.0% by mass or more. good. As the upper limit, 30% by mass or less is preferable, 20% by mass or less is more preferable, 15% by mass or less is more preferable, and 10% by mass or less is even more preferable. The photopolymerization initiator may contain only one type or two or more types. When two or more types of photopolymerization initiators are contained, the total amount is preferably in the above range.

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

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 still more preferably 5 to 15% by mass. The thermal polymerization initiator may contain only one type or two or more types. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above-mentioned range.

＜Polymerizable compound＞ The photosensitive resin composition of the present invention contains a polymerizable compound, and preferably contains a radical polymerizable compound. As the polymerizable group, examples of the above-mentioned polymerizable group Ps can be given, among them, groups having ethylenically unsaturated bonds such as vinyl, allyl, vinylphenyl, (meth)acryloyl group, etc. Et example. It is particularly preferable that the polymerizable group contained in the polymerizable compound is a (meth)acryloyl group.

The number of polymerizable groups possessed by the polymerizable compound may be one or two or more. However, the polymerizable compound preferably has two or more polymerizable groups, and more preferably has three or more polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

The molecular weight of the polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and 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 more polymerizable compound containing two or more polymerizable groups (preferably radical polymerizable groups), and at least One type of polymerizable compound having three or more functions is more preferable. In addition, 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 polymerizable compound refers to the number of polymerizable groups in one molecule.

As a specific example of the polymerizable compound, the compound described in paragraphs 0056 to 0100 of the pamphlet of International Publication No. WO2015/199220 can be referred to, and these are incorporated into this specification by quoting.

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

Commercial products of polymerizable compounds include, for example, SR-494 manufactured by Sartomer Company, Inc as a 4-functional acrylate having 4 ethoxy chains, and SR-494 as a difunctional acrylic having 4 ethyleneoxy chains. SR-209, 231, 239 manufactured by Sartomer Company, Inc. of methyl ester, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a 6-functional acrylate with 6 pentyloxy chains, as having 3 different extensions Butoxy chain trifunctional acrylate TPA-330, urethane oligomer UAS-10, urethane oligomer UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

The content of the polymerizable compound is preferably 1% by mass or more with respect to the total solid content of the photosensitive resin composition of the present invention, more preferably 3% by mass or more, and even more preferably 5% by mass or more. As the upper limit, 60% by mass or less is preferable, 50% by mass or less is more preferable, and 30% by mass or less is more preferable. From the viewpoint of pattern formation, it is preferable that the use of a polymerizable compound above the above lower limit has advantages. In addition, from the viewpoint of elongation at break, it is preferable that the use of a polymerizable compound below the above upper limit has advantages. The other polymerizable compounds may be used singly or in combination of two or more kinds. When two or more types are used at the same time, the total amount is preferably in the above-mentioned range.

＜Solvent＞ The photosensitive resin composition of the present invention preferably contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfenes, and amines. As esters, for example, preferred ones include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate Ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate (for example, methyl alkoxy acetate, Ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate Etc.)), 3-alkoxypropionic acid alkyl esters (for example, 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (for example, 3-methoxy propionic acid methyl ester , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (for example, 2- Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2-methoxypropionic acid propyl ester, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester)), 2-alkoxy-2-methylpropionic acid methyl ester and 2- Ethyl alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate Ester, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. As ethers, for example, preferred ones include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, 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 the ketones, for example, preferred ones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and the like. As aromatic hydrocarbons, for example, preferable ones include toluene, xylene, anisole, limonene and the like. As the sulfenite, for example, a preferable one includes dimethyl sulfenite. As the amides, preferred ones include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Dimethylformamide and so on.

Regarding the solvent, from the viewpoint of improvement of the coating surface shape, etc., a form in which two or more types are mixed is also preferable. In the present invention, it is selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate , Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfene, ethyl carbitol acetate, butyl carbitol One solvent of acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or a mixed solvent composed of two or more types is preferred. It is particularly preferable to use dimethyl sulfoxide and γ-butyrolactone at the same time.

