JPWO2020066315A1 - Photosensitive resin composition, cured film, laminate, method for manufacturing cured film, 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, a cured film, a laminate, a method for producing a cured film using the same, and a semiconductor device. The photosensitive resin composition contains a thermobase generator and a polyimide precursor, and the thermobase generator generates a base at 200 ° C. or lower and has a polymerizable group at a site where the base is generated.

Description

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

A cyclized and cured resin such as a polyimide resin or a polybenzoxazole resin has excellent heat resistance and insulating properties, and is therefore applied to various applications (see, for example, Non-Patent Documents 1 and 2). The application is not particularly limited, and examples of semiconductor devices for mounting include the use as a material for an insulating film and a sealing material, or as a protective film for an insulating film. It is also used as a base film and coverlay 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 a precursor before the cyclization reaction is often used. As a result, excellent handleability can be realized, and when each product as described above is manufactured, it can be applied to a substrate or the like in various forms and processed. After that, a cured product can be formed by forming a structure in which a precursor such as polyimide is cyclized. In addition to the high performance of polyimide resin, from the viewpoint of excellent manufacturing adaptability, its industrial application development is expected more and more.

As described above, attempts have been made to apply polyimide as a protective film for an interlayer insulating film.

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 active light, a specific compound having an ethylene oxide 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.

Japanese Unexamined Patent Publication No. 2015-108053 Japanese Unexamined Patent Publication No. 2014-201695 Japanese Unexamined Patent Publication No. 2006-228880

Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008 Masaaki Kakimoto / Supervision, CMC Technical Library "Basics and Development of Polyimide Materials" published in November 2011

As described in the above patent documents and the like, the polyimide precursor and the polybenzoxazole precursor (hereinafter, these may be collectively referred to as "polymer precursor") are cyclized (ring-closed) as described above. It is possible to cure the resin composition. The polymer precursor is cyclized by heating, and in the presence of a base at this time, this acts as a catalyst to promote cyclization and cure rapidly. Therefore, it is conceivable to add a thermobase generator that generates a base during heating to promote the cyclization reaction of the polymer precursor. Such a thermobase generator is also required to achieve stability during storage by avoiding curing due to inadvertent progress of cyclization because the base is not released before heating.

Further, in the conventional thermal base generator, the molecule which is the base generated from the agent is small and volatile. Therefore, in an environment heated to a predetermined temperature, the base may volatilize from the system. If the base volatilizes in the composition, the effect of cyclization of the polymer precursor due to the use of the base cannot be expected, resulting in inferior elongation at break of the obtained film.

In view of the technical problems in such a photosensitive resin composition, the present invention relates to a photosensitive resin composition containing a polymer precursor, a photosensitive resin composition capable of realizing curability by sufficient heating, and a photosensitive resin composition. It is an object of the present invention to provide a cured film, a laminate, a method for producing a cured film using the cured film, and a semiconductor device. In particular, the provision of a photosensitive resin composition having excellent storage stability and excellent elongation at break when made into a cured film, a method for producing a cured film, a laminate, and a cured film using the same, and a semiconductor device. With the goal.

As a result of the study, the present inventors have studied to impart a polymerizable group to the generated base. That is, a polymerizable group was introduced into the thermal base generator, and the decomposed base had a polymerizable group. By polymerizing the generated base with another molecule via a polymerizable group, the base is present in the system in a state in which the activity is maintained and in a state of being higher than the conventional one. It has been found that this can suppress the volatilization of the base and effectively promote the cyclization of the polymer precursor during heat curing. Specifically, the above problems have been solved by the following means.

式（Ｎ１）中、Ｘは単結合または２価の連結基であり、Ｒ¹はそれぞれ独立に水素原子または有機基を表し、ｎ１およびｎ２は１または２であり、ｎ１＋ｎ２は３であり、ｎ３は０または１であり、ｎ３が１のときにＸが単結合であることはなく、ｎ１が２のとき２つの［ ］内の基は互いに同じでも異なっていてもよく、ｎ２が２のとき２つのＲ¹は互いに同じでも異なっていてもよく、２つのＲ¹は互いに連結して環状構造を形成していてもよく、Ｒ¹の少なくとも１つは重合性基を有する；

式（Ｎ２）中、Ｒ²は水素原子または有機基を表し、Ｒ³は有機基を表し、ｎ４およびｎ５は１または２であり、ｎ４＋ｎ５は３であり、ｎ４が２のとき（ ）内の基は互いに同じでも異なっていてもよく、ｎ５が２のとき２つのＲ²は互いに同じでも異なっていてもよく、２つのＲ²は互いに連結して環状構造を形成していてもよく、Ｒ²の少なくとも１つは重合性基を有する；

式（Ｎ３）中、Ｒ⁴はｎ８価の有機基を表し、Ｒ⁵およびＲ⁶はそれぞれ独立に水素原子または炭化水素基を表し、Ｒ⁷〜Ｒ⁹はそれぞれ独立に炭化水素基を表し、Ａはｍ価の酸アニオンを表し、ｍは１〜４の整数であり、ｎ７は１〜１２の整数を表し、ｎ８およびｎ９は１〜１２の整数を表し、ｎ８＝ｎ９であり、Ｒ⁵およびＲ⁶が連結して環状構造を形成してもよく、Ｒ⁷〜Ｒ⁹はそれぞれその２つ以上が連結して環状構造を形成してもよく、Ｒ⁷〜Ｒ⁹の少なくとも１つは重合性基を有する。

＜３＞上記発生する塩基となる部位が有する重合性基が、エポキシ基、オキセタン基、エチレン性不飽和基、または下記式（Ｚ）で表される基である、＜１＞または＜２＞に記載の感光性樹脂組成物；

式（Ｚ）中、Ｒｃは酸素原子、窒素原子または（ｎ＋２）価の芳香族基を表し、ＲａおよびＲｂはそれぞれ独立に水素原子または有機基を表し、ｎは０〜６の整数を表し、Ｒｃが酸素原子の場合ｎは０であり、Ｒｃが窒素原子の場合ｎは１であり、＊は結合手を表す。

＜４＞上記ポリマー前駆体がポリイミド前駆体を含む、＜１＞〜＜３＞のいずれか１項に記載の感光性樹脂組成物。

＜５＞上記ポリイミド前駆体が下記式（１）で表される構成単位を有する、＜４＞に記載の感光性樹脂組成物；

式（１）中、Ａ¹およびＡ²は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ¹¹¹は、２価の有機基を表し、Ｒ¹¹⁵は、４価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴は、それぞれ独立に、水素原子または１価の有機基を表す。

＜６＞上記式（１）におけるＲ¹¹³およびＲ¹¹⁴の少なくとも一方がラジカル重合性基を含む、＜５＞に記載の感光性樹脂組成物。

＜７＞再配線層用層間絶縁膜の形成に用いられる、＜１＞〜＜６＞のいずれか１項に記載の感光性樹脂組成物。

＜８＞＜１＞〜＜７＞のいずれか１項に記載の感光性樹脂組成物を硬化してなる硬化膜。

＜９＞＜８＞に記載の硬化膜を２層以上７層以下で有し、この硬化膜の間に金属層を有する、積層体。

＜１０＞＜１＞〜＜７＞のいずれか１項に記載の感光性樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。

＜１１＞上記膜を８０〜４５０℃で加熱する加熱工程を含む、＜１０＞に記載の硬化膜の製造方法。

＜１２＞上記膜を露光する露光工程および上記膜を現像する現像工程を有する、＜１０＞または＜１１＞に記載の硬化膜の製造方法。

＜１３＞＜８＞に記載の硬化膜または＜９＞に記載の積層体を有する、半導体デバイス。

<1> A photosensitive resin composition containing a thermal base generator, a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, a photopolymerization initiator, and a polymerizable compound, which is a thermal base. A photosensitive resin composition in which a generator generates a base at 200 ° C. or lower and has a polymerizable group at a site where the base is generated.

<2> The photosensitive resin composition according to <1>, wherein the thermal base generator has a structure represented by any of the following formulas (N1) to (N3);

In formula (N1), X is a single bond or a divalent linking group, R ¹ independently represents a hydrogen atom or an organic group, n1 and n2 are 1 or 2, n1 + n2 is 3, and n3. Is 0 or 1, X is not a single bond when n3 is 1, and the groups in the two [] are the same or different when n1 is 2, and when n2 is 2. two R ¹ may be the same or different, two R ¹ may form a cyclic structure via connection to each other, 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 in parentheses. groups may be the same as or different from each other, n5 is or different and the two R ² when 2 identical to each other, the two R ² may be linked to each other to form a cyclic structure, R ^At least one of 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, and R ^{7 to} R ⁹ each independently represent a hydrocarbon group. A represents an m-valent acid anion, m is an integer of 1 to 4, n7 is an integer of 1 to 12, n8 and n9 are integers of 1 to 12, n8 = n9, and R ⁵ And R ⁶ may be connected to form an annular structure, and ^{two or more of R 7 to} R ⁹ may be connected to form an annular structure, and at least one of ^{R 7 to} R ^{9 may be connected to form an annular structure.} It has a polymerizable group.

<3> The polymerizable group possessed by the site to be the base to be generated is an epoxy group, an oxetane group, an ethylenically unsaturated group, or a group represented by the following formula (Z), <1> or <2>. The photosensitive resin composition according to

In formula (Z), Rc represents an oxygen atom, a nitrogen atom or a (n + 2) -valent aromatic group, Ra and Rb independently represent a hydrogen atom or an organic group, and n represents an integer of 0 to 6. When Rc is an oxygen atom, n is 0, when Rc is a nitrogen atom, n is 1, and * represents a bond.

<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the polymer precursor contains 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);

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

<6> The photosensitive resin composition according to <5>, wherein at least one ^{of R 113} and R ¹¹⁴ in the above formula (1) contains a radically polymerizable group.

<7> The photosensitive resin composition according to any one of <1> to <6>, which is used for forming an interlayer insulating film for a rewiring layer.

<8> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <7>.

<9> A laminate having the cured film according to <8> in two or more and seven or less layers, and having a metal layer between the cured films.

<10> A method for producing a cured film, which comprises a film forming step of applying the photosensitive resin composition according to any one of <1> to <7> to a substrate to form a film.

<11> The method for producing a cured film according to <10>, which comprises a heating step of heating the film at 80 to 450 ° C.

<12> The method for producing a cured film according to <10> or <11>, which comprises an exposure step for exposing the film and a developing step for developing the film.

<13> A semiconductor device having the cured film according to <8> or the laminate according to <9>.

According to the present invention, with respect to a photosensitive resin composition containing a polymer precursor, a photosensitive resin composition capable of realizing curability by sufficient heating, and production of a cured film, a laminate, and a cured film using the photosensitive resin composition. It has become possible to provide methods, methods for manufacturing laminates, and semiconductor devices. In particular, a photosensitive resin composition having excellent storage stability and excellent mechanical properties (break elongation) when made into a cured film, and a method for producing a cured film, a laminate, and a cured film using the same, and It has become possible to provide semiconductor devices.

Hereinafter, the contents of the present invention will be described in detail. In addition, in this specification, "~" is used in the meaning that the numerical values described before and after it are included as the lower limit value and the upper limit value.

The description of the components in the present invention described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In the notation of a group (atomic group) in the present specification, the notation that does not describe substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, the term alkyl group may be chain or cyclic, and the chain may be linear or branched. These things are also synonymous with the alkenyl group, the alkylene group, and the alkenylene group.

In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Further, as the light used for exposure, generally, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation can be mentioned.

In the present specification, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacryl", or. Representing either, "(meth) acryloyl" represents both "acryloyl" and "methacryloyl", or either.

In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..

Unless otherwise specified, the physical property values in the present invention are values at a temperature of 23 ° C. and an atmospheric pressure of 101325 Pa.

In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, the eluate shall be measured using THF (tetrahydrofuran). Unless otherwise specified, a detector having a wavelength of 254 nm for UV rays (ultraviolet rays) is used for detection.

The photosensitive resin composition of the present invention (hereinafter, may be simply referred to as “the composition of the present invention” or “the resin composition of the present invention”) is a thermal base generator having a polymerizable group (hereinafter, “specification”. It is characterized by containing a polymer precursor, a photopolymerization initiator, and a polymerizable compound. Hereinafter, the present invention will be described in detail with reference to preferred embodiments.

<Specific thermal base generator>

A specific thermal base generator generates a base at 200 ° C. or lower, and has a polymerizable group at a site where the base is generated.