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

＜Migration inhibitor＞ The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer. The migration inhibitor is not particularly limited, and examples include heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetra Azole ring, pyridine ring, pyran ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, oromoline ring, 2H-pyran ring and 6H-pyran ring, tri-pyran ring) compounds, with Thiourea and mercapto compounds, hindered phenol compounds, salicylic acid derivative compounds, and hydrazine derivative compounds. 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, ion trapping agents that trap anions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711, and JP 2011 can be used. -059656, the compound described in paragraph 0052, the compound described in paragraph 0114, paragraph 0116, and paragraph 0118 of JP 2012-194520, etc.

As specific examples of migration inhibitors, the following compounds can be given. [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 relative to the total solid content of the photosensitive resin composition, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0 The mass% is more preferable. There may be only one type of migration inhibitor, or two or more types. When two or more types of migration inhibitors are used, the total of them is preferably in the above-mentioned range.

＜Polymerization inhibitor＞ The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, 4-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4- Methyl-6-tertiary butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitroso diphenylamine, N-phenylnaphthylamine, ethylene diphenylamine Aminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyl 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-tertiarybutyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compound 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% by mass relative to the total solid content of the photosensitive resin composition of the present invention, and 0.02 to 3% by mass More preferably, 0.05 to 2.5% by mass is still more preferable. There may be only one type of polymerization inhibitor, or two or more types. When there are two or more kinds of polymerization inhibitors, it is preferable that the sum total is the above range.

＜Metal adhesion improver＞ The photosensitive resin composition of the present invention preferably contains a metal adhesion modifier for improving the adhesion with metal materials used for electrodes, wiring, and the like. As a metal adhesion improver, a silane coupling agent etc. are mentioned.

Examples of silane coupling agents include the compounds described in paragraphs 0062 to 0073 of JP 2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication WO2011/080992A1, and JP The compound described in paragraphs 0060 to 0061 of 2014-191252, the compound described in paragraphs 0045 to 0052 of JP 2014-041264, and the compound described in paragraph 0055 of International Publication WO2014/097594. In addition, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP 2011-128358 A. 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, the metal adhesion improver can also use the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A, and the sulfides described in paragraphs 0032 to 0043 of JP 2013-072935 A.

When the photosensitive resin composition of the present invention has a metal adhesion improver, its content is 0.1-30% by mass, more preferably 0.5-15% by mass relative to the total solid content of the photosensitive resin composition of the present invention The range of is more preferably the range of 0.5 to 5 mass%. By setting it as the above-mentioned lower limit or more, the adhesiveness of the cured film after a hardening process becomes good, and by setting it as below the said upper limit, the heat resistance and mechanical properties of the cured film after a hardening process become good. There may be only one type of metal adhesion improver, or two or more types. When two or more types are used, it is preferable that the sum total is the above-mentioned range.

＜Other additives＞ The photosensitive resin composition of the present invention can add various additives, such as light curing accelerators, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, as needed, within the range that does not impair the effects of the present invention. , Inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. are blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the 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 an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with a thermal hardening accelerator, a thermal polymerization initiator, a photopolymerization initiator, etc., to produce effects such as electron transfer, energy transfer, and heat generation. Thereby, the thermal hardening accelerator, thermal polymerization initiator, and photopolymerization initiator undergo chemical changes to decompose and generate radicals, acids, or bases. For the details of the sensitizing dye, refer to the description in paragraphs 0161 to 0163 of JP 2016-027357 A, and the contents are incorporated into this specification.

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

＜＜Chain transfer agent＞＞ The photosensitive resin composition of this invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in pages 683-684 of the third edition of the Polymer Dictionary (Edited by The Society of Polymer Science (Japan), 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These low-activity free radicals are supplied with hydrogen to generate free radicals, or after oxidation, free radicals can be generated by deprotonation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptopolybenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) can be preferably used. 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, 1 to 10 Parts by mass is more preferable, and 1 to 5 parts by mass is still more preferable. The chain transfer agent may be only one type or two or more types. When there are two or more chain transfer agents, the total range is preferably the above range.

<<Surfactant>> From the viewpoint of further improving coating properties, various surfactants can be added to the photosensitive resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. In addition, 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 with respect to the total solid content of the photosensitive resin composition of the present invention, more preferably 0.005 to 1.0 quality%. The surfactant may be only one type or two or more types. When there are two or more surfactants, the total range is preferably the above-mentioned range.

＜＜Higher fatty acid derivatives＞＞ In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the photosensitive resin composition of the present invention, which is partially present 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. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more higher fatty acid derivatives, the total range is preferably the above range.

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

From the viewpoint of insulation, the photosensitive resin composition of the present invention preferably has a metal content of less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and less than 0.5 mass ppm. Further better. Examples of metals 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 in the above range. In addition, as a method for reducing the metal impurities accidentally included in the photosensitive resin composition of the present invention, it is possible to exemplify the selection of a raw material with a small metal content as the raw material constituting the photosensitive resin composition of the present invention. The raw material of the photosensitive resin composition is filtered by a filter, the inside of the device is lined with polytetrafluoroethylene, and distillation is carried out under the condition of suppressing pollution as much as possible.

Considering the use as a semiconductor material and from the viewpoint of wiring corrosion, the photosensitive resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm. ppm is more preferable. Among them, less than 5 mass ppm is preferable in the state of halogen ion, less than 1 mass ppm is more preferable, and less than 0.5 mass ppm is more preferable. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of the chlorine atom and the bromine atom or the chlorine ion and the bromine ion be in the above-mentioned ranges.

As the storage container of the photosensitive resin composition of the present invention, a conventionally known storage container can be used. In addition, as a storage container, for the purpose of suppressing the mixing of impurities into the raw material or composition, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 types of 6-layer resins, and a bottle in which 6 types of resins are formed into a 7-layer structure. Examples of these containers include those described in JP 2015-123351 A.

＜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 or particles in the composition, it is preferable to perform filtration using a filter. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be cleaned in advance with an organic solvent. In the filtration step of the filter, multiple filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering for multiple times, it can be cyclic filtering. Furthermore, filtration may be performed after pressurization. When filtering is performed after pressurization, the pressurization pressure is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, it can also be used to remove impurities using adsorbents. It can also be combined with filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

<Cured film, laminate, semiconductor device, and manufacturing methods of these> Next, the cured film, the laminated body, the semiconductor device, and the manufacturing method thereof will be described. The cured film of the present invention is formed by curing the photosensitive resin composition of the present invention. The film thickness of the cured film of the present invention can be 0.5 μm or more, or can be 1 μm or more, for example. Moreover, as an upper limit, it can be 100 micrometers or less, and can also be 30 micrometers or less.

Two or more layers of the cured film of the present invention can be laminated, and 3 to 7 layers can be laminated as a laminated body. It is preferable that the seed layer system of the cured film of the present invention having two or more layers has a metal layer between the cured films. These metal layers can be preferably used as metal wiring such as rewiring 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. In addition, examples include sealing films, substrate materials (base film or cap layer of flexible printed circuit boards, interlayer insulating films), or patterning of insulating films for actual mounting purposes by etching, etc. . For these uses, for example, you can refer to Science & Technology Co., Ltd. "High-functionalization and Application Technology of Polyimide" April 2008, Kakimoto Masaki/Supervisor, CMC Technical Library "Polyimide Materials The foundation and development of "Polyimine" issued in November 2011, Japan Polyimine and Aromatic Polymer Research Society/Edition "The latest polyimine basics and applications" NTS, August 2010, etc.

In addition, the cured film in the present invention can also be used in the production of offset printing plates or screen plates, the use of molded parts, and the production of protective paints 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 including (a) and (d), and more preferably the step including (a) to (d). (A) Film formation step of applying photosensitive resin composition to a substrate to form a film (B) Exposure step of exposing the film after the film formation step (C) Development step of developing the exposed photosensitive resin composition layer (D) A heating step of heating the developed photosensitive resin composition at 80-450°C Like this embodiment, the exposed resin layer can be cured by heating after development. In this heating step, the thermal alkali generator of the present invention acts to obtain sufficient curability.