Generating a base at 200 ° C. or lower means that the compound is isomerized or decomposed at a temperature of 200 ° C. or lower to change to a compound having a higher pKa of a conjugate acid than the original compound.

The temperature at which the specific thermobase generator generates a base (thermobase generation temperature) is preferably 180 ° C. or lower, and may be 150 ° C. or lower. The lower limit of the thermal base generation temperature is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, and even more preferably 80 ° C. or higher. By setting the temperature at which the base of the thermal base generator is generated to be equal to or lower than the above upper limit value, the base can be generated with lower energy consumption and the resin can be cured as compared with the temperature at which the base is generated at a higher temperature, which is preferable. On the other hand, by setting the temperature at which the base is generated to be equal to or higher than the above lower limit, the compound is decomposed during storage such as storage at room temperature to generate the base, which suppresses or prevents the resin from curing. It is preferable because it can be used.

Further, it is preferable that the specific thermal base generator generates a base within the above temperature range in the heating step described later.

The specific thermal base generator is preferably a compound that generates a base below the heat resistant temperature of the cured film.

As an embodiment of the present invention, two or more specific thermobase generators having different temperatures at which bases are generated can be blended. With such a configuration, for example, bases are generated stepwise, and the cyclization reaction of the polymer precursor during heating can proceed more efficiently.

<< Polymerizable group >>

Certain thermal base generators have polymerizable groups. The polymerizable group is located at the site where the base is generated. The number of polymerizable groups contained in the specific thermal base generator is not particularly limited, and may be one or a plurality of polymerizable groups. From the viewpoint of suppressing the molecular weight of the specific thermobase generator, the number of polymerizable groups in one molecule is preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. .. The lower limit is not particularly limited and may be 1 or more.

Examples of the polymerizable group include those that carry out radical polymerization, those that carry out polyaddition, those that carry out polycondensation, and the like. Those that carry out radical polymerization and those that carry out polyaddition are preferable, and those that carry out radical polymerization are more preferable.

Examples of the polymerizable group include an epoxy group (including a glycidyl group), an oxetane group, an ethylenically unsaturated group, and a group represented by the following formula (Z).

As ethylenically unsaturated groups, vinyl group, vinyloxy group, allyl group, methylallyl group, propenyl group, butenyl group, vinylphenyl group, (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino Examples thereof include a vinyl group, a vinylphenyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloylamino group. (Meth) acrylate the amino group of the acryloyl amino group is not limited to -NH-, -NR ^N - (R ^N is an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or a heterocyclic group, specifically, It may have a structure (selected from the alkyl groups and the like described in the substituent T described later). R ^N is connected to a base structure of the linking group or a thermal base generator polymerizable group are linked may form a ring. Examples of the ring formed include an example of ring Cn described later. In the present specification, the ethylenically unsaturated group exemplified here is referred to as Et, and the polymerizable group containing this is referred to as Ps.

式（Ｚ）中、Ｒｃは酸素原子、窒素原子または（ｎ＋２）価の芳香族基を表す。ＲａおよびＲｂはそれぞれ独立に水素原子または有機基を表す。ｎは０〜６の整数を表す。Ｒｃが酸素原子の場合ｎは０である。Ｒｃが窒素原子の場合ｎは１である。Ｒｃが例えばベンゼン環の場合ｎは０〜４の整数である。＊は結合手を表す。

（ｎ＋２）価の芳香族基としては芳香族炭化水素基（炭素数６〜２２が好ましく、６〜１８がより好ましく、６〜１０がさらに好ましい）または芳香族複素環基（炭素数１〜２４が好ましく、１〜１２がより好ましく、１〜６がさらに好ましい）が挙げられ、より具体的には、後述する芳香族炭化水素環Ａｒｙおよび芳香族複素環Ａｒｏを含む基が挙げられる。

ＲａおよびＲｂが有機基のとき、その有機基としては、それぞれ独立に、アルキル基（炭素数１〜１２が好ましく、１〜６がより好ましく、１〜３がさらに好ましい）、アルケニル基（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜３がさらに好ましい）、アリール基（炭素数６〜２２が好ましく、６〜１８がより好ましく、６〜１０がさらに好ましい）、アリールアルキル基（炭素数７〜２３が好ましく、７〜１９がより好ましく、７〜１１がさらに好ましい）が挙げられる。なかでもアルキル基が好ましく、具体的には、後述するＡｌｋの例が挙げられる。

In formula (Z), Rc represents an oxygen atom, a nitrogen atom or a (n + 2) -valent aromatic group. Ra and Rb independently represent a hydrogen atom or an organic group, respectively. n represents an integer from 0 to 6. When Rc is an oxygen atom, n is 0. When Rc is a nitrogen atom, n is 1. When Rc is, for example, a benzene ring, n is an integer of 0 to 4. * Represents a bond.

As the (n + 2) -valent aromatic group, an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms) or an aromatic heterocyclic group (1 to 24 carbon atoms). 1 to 12, more preferably 1 to 6), and more specifically, a group containing an aromatic hydrocarbon ring Ary and an aromatic heterocycle Aro, which will be described later, can be mentioned.

When Ra and Rb are organic groups, the organic groups are independently an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms) and an alkenyl group (carbon number of carbon atoms). 2-12 are preferred, 2-6 are more preferred, 2-3 are more preferred), aryl groups (6-22 carbon atoms are preferred, 6-18 are more preferred, 6-10 are more preferred), arylalkyl groups. (Preferably, the number of carbon atoms is 7 to 23, 7 to 19 is more preferable, and 7 to 11 is further preferable). Of these, an alkyl group is preferable, and specific examples thereof include an Alk described later.