The manufacturing method of the laminated body of the 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 forms a cured film according to the above-mentioned manufacturing method of a cured film, and then performs step (a) or steps (a) to (c) or steps (a) to (d) again . In particular, it is preferable to sequentially perform the above-mentioned steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured film in this way, a laminate can be formed. In the present invention, it is particularly preferable to provide a metal layer on the upper side of the part where the cured film is provided, between the cured films, or both. In addition, it is not necessary to repeat all the steps (a) to (d) in the production of the laminate. As mentioned above, by performing at least (a), preferably (a) to (c) or (a) to ( In the step d), a laminate of a cured film can be obtained. Hereinafter, these will be explained in detail.

＜＜Film forming step (layer forming step)＞＞ The manufacturing method of the preferred embodiment of the present invention includes a film forming step (layer forming step) of applying a photosensitive resin composition to a substrate to form a film (layered). The type of substrate can be appropriately set according to the application, but is not particularly limited. Examples include semiconductor substrates 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, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, etc. In the present invention, semiconductor substrates are particularly preferred, and silicon substrates are more preferred. Furthermore, when the photosensitive resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes a substrate. As a method of applying the photosensitive resin composition to the substrate, coating is preferred. Specifically, as the application method, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, 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. By adjusting the appropriate solid content concentration or coating conditions according to the method, a resin layer with a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a round substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and as long as it is a rectangular substrate, the slit coating method Or spraying method, inkjet method, etc. are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

＜＜Drying step＞＞ The manufacturing method of the present invention may further include a step of drying in order 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 even more preferably 90-110°C. As the drying time, 30 seconds to 20 minutes are exemplified, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<<Exposure Step>> The manufacturing method of the present invention may include an exposure step to expose the photosensitive resin composition layer. The exposure amount is not particularly limited within the range that can harden the photosensitive resin composition. For example, it is preferable to irradiate 100 to 10,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, and more preferably to irradiate 200 to 8000 mJ/cm ² . The exposure wavelength can be appropriately set in the range of 190-1000 nm, preferably 240-550 nm. Regarding the exposure wavelength, if it is described in terms of the relationship with 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), wide (3 wavelengths of g, h, and i rays), (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 based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. In this way, particularly high exposure sensitivity can be obtained.

＜＜Development processing steps＞＞ The manufacturing method of the present invention may include a development process step to perform a development process on the exposed photosensitive resin composition layer. By developing, the unexposed part (non-exposed part) is removed. The development method is not particularly limited as long as a desired pattern can be formed. For example, development methods such as spin immersion, spray, immersion, and ultrasonic can be used. The development is performed using a developer. Regarding the developer, as long as the unexposed part (non-exposed part) can be removed, it can be used without particular limitation. It is preferable that the developer contains an organic solvent, and it is more preferable that the developer contains 90% or more of an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably an organic solvent having a ClogP value of 0 to 3. The ClogP value can be calculated as a calculated value by inputting the structural formula in ChemBioDraw (Chemical Biological Diagram). As the organic solvent, those exemplified in the item 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. An organic solvent of 50% by mass or more of the developer is preferable, an organic solvent of 70% by mass or more is more preferable, and an organic solvent of 90% by mass or more is more preferable. In addition, 100% by mass in the developer may be an organic solvent.

As the development time, 10 seconds to 5 minutes are preferred. The temperature of the developing solution during development is not particularly limited, and it can usually be performed at 20 to 40°C. After treatment with developer, it can be rinsed. Rinsing is preferably performed with a solvent different from the developer. For example, it can be rinsed using the solvent contained in the photosensitive resin composition. Preferably, the washing time is 5 seconds to 1 minute.