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

式中のＲａ¹は有機基である。有機基の例としては、アルキル基（炭素数１〜１２が好ましく、１〜６がより好ましく、１〜３がさらに好ましい）、アルケニル基（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜３がさらに好ましい）、アリール基（炭素数６〜２２が好ましく、６〜１８がより好ましく、６〜１０がさらに好ましい）、アリールアルキル基（炭素数７〜２３が好ましく、７〜１９がより好ましく、７〜１１がさらに好ましい）が挙げられる。なかでもアルキル基が好ましく、具体的には、後述するＡｌｋの例が挙げられる。

Ｒｂ¹は水素原子またはメチル基である。

ｎｂは１〜５の整数である。ｎａは５−ｎｂとなる整数である。＊は結合手である。

Ａｒ¹は芳香族炭化水素基（炭素数６〜２２が好ましく、６〜１８がより好ましく、６〜１０がさらに好ましい）または芳香族複素環基（炭素数１〜２４が好ましく、１〜１２がより好ましく、１〜６がさらに好ましい）が挙げられ、より具体的には、後述する芳香族炭化水素環Ａｒｙおよび芳香族複素環Ａｒｏを含む基が挙げられる。なかでも、Ａｒ¹はフェニル基であることが好ましい。

^{Ra 1} in the formula is an organic group. Examples of the organic group include an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 6 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). , 2-3), aryl group (preferably 6-22 carbons, more preferably 6-18, even more preferably 6-10), arylalkyl group (preferably 7-23 carbons, 7-19 Is more preferable, and 7 to 11 is even more preferable). Of these, an alkyl group is preferable, and specific examples thereof include an Alk described later.

Rb ¹ is a hydrogen atom or a methyl group.

nb is an integer of 1-5. na is an integer such that 5 nb. * Is a bond.

Ar ¹ is an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms) or an aromatic heterocyclic group (preferably 1 to 24 carbon atoms, 1 to 12 carbon atoms). More preferably, 1 to 6 are more preferable), and more specifically, a group containing an aromatic hydrocarbon ring Ary and an aromatic heterocycle Aro, which will be described later, can be mentioned. Of these, Ar ¹ is preferably a phenyl group.

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 more preferably an epoxy group or an ethylenically unsaturated group.

<< Linking group >>

In a particular thermal base generator, the polymerizable group may be introduced into the compound via a linking group. The structure in which the polymerizable group is introduced with or without a linking group can be represented by, for example, the following formula (Zp). In addition, in this specification, when it says "having a polymerizable group", "containing a polymerizable group", etc., it includes an embodiment in which the polymerizable group is introduced into the mother structure by a linking group in this way.

* -Zp-Ps formula (Zp)

* Represents the binding position of the thermobase generator with the matrix structure. Ps is synonymous with the above-mentioned polymerizable group Ps.

Zp is a single bond or a linking group (hereinafter, it may be referred to as a linking group Zp or simply Zp in the sense of including a single bond). The linking group Zp may be any as long as it can link the polymerizable group to the mother structure of the base generator, and the structure is not particularly limited. Therefore, it may be a linking group of any structure as long as it is not too long or too large. For example, when a polymerizable group is introduced into the mother structure of a thermobase generator, it can be appropriately determined in consideration of the reactivity of the site serving as a linking group, the reactivity with the mother structure or the polymerizable group, and the like.

The linking chain length of Zp is also not particularly limited, but considering the practical structure of the linking group, 0 to 24 is preferable, 0 to 12 is more preferable, and 0 to 6 is further preferable (0 means a single bond).

When Zp is a linking group, it is preferable that the atoms constituting the linking group include a carbon atom, a hydrogen atom, and if necessary, a hetero atom (at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, etc.). The number of carbon atoms in the linking group is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6. The hydrogen atom may be determined according to the number of carbon atoms and the like. The number of heteroatoms, such as oxygen atom, nitrogen atom, and sulfur atom, is preferably 0 to 12, more preferably 0 to 6, and even more preferably 0 to 3, respectively.

Specific types of linking groups include a wide range of examples of linking group L, which will be described later.

Among them, Zp has an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 6 carbon atoms) and an arylene group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6). 10 to 10 is more preferable), an oxygen atom (oxy group), a carbonyl group, -NH-, -NR ^N- , and a group in which they are combined are preferable. ^RN may be connected to other parts to form an annular structure. Specifically, the following ring Cn is an example of the formed cyclic structure.

The linking group Zp is more preferably a linking group represented by the following formulas z1 to z8 or a combination thereof. nz is an integer of 0 to 12, preferably 0 to 6, more preferably 0 to 3. * Is the binding position of the thermobase generator with the matrix structure. ** is the connection position with Ps. ^RM is a hydrogen atom or a group defined by ^{RN above.} R ^M, in formula Z5～z8, include embodiments in conjunction with a methylene group in the parentheses of nz to form a cyclic structure. Specific examples include the following ring Cn, and more specifically, a piperidine ring.

The particular thermobase generator may be a quaternary ammonium salt or a carboxylic acid amide and a carbamic acid ester, but is preferably a carboxylic acid amide. Since the thermobase generator has a carboxylic acid amide structure, the conjugate acid pKa before the compound structure is changed by heating tends to be low, and the storage stability of the composition tends to be improved.

<< Equation (N1) >>

The specific thermobase generator preferably has a structure represented by the following formula (N1).

In formula (N1), X is a single bond or divalent linking group. Examples of the divalent linking group include a linking group L described later. Of these, a hydrocarbon group is preferable, and an alkylene group, an alkaneylene group, an arylene group or a combination thereof is preferable. When X is a divalent linking group, the number of carbon atoms is preferably 2 to 18, more preferably 2 to 12, and even more preferably 2 to 8. When X is a divalent linking group, the linking chain length is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 6. Specific examples thereof include an ethylene group, a propylene group, a butylene group, a vinylene group, a phenylene group, a phenylene methylene group, a phenylene ethylene group and a methylene phenylene methylene group. X may have a substituent T as appropriate within the range in which the effects of the present invention are exhibited. For example, an embodiment having a hydroxy group or a carboxy group as a predetermined linking group can be mentioned.

R ¹ independently represents a hydrogen atom or an organic group. Examples of the organic group include organic groups defined in the substituent T described later. The organic group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms. Among them, R ¹ is preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms). R ¹ may have a substituent T as long as the effects of the present invention are exhibited.

n2 is never R ¹ 2 is 2 Tsunotoki both two hydrogen atoms.

n1 and n2 are 1 or 2, and n1 + n2 is 3.

n3 is 0 or 1.

However, 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.

n2 are two R ¹ when 2 may be the same as or different from each other.

When n2 is 2, two R ¹ may be linked to each other to form a cyclic structure. The cyclic structure formed includes an aliphatic hydrocarbon ring (the one exemplified below is referred to as ring Cf) (for example, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclopropene ring, cyclobutene ring, cyclopentene). Rings, cyclohexene rings, etc.), aromatic hydrocarbon rings (the ones exemplified below are referred to as ring Cr) (benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc.), nitrogen-containing heterocycles (exemplified below). Ring Cn) (for example, pyrrol ring, imidazole ring, pyrazole ring, pyridine ring, pyrrolin ring, pyrrolidine ring, imidazolidine ring, pyrazolidine ring, piperidine ring, piperazine ring, morpholin ring, etc.), oxygen-containing heterocycle (The ones exemplified below are referred to as ring Co) (furan ring, pyran ring, oxylan ring, oxetan ring, tetrahydrofuran ring, tetrahydropyran ring, dioxane ring, etc.), sulfur-containing heterocycle (the one exemplified below is ring Cs. ) (Thiophene ring, thiirane ring, thietane ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, etc.) and the like. These rings are collectively referred to as ring Cy.

At ^{least one of R 1} has a polymerizable group. Examples of the polymerizable group include the above-mentioned Ps, and examples of the linking mode thereof include the above-mentioned example of the linking group Zp.

式（Ｎ１−１）中、Ｘ¹は２価の連結基であり、その好ましい範囲としては上記Ｘの例が挙げられる。Ｘ¹は本発明の効果を奏する範囲で、適宜置換基Ｔを有していてもよい。

Ｒ¹¹およびＲ¹²はそれぞれ独立に水素原子または有機基を表す。Ｒ¹¹およびＲ¹²の有機基としては、それぞれ独立に、後述する置換基Ｔの中で規定される有機基が挙げられる。有機基の炭素数は、１〜１８であることが好ましく、１〜１２であることがより好ましく、１〜６であることがさらに好ましい。特に、Ｒ¹¹およびＲ¹²はそれぞれ独立にアルキル基（炭素数１〜１２が好ましく、１〜６がより好ましく、１〜３がさらに好ましい）が好ましい。ただしＲ¹¹およびＲ¹²の両方が水素原子であることはない。Ｒ¹¹およびＲ¹²は本発明の効果を奏する範囲で置換基Ｔを有していてもよい。

Ｒ¹¹およびＲ¹²は互いに連結して環状構造を形成していてもよい。形成される環としては環Ｃｙの例が挙げられる。

Ｒ¹¹およびＲ¹²の少なくとも１つは重合性基を有する。重合性基については上記Ｐｓの例が挙げられ、その連結の態様としては上記の連結基Ｚｐの例が挙げられる。

The above formula (N1) is preferably any of the following formulas (N1-1), formulas (N1-2) and formulas (N1-3).

In the formula (N1-1), X ¹ is a divalent linking group, and examples of the above X can be mentioned as a preferable range thereof. X ¹ may appropriately have a substituent T as long as the effects of the present invention are exhibited.

R ¹¹ and R ¹² independently represent a hydrogen atom or an organic group, respectively. Examples ^{of the organic groups of R 11} and R ¹² include organic groups defined in the substituent T described later, respectively. The organic group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms. In particular, R ¹¹ and R ¹² are each independently preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms). However ^{, both R 11} and R ¹² are not hydrogen atoms. R ¹¹ and R ¹² may have a substituent T as long as the effects of the present invention are exhibited.

R ¹¹ and R ¹² may be connected to each other to form an annular structure. Examples of the ring formed include a ring Cy.

At ^{least one of R 11} and R ¹² has a polymerizable group. Examples of the polymerizable group include the above-mentioned Ps, and examples of the linking mode thereof include the above-mentioned example of the linking group Zp.

In the formula (N1-2), X ² is a divalent linking group, and examples of the above X can be mentioned as a preferable range thereof. X ² may have a substituent T as appropriate within the range in which the effects of the present invention are exhibited.

R ¹³ and R ¹⁴ independently represent a hydrogen atom or an organic group, respectively. Examples ^{of the organic groups of R 13} and R ¹⁴ include organic groups defined in the substituent T described later, respectively. The organic group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms. In particular, R ¹³ and R ¹⁴ are each independently preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms). However ^{, both R 13} and R ¹⁴ are not hydrogen atoms. R ¹³ and R ¹⁴ may have a substituent T as long as the effects of the present invention are exhibited.

R ¹³ and R ¹⁴ may be connected to each other to form an annular structure. Examples of the ring formed include a ring Cy.

At ^{least one of R 13} and R ¹⁴ has a polymerizable group. Examples of the polymerizable group include the above-mentioned Ps, and examples of the linking mode thereof include the above-mentioned example of the linking group Zp.

In the formula (N1-3), X ³ is a 2 + m4 valent linking group, and among them, an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10). Is preferable, and in terms of the ring structure, an example of the aromatic hydrocarbon ring Ary, which will be described later, can be mentioned. X ³ may have a substituent T as appropriate within the range in which the effects of the present invention are exhibited.

Y ¹ is a group represented by − (CO) _m3 −OH, and m3 is 0 or 1.

R ^{15 to} R ¹⁸ independently represent a hydrogen atom or an organic group. Examples of the organic groups of R ^{15 to R 18} include organic groups defined in the substituent T described later, respectively. The organic group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms. In particular, R ^{15 to} R ¹⁸ are each independently preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms).

m4 is an integer of 0 to 12, preferably an integer of 0 to 8, and more preferably an integer of 0 to 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. Examples of the ring formed include a ring Cy. At ^{least one of R 15} and R ¹⁶ has a polymerizable group. Examples of the polymerizable group include the above-mentioned Ps, and examples of the linking mode thereof include the above-mentioned example of the linking group Zp. R ¹⁵ and R ¹⁶ may have a substituent T as long as the effects of the present invention are exhibited.

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. Examples of the ring formed include a ring Cy. At ^{least one of R 17} and R ¹⁸ has a polymerizable group. Examples of the polymerizable group include the above-mentioned Ps, and examples of the linking mode thereof include the above-mentioned example of the linking group Zp. R ¹⁷ and R ¹⁸ may have a substituent T as long as the effects of the present invention are exhibited.

When X ³ is a linking group composed of an aromatic ring, it is preferably a benzene ring, and in this case, for example, an embodiment in which two carboxy groups are substituted as ^{Y 1 can be mentioned.} Specifically, the following formula (N1-3a) can be mentioned.