＜＜Heating step＞＞ The manufacturing method of the present invention preferably includes a step of heating after the film formation step (layer formation step), drying step, or development step. In the heating step, the cyclization reaction of the polymer precursor proceeds. In this case, the specific thermal alkali generator does not hinder photosensitivity and can achieve good exposure and developability. In addition, by heating the resin pattern remaining after development, the specific thermal alkali generator releases alkali to rapidly and fully perform curing by cyclization of the resin. As the heating temperature (maximum heating temperature) of the layer in the heating step, 50°C or higher is preferred, 80°C or higher is more preferred, 140°C or higher is even more preferred, 150°C or higher is even more preferred, and 160°C or higher is It is even more preferable, and 170°C or higher is still more preferable. As the upper limit, 500°C or less is preferred, 450°C or less is more preferred, 350°C or less is even more preferred, 250°C or less is even more preferred, 220°C or less is even more preferred, and 200°C or less is even more preferred good. Regarding heating, it is preferable to perform heating at a temperature increase rate of 1-12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2-10°C/min, and still more preferably 3-10°C/min. By setting the heating rate to 1°C/min or more, it is possible to prevent excessive volatilization of alkali while ensuring productivity, and by setting the heating rate to 12°C/min or less, the residual stress of the cured film can be alleviated. The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the highest heating temperature. For example, when the photosensitive resin composition is applied to the substrate and dried, the temperature of the film (layer) after drying, for example, is 30 to 200 lower than the boiling point of the solvent contained in the photosensitive resin composition It is better to increase the temperature gradually at °C. The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and more preferably 30 to 240 minutes. In particular, when forming a multilayer laminate, from the viewpoint of the adhesion between the layers of the cured film, 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. Although the reason is not certain, it is thought that the reason is as follows. That is, by setting the temperature at this temperature, the ethynyl groups of the polymer precursors between the layers undergo a crosslinking reaction.

Heating can be carried out in stages. As an example, you can increase the temperature from 25°C to 180°C at 3°C/min, and keep it at 180°C for 60 minutes, and increase the temperature from 180°C to 200°C at 2°C/min, and keep it at 200°C for 120 minutes. . The heating temperature as the pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and further preferably 120 to 185°C. In this pretreatment step, it is also preferable to perform treatment while irradiating ultraviolet rays as described in U.S. Patent No. 9159547. The characteristics of the film can be improved by these pretreatment steps. The pretreatment step can be performed in a short time of about 10 seconds to 2 hours, and 15 seconds to 30 minutes is more preferable. The pretreatment may be a two-stage or more step. For example, the pretreatment step 1 may be performed in the range of 100 to 150°C, and then the pretreatment step 2 may be performed in the range of 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.

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

＜＜Steps of forming metal layer＞＞ The manufacturing 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 development. The metal layer is not particularly limited, and existing metal types can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable, and copper is more preferable. The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, and Japanese Patent Application Publication No. 2004-101850 can be used. For example, methods such as photolithography, peeling, electrolytic plating, electroless plating, etching, printing, and combinations can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be cited. The thickness of the metal layer is preferably 0.1-50 μm at the thickest part, and more preferably 1-10 μm.

＜＜Layering Step＞＞ Preferably, the manufacturing method of the present invention further includes a layering step. The layering step refers to the step of performing (a) film formation step (layer formation step), (b) exposure step, (c) development treatment step, and (d) heating step again in sequence on the surface of the cured film (resin layer) or metal layer A series of steps. Among them, the heating step (d) may be carried out at the end or in the middle of the build-up. That is, it is possible to set the laminated photosensitive resin composition layer to harden collectively by repeating the steps (a) to (c) a predetermined number of times and then heating (d). In addition, after the (c) development step, (e) the metal layer forming step may be included. In this case, the heating of (d) may be performed each time, or the heating of (d) may be performed after a predetermined number of laminations. It goes without saying that the above-mentioned drying step, heating step, etc. can also be appropriately included in the layering step. When the layering step is further performed after the layering step, the surface activation treatment step may be further performed after the heating step, and after the exposure step, or after the metal layer forming step. As the surface activation treatment, plasma treatment is exemplified. The above-mentioned layering step is preferably performed 2 to 5 times, and more preferably 3 to 5 times. For example, a resin layer such as a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably a structure having 3 layers or more and 7 layers or less, and more preferably 3 layers or more and 5 layers or less. That is, in the present invention, it is particularly preferable to form the cured film (resin layer) of the photosensitive resin composition so as to cover the metal layer after the metal layer is provided. Specifically, it can be mentioned that (a) film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, (d) heating step are repeated in sequence, or (a) repeated in sequence The film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step are set at the end or in the middle. By alternately performing the laminating 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 in which the photosensitive resin composition of the present invention is used in the formation of an interlayer insulating film for a rewiring layer, refer to the description in paragraphs 0213 to 0218 of JP 2016-027357 A and FIG. 1 Record and incorporate such content into this manual. [Example]

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

<Synthesis Example 1> [Polyimine precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and benzyl alcohol (A-1: without radical polymerizable group) Synthesis of polyimide precursor] 14.06g (64.5 millimoles) of pyromellitic dianhydride (dried at 140°C for 12 hours) and 14.22g (131.58 millimoles) of benzyl alcohol were suspended in 50 mL The N-methylpyrrolidone was dried with 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 millimoles) 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 millimoles) of SOCl _{2 was} added over 10 minutes while maintaining the temperature at -10±4°C. During the addition of SOCl ₂ , the viscosity 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 millimoles) of 4,4'-diaminodiphenyl ether was dissolved in 100 mL of N-methylpyrrolidone into the reaction mixture at -5～0°C for 20 minutes. From the solution. Next, after reacting the reaction mixture at 0°C for 1 hour, 70 g of ethanol was added and stirred at room temperature overnight. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimine 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, under reduced pressure, the obtained polyimide precursor was dried at 45°C for 3 days. 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: Free [Synthesis of polyimide precursors based on polymerizable groups]] 14.06g (64.5 millimoles) of pyromellitic dianhydride (dried at 140°C for 12 hours), 16.8g (129 millimoles) ) 2-hydroxyethyl methacrylate, 0.05g hydroquinone, 20.4g pyridine (258 millimoles) and 100g diglyme (diethylene glycol dimethyl ether) are mixed , Stirred at a temperature of 60°C for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Then, after chlorinating the obtained diester with SOCl _2, it was converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same way as in Synthesis Example 1, and compared with Synthesis Example 1. 1 The same method was used to obtain 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 precursors with radical polymerizable groups] 20.0 g (64.5 millimoles) of 4,4'-oxydiphthalic anhydride (dried at 140°C) For 12 hours), 16.8g (129 millimoles) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g of pyridine (258 millimoles) of pyridine and 100g of diethylene glycol Dimethyl ether was mixed and stirred at a temperature of 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. Then, after chlorinating the obtained diester with SOCl _2, it was converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same way as in Synthesis Example 1, and compared with Synthesis Example 1. 1 The same method was used to obtain the polyimide precursor. The weight average molecular weight of the polyimide precursor was 18,000.

A-3 [Chemical formula 33]

<Synthesis example 4> [From 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (o-xylene) 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), 16.8g (129 millimoles) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g of pyridine ( 258 millimoles) and 100 g of diglyme were mixed, and stirred at a temperature of 60°C for 18 hours to produce 4,4'-oxydiphthalic anhydride and methacrylic acid-2-hydroxyethyl The diester of an ester. Next, after chlorinating the obtained diester with SOCl _2, it was converted into polyimide using 4,4'-diamino-2,2'-dimethylbiphenyl in the same method as in Synthesis Example 1. The precursor, and the polyimide precursor was obtained by the same method as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor was 19,000.