式中、Ｒ¹⁵〜Ｒ¹⁸はそれぞれ独立に水素原子または有機基を表す。Ｒ¹⁵〜Ｒ¹⁸の好ましい態様は先に式（Ｎ１−３）で定義したものと同義である。Ｒ¹⁵とＲ¹⁶、Ｒ¹⁷とＲ¹⁸はそれぞれその両者が水素原子であることはなく、環Ｃｙを形成してもよい。Ｒ¹⁵とＲ¹⁶の少なくともいずれか、また、Ｒ¹⁷とＲ¹⁸の少なくともいずれかは重合性基Ｐｓを有し、重合性基は連結基Ｚｐを介在して母構造に導入されていてもよい。

In the formula, R ^{15 to} R ¹⁸ independently represent a hydrogen atom or an organic group. Preferred embodiments of R ^{15 to} R ¹⁸ are synonymous with those defined above in the formula (N1-3). Both R ¹⁵ and R ¹⁶ and R ¹⁷ and R ¹⁸ are not hydrogen atoms, and may form a ring Cy. At ^{least one of R 15} and R ¹⁶ and at least one of R ¹⁷ and R ¹⁸ may have a polymerizable group Ps, and the polymerizable group may be introduced into the matrix structure via a linking group Zp. ..

Hereinafter, compounds forming a specific thermobase generator represented by the formula (N1) will be illustrated, but the present invention is not construed as being limited thereto.

式（Ｎ２）中、Ｒ²は水素原子または有機基を表す。Ｒ²の有機基としては、後述する置換基Ｔの中で規定される有機基が挙げられる。有機基の炭素数は、１以上であることが好ましい。上限としては、３０以下であることが好ましく、１８以下であることがより好ましく、１４以下であることがさらに好ましい。特に、Ｒ²は、アルキル基（炭素数１〜１２が好ましく、１〜６がより好ましく、１〜３がさらに好ましい）、アリール基（炭素数６〜２２が好ましく、６〜１８がより好ましく、６〜１０がさらに好ましい）またはアリールアルキル基（炭素数７〜２３が好ましく、７〜１９がより好ましく、７〜１１がさらに好ましい）が好ましい。Ｒ²は本発明の効果を奏する範囲で置換基Ｔを有していてもよい。

<< Formula (N2) >>

It is also preferable that the specific thermobase generator has a structure represented by the following formula (N2).

In formula (N2), R ² represents a hydrogen atom or an organic group. Examples ^{of the organic group of R 2} include the organic group defined in the substituent T described later. The organic group preferably has 1 or more carbon atoms. The upper limit is preferably 30 or less, more preferably 18 or less, and even more preferably 14 or less. In particular, R ² has an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 6 carbon atoms) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms). 6 to 10 are more preferred) or arylalkyl groups (7 to 23 carbon atoms are preferred, 7 to 19 are more preferred, 7 to 11 are even more preferred). R ² may have a substituent T as long as the effects of the present invention are exhibited.

R ³ is an organic group, which comprises an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 14 carbon atoms) and an aryl group (preferably 6 to 30 carbon atoms, 6 to 24 carbon atoms). More preferably, 6-18 is even more preferred), an arylalkyl group (7-31 carbons is preferred, 7-25 is more preferred, 7-19 is even more preferred), or a heterocyclic group-containing group (1-30 carbons). 2 to 24 are more preferable, and 3 to 18 are more preferable; heterocyclic compounds are preferably 5-membered rings, 6-membered rings, or a combination thereof; specific examples of the heterocyclic group are the substituent T described later. For example) is preferred. R ³ may have a substituent T as long as the effects of the present invention are exhibited.

n4 and n5 are 1 or 2, and n4 + n5 is 3. n5 is R ² when 2 is that no two even hydrogen atom. When n4 is 2, the groups in parentheses may be the same or different from each other. n5 are two R ² when 2 may be the same as or different from each other. The two R ^2s may be connected to each other to form an annular structure, and examples of the formed ring include a ring Cy.

At ^{least one of R 2} has a polymerizable group. Examples of the type of the polymerizable group include the polymerizable group Ps, and examples of the linking to the matrix structure include the linking group Zp.

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

In formula (N2-1), R ²¹ and R ²² independently represent a hydrogen atom or an organic group, respectively. However, ^{both R 21} and R ²² are not hydrogen atoms. When R ²¹ and R ²² are organic groups, examples of the organic group include the organic group of the substituent T described later. Of these, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms) is preferable. R ²¹ and R ²² may have a substituent T as long as the effects of the present invention are exhibited.

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 linking to the R 21} and R ²² sides can be made by the linking group Zp. R ²¹ and R ²² may be connected to each other to form a ring. Examples of the ring formed include a ring Cy.

R ³¹ is an organic group, preferably an alkyl group. The alkyl group at this time preferably has 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, and particularly a tertiary alkyl group (for example, a t-butyl group or a 1,1-dimethylpropyl group). , Adamantyl group is mentioned). R ³¹ may have a substituent T as long as the effects of the present invention are exhibited.

In formula (N2-2), R ²³ and R ²⁴ independently represent a hydrogen atom or an organic group, respectively. However, ^{both R 23} and R ²⁴ are not hydrogen atoms. When R ²³ and R ²⁴ are organic groups, examples of the organic group include the organic group of the substituent T described later. Of these, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms) is preferable. R ²³ and R ²⁴ may have a substituent T as long as the effects of the present invention are exhibited.

At ^{least one of R 23} and R ²⁴ has a polymerizable group. Examples of the polymerizable group include the above-mentioned polymerizable group Ps, ^{and the linking to the R 23} and R ²⁴ sides can be made by the linking group Zp. R ²³ and R ²⁴ may be connected to each other to form a ring. Examples of the ring formed include a ring Cy.

L ¹ is a single bond or a linking group, and is particularly preferably a linking group. When L ¹ is a linking group, examples of the linking group L described later can be mentioned, and among them, an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) is preferable.

Ar ² is an aromatic ring, which is an aromatic hydrocarbon ring (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 14 carbon atoms; a 5-membered ring, a 6-membered ring, or at least one of them. It is preferably a ring; specific examples include the example of Ary) or an aromatic heterocycle (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 2 to 12; as a heteroatom. , Oxygen atom, nitrogen atom, sulfur atom are preferable, and the number of heteroatoms is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 6; specific examples include Aro or Thioxanthene 10,10-dioxide is preferred). Ar ² may have a substituent T as long as the effect of the present invention is exhibited.