A-4 [Chemical formula 34]

＜Synthesis example 5＞ [Polybenzoxazole precursor derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-oxodityl chloride (A-5) Synthesis] 13.92 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to 100 mL of N-methyl-2-pyrrolidone, and the mixture was stirred and dissolved. Next, 11.21 g of 4,4'-oxodityl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5°C, and then 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 under reduced pressure for 3 days. The weight average molecular weight of this polybenzoxazole precursor was 15,000.

A-5 [Chemical formula 35]

Examples and comparative examples <Preparation of photosensitive resin composition> The components described in Table 2 below were mixed to obtain each photosensitive resin composition. The obtained photosensitive resin composition was filtered under pressure through a filter having a pore width of 0.8 μm. The detailed content of the name or structure of the compound described in the table is shown below the table as a label. The following evaluation tests were conducted for each photosensitive resin composition prepared. The results are shown in Table 3.

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

<Elongation at break> Each photosensitive resin composition after the filtration was applied in a layer form on a silicon wafer by a spin coating method to form a photosensitive resin composition layer. The silicon wafer on which the photosensitive resin composition layer was formed was dried on the hot plate at 100°C for 5 minutes to form a uniform photosensitive resin composition layer with a thickness of 20 μm on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C), the photosensitive resin composition layer on the silicon wafer was exposed at an exposure energy of 500mJ/cm ² and exposed to a temperature of 10°C/min in a nitrogen environment. The temperature of the photosensitive resin composition layer (resin layer) was increased 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 from the silicon wafer to obtain a resin film 1.

The elongation at break of the resin film 1 was measured using a tensile testing machine (TENSILON). Specifically, it is measured in accordance with JIS-K6251:2017 at 25°C and 65% relative humidity (RH) with a crosshead speed of 300mm/min, a width of 10mm, and a sample length of 50mm in the longitudinal direction and width direction of the film. The elongation at break. The elongation at break is defined by E _b (%) = (L _b -L ₀ )/L ₀ (E _b : the elongation during cutting, L ₀ : the length of the test piece before the test, and L _b : the test piece has been cut The length of the test piece when broken) is calculated. In the evaluation, the elongation at break in each of the longitudinal direction and the width direction was measured 5 times, and the average value of 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 70% or less

[Table 2] Polymer precursor Thermal alkali generator Photopolymerization initiator Polymeric compound Polymerization inhibitor Migration inhibitor Metal adhesion improver Solvent species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts 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 in the synthesis example shown above

[化學式37]

(B) Thermal alkali generator, etc. [Chemical formula 36]

[Chemical formula 37]

Regarding the thermal base generator, the relationship between the exemplified number in the above-mentioned examples and the number of the compound exemplified 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 - -

Compound of Comparative Example [Chemical Formula 38]

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

D-3：A-TMMT（Shin-Nakamura Chemical Co.,Ltd.製）(D) Polymerizable 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 inhibitor E-1: 2,6-Di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) E-2: p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) E-3: p-Methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

(F) Migration inhibitor F-1: The compound exemplified above M-1 F-2: The compound exemplified above M-2 F-3: The compound exemplified above M-3 F-4: The compound exemplified above M-4

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

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

From the above results, it can be seen that in the photosensitive resin composition of the example using the thermal alkali generator having a polymerizable group in the part of the generated alkali, any cured film showed good breaking elongation (80% or more) ) (Examples 1-25). The high elongation at break of the cured film means that the photosensitive resin composition is sufficiently thermally cured, and it is considered that the thermal alkali generators B-1 to B-20 effectively generate alkali at 180°C, which is the film curing temperature. And suppress the volatilization of the alkali produced. In addition, it is understood that the photosensitive resin composition can be prepared as required to have excellent storage stability (Examples 1, 3 to 7, 9, 11 to 24), in which the alkalinity before heating is suppressed to a low level. Long-term hardening of polymer precursors. On the other hand, in the photosensitive resin composition of the comparative example using a thermal base generator without a polymerizable group, it is considered that the curing reaction of the thermosetting resin does not proceed sufficiently, and as a result, the elongation at break of the cured film is large and poor. . In addition, in terms of storage stability, Comparative Examples 1 and 2 were very low.