The following compounds can be exemplified as the thermobase generator represented by the formula (N2), but the present invention is not construed as being limited thereto.

<< Formula (N3) >>

It is also preferable that the specific thermobase generator has a structure represented by the following formula (N3).

In formula (N3), R ⁴ represents an n8-valent organic group. Examples of the organic group include an organic group of the substituent T described later (however, the valence is interpreted as n8). Among them, n8-valent alkane-structured groups (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms) or aryl-structured groups (preferably 6 to 22 carbon atoms, 6 to 18 carbon atoms). Is more preferable, and 6 to 10 is even more preferable). R ⁴ may have a substituent T as long as the effects of the present invention are exhibited.

R ⁵ and R ⁶ independently represent a hydrogen atom or an organic group, respectively. The organic group is preferably a hydrocarbon group, an aliphatic hydrocarbon group (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms) and an aromatic hydrocarbon group (carbon number of carbon atoms). 6 to 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), and an alkyl group (1 to 12 carbon atoms is preferable, 1 to 6 is more preferable, and 1 to 3 is more preferable) is preferable. More preferred. It is particularly preferable that both R ⁵ and R ^{6 are hydrogen atoms.} When R ⁵ and R ⁶ are organic groups, they may have a substituent T as long as the effects of the present invention are exhibited. R ⁵ and R ⁶ may be connected to each other to form a ring. Examples of the ring formed include the ring Cf.

R ^{7 to} R ⁹ independently represent hydrocarbon groups. Examples of the hydrocarbon groups of R ^{7 to} R ⁹ include hydrocarbon groups defined in the substituent T described later, respectively. The hydrocarbon group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms. In particular, R ^{7 to} R ⁹ are each independently preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms). The hydrocarbon groups R ^{7 to} R ⁹ may have a substituent T as long as the effects of the present invention are exhibited. Two or more of R ^{7 to} R ⁹ may be connected to form a ring. Examples of the ring to be formed include a ring Cy, more specifically an example of Cn, and a piperidine ring among them.

A represents an m-valent acid anion. Specific examples of A, * - COO - ^(carboxylate anion) groups comprising (* represents a bond to another site) are exemplified, * - COO ^- are preferred. The formula amount of A is preferably 44 or more, preferably 300 or less, and more preferably 200 or less.

m is an integer of 1 to 4. n7 represents an integer of 1-12. n8 and n9 represent integers from 1 to 12. However, n8 = n9.

At ^{least one of R 7 to} R ⁹ has a polymerizable group. Examples of the polymerizable group include the above-mentioned polymerizable group Ps, and examples of the linking form include the linking group Zp.

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

In formula (N3-1), R ⁴¹ represents an organic group. ^Examples of the organic group of R 41 include the organic group of the substituent T described later. Among them, an alkyl group (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms) or an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 carbon atoms). Is more preferable). R ⁴¹ may have a substituent T or a polymerizable group Ps via a linking group Zp (including a single bond) as long as the effects of the present invention are exhibited.

R ⁷¹ , R ⁸¹ and R ⁹¹ each independently represent a hydrocarbon group. Examples of the hydrocarbon groups of R ⁷¹ , R ⁸¹ and R ⁹¹ include the hydrocarbon groups defined in the substituent T described later, respectively. The hydrocarbon group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms. In particular, R ⁷¹ , R ⁸¹ and R ⁹¹ are each independently preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms). R ⁷¹ , R ⁸¹ and R ⁹¹ may have a substituent T as long as the effects of the present invention are exhibited. Two or more of R ⁷¹ , R ^81, and R ⁹¹ may be connected to form a ring. Examples of the ring to be formed include a ring Cy, more specifically an example of Cn, and a piperidine ring among them.

At ^{least one of R 71} , R ⁸¹ and R ⁹¹ has a polymerizable group. Examples of the polymerizable group include the above-mentioned polymerizable group Ps, and examples of the linking form include the linking group Zp.

A is an acid anion, and the preferable range is the same as that of the formula (N3).

In formula (N3-2), R ⁴² represents an organic group. ^Examples of the organic group of R 42 include the organic group of the substituent T described later. Among them, an alkyl group (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms) or an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 carbon atoms). Is more preferable). R ⁴² may have a substituent T or a polymerizable group Ps via a linking group Zp (including a single bond) as long as the effects of the present invention are exhibited.

R ⁸² represents a hydrocarbon group. Examples of this hydrocarbon group include hydrocarbon groups defined in Substituent T, which will be described later. The hydrocarbon group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms. In particular, R ⁸² is preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms). R ⁸² may have a substituent T as long as the effects of the present invention are exhibited.

m1 is an integer from 0 to 10.

R ⁹² represents a substituent. Examples of the substituent of R ⁹² include the substituent T described later. When there are two or more R ^92s, they may be connected to each other to form a ring. Examples of the ring formed include a ring Cy.

At ^{least one of R 82} and R ⁹² and the piperidine ring has a polymerizable group. Examples of the polymerizable group include the above-mentioned polymerizable group Ps, and examples of the linking form include the linking group Zp.

A is an acid anion, and the preferable range is the same as that of the 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 mentioned. Among them, an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms) and a (oligo) alkyleneoxy group (the number of carbon atoms of the alkylene group in one structural unit is 1 to 1). 12 is preferable, 1 to 6 is more preferable, 1 to 3 is further preferable; the number of repetitions is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30; the terminal oxygen atom is an element to be linked. The number may be increased or decreased depending on the type of the group), an arylene group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and a group related to a combination thereof is preferable. R ⁴³ may have a substituent T or a polymerizable group Ps via a linking group Zp (including a single bond) as long as the effects of the present invention are exhibited.

R ⁷³ , R ⁸³ , R ⁹³ , R ⁷⁴ , R ⁸⁴ and R ⁹⁴ each independently represent a hydrocarbon group. Examples of the hydrocarbon group include hydrocarbon groups defined in the substituent T described later, respectively. The hydrocarbon group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms. In particular, R ⁷³ , R ⁸³ , R ⁹³ , R ⁷⁴ , R ⁸⁴ and R ⁹⁴ each independently have an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms). preferable. R ⁷³ , R ⁸³ , R ⁹³ , R ⁷⁴ , R ⁸⁴ and R ⁹⁴ may have a substituent T as long as the effects of the present invention are exhibited.