<Example 100> The photosensitive resin composition 1 of Example 1 was pressure-filtered through a filter with a pore width of 1.0 μm, and then spin-molded (3500 rpm, 30 seconds) and apply. After drying the photosensitive resin composition applied to the resin substrate at 100°C for 2 minutes, it was exposed using a stepper (manufactured by Nikon Corporation, NSR1505i6). The exposure was performed through a mask at a wavelength of 365 nm with an exposure amount of 200 mJ/cm ² . After exposure, baking was performed, developed with cyclopentanone for 30 seconds, and washed with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds, thereby obtaining a pattern. Then, it heated at 230 degreeC for 3 hours, and the interlayer insulating film for rewiring layers was formed. The interlayer insulating film for the rewiring layer has excellent insulating properties.

In addition, the compounds X-4 and X-5 described in Patent Document 3 (Japanese Patent Application Laid-Open No. 2006-282880) generate bases by light irradiation, but the generation of bases is not confirmed at 200°C or lower.

no

no

no.

Claims (13)

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 at 200°C or lower, and has a polymerizable group at a site that becomes the generated salt. The photosensitive resin composition described in item 1 of the scope of patent application, wherein the thermal alkali generator has a structure represented by any one of the following formulas (N1) to (N3),

In formula (N1), X is a single bond or a divalent linking group, R ¹ each 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 [] may be the same or different from each other, when n2 is 2, the two R ¹ may be the same or different from each other, and 2 R ¹ May be linked to each other to form a cyclic structure, at least one of R ¹ 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 n4 is 2, the groups in () can be mutually The same or different. When n5 is 2, the two R ² may be the same or different from each other, the two R ² may be connected to each other to form a cyclic structure, and at least one of R ² has a polymerizable group,

In formula (N3), R ⁴ represents an n8-valent organic group, R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, R ⁷ to R ⁹ each independently represent a hydrocarbon group, A represents an m-valent acid anion, m It is an integer from 1 to 4, n7 represents an integer from 1 to 12, n8 and n9 represent an integer from 1 to 12, and n8=n9, R ⁵ and R ⁶ may be connected to form a cyclic structure, R ⁷ to R ⁹ Two or more may be connected separately to form a cyclic structure, and at least one of R ⁷ to R ⁹ has a polymerizable group. The photosensitive resin composition as described in item 1 or item 2 of the scope of patent application, wherein the polymerizable group in the site that becomes the base produced is epoxy group, oxetane group, and ethylenically unsaturated Group or a group represented by the following formula (Z),

In formula (Z), Rc represents an oxygen atom, nitrogen atom or (n+2) valence aromatic group, Ra and Rb each 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, and when Rc is a nitrogen atom, n is 1, and * represents a bonding bond. The photosensitive resin composition described in item 1 or item 2 of the scope of patent application, wherein The polymer precursor includes a polyimide precursor. The photosensitive resin composition described in item 4 of the scope of patent application, wherein the polyimide precursor has a structural unit represented by the following formula (1),

In formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent hydrogen Atom or monovalent organic group. The photosensitive resin composition according to claim 5, 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 item 1 or item 2 of the scope of patent application is used for the formation of an interlayer insulating film for a rewiring layer. A cured film obtained by curing the photosensitive resin composition described in any one of items 1 to 7 in the scope of the patent application. A laminate having two or more layers and seven or less layers of the cured film described in item 8 of the scope of patent application, and having a metal layer between the cured films. A method for manufacturing a cured film, which includes a film forming step of applying the photosensitive resin composition described in any one of items 1 to 7 of the scope of patent application to a substrate to form a film. The method for manufacturing a cured film as described in the tenth item of the scope of patent application includes a heating step of heating the film at 80°C to 450°C. The method for manufacturing a cured film as described in item 10 or item 11 of the scope of the patent application has an exposure step of exposing the film and a developing step of developing the film. A semiconductor device having the cured film described in the 8th patent application or the laminated body described in the 9th patent application.