Two or more of R ⁷³ , R ⁸³ , and R ⁹³ may be connected to form a ring. Examples of the ring to be formed include a ring Cy, more specifically an example of Cn, and a piperidine ring among them.

Two or more of R ⁷⁴ , R ⁸⁴ , and R ⁹⁴ may be connected to form a ring. Examples of the ring to be formed include a ring Cy, more specifically an example of Cn, and a piperidine ring among them.

At ^{least one of R 73} , R ⁸³ and R ⁹³ has a polymerizable group. Examples of the polymerizable group include the above-mentioned polymerizable group Ps, and examples of the linking form include the linking group Zp.

At ^{least one of R 74} , R ⁸⁴ and R ⁹⁴ has a polymerizable group. Examples of the polymerizable group include the above-mentioned polymerizable group Ps, and examples of the linking form include the linking group Zp.

A is an acid anion, and the preferable range is the same as that of the formula (N3).

The following compounds can be exemplified as the thermobase generator represented by the formula (N3), but the present invention is not construed as being limited thereto.

Among the formulas (N1) to (N3), the thermobase generator according to the formula (N1) or the formula (N2) is more preferable. In the hot base generator in the form of a salt contained in formula (N3), basic ammonium ions may promote cyclization of the polymer precursor. From the viewpoint of not having such an action and further enhancing the storage stability, a specific thermobase generator that does not take the form of a salt is preferable.

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

The specific thermobase generator has a pKa of the conjugate acid of the protonated portion on the nitrogen atom (hereinafter, may be simply referred to as “pKa of the conjugate acid of the specific thermobase generator”) of 4 or less. It is preferably 2 or less, more preferably 1 or less, and even more preferably 0.4 or less. It is practical that the lower limit of the pKa is −5 or more. By setting the pKa of the conjugate acid of the specific thermobase generator to the above upper limit value or less, it is preferable in that it does not inhibit the cyclization reaction of the polymer precursor.

The term "pKa" as used herein means a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is represented by its negative common logarithm pKa. The smaller the pKa, the stronger the acid. Unless otherwise specified, pKa is a value calculated by ACD / ChemSchetch. Alternatively, the values published in "Revised 5th Edition Chemistry Handbook Basics" edited by the Chemical Society of Japan may be referred to.

Regarding the pKa of the conjugate acid of a specific thermobase generator, the increase (ΔpKa) (difference in pKa before and after heating) of the same pKa by heating is preferably 2 or more, more preferably 5 or more, and 8 The above is more preferable.

The pKa of the conjugate acid of some of the exemplary compounds of a particular thermobase generator is listed below.

The molecular weight of the specific thermobase generator is not particularly limited, but is preferably 2,000 or less, more preferably 1,000 or less, and even more preferably 500 or less. In order to suppress the volatilization of the generated base, it is conceivable to use a high molecular weight base or thermobase generator. However, polymer additives can cause problems with solubility in compositions and compatibility with polymer precursors. On the other hand, in the specific thermobase generator according to the present invention, the base can be immobilized in the system via a polymerizable group, so that the thermobase generator does not need to have a high molecular weight. , It is preferable in that it can solve the problem of solubility. It is also preferable to use a low molecular weight thermobase generator because the amount of bases generated per compounding amount (number of moles) can be increased. The lower limit of the molecular weight of a specific thermobase generator is not particularly limited, but it is practically 80 or more.

The specific thermobase generator is preferably 0.0025% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.02% by mass or more in the photosensitive resin composition. preferable. The upper limit is, for example, preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and may be 3% by mass or less.

With respect to 100 parts by mass of the polymer precursor, it is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and further preferably 0.1 part by mass or more. The upper limit is, for example, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, further preferably 7.5 parts by mass or less, and even 5.0 parts by mass or less. good.

By setting the content of the specific thermobase generator to the above lower limit value or more, it is preferable in that good storage stability can be ensured. On the other hand, it is preferable that the value is not more than the above upper limit value because the corrosion resistance of the metal can be ensured.

Furthermore, as described above, in a specific thermal base generator, the generated base has a polymerizable group and is polymerized, so that its volatilization is effectively suppressed. As a result, the base becomes more likely to be present in the composition, and a more effective cyclization promoting action can be expected. As a result, the amount of the thermal base generator added can be suppressed, the secondary effect of the addition can be reduced, and the physical characteristics of the photosensitive resin composition and the performance of the cured film thereof can be improved. Can be done.

The specific thermobase generator may be used alone or in combination of two or more. When multiple items are used, the total amount is within the range specified above. When the composition of the present invention contains two or more kinds of base generators, preferably 80% by mass or more (further, 90% by mass or more, particularly 95% by mass or more) contained in the composition is a specific thermobase generator. Is preferable.

The compound of the other party to which the base is fixed via the polymerizable group is not particularly limited. For example, an embodiment in which the generated bases are bonded or polymerized can be mentioned. Further, it may be polymerized with a polymerizable compound. Furthermore, if the polymer precursor has a polymerizable group, it may be polymerized with such a polymerizable group. Further, the mode in which these polymerizations proceed in a complex manner may be used.

As the substituent T, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms) and an arylalkyl group (preferably 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms). , 7-11 is more preferred), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 and even more preferably 2 to 6), an alkynyl group (preferably 2 to 24 carbon atoms, 2 to 12). More preferably, 2 to 6 are more preferred), an organic amino group (-NR ^N ₂ ) (preferably 1 to 24 carbon atoms, more preferably 1 to 12 and even more preferably 1 to 6), an aryl group (6 carbon atoms). ~ 22 is preferable, 6-18 is more preferable, 6-10 is more preferable), an arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, 7 to 11 is more preferable), and an alkoxy group (is preferable. 1 to 12 carbon atoms are preferable, 1 to 6 are more preferable, 1 to 3 are more preferable), an aryloxy group (6 to 22 carbon atoms are preferable, 6 to 18 is more preferable, and 6 to 10 are more preferable). An acyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3), an acyloxy group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms). ), Allylloyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11), allylloyloxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, 7 to 19). 11 is more preferred), carbamoyl group (preferably 1-12 carbon atoms, more preferably 1-6, more preferably 1-3), sulfamoyl group (preferably 0-12 carbon atoms, more preferably 0-6). 0 to 3 is more preferable), an alkylsulfonyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 3), an arylsulfonyl group (preferably 6 to 22 carbon atoms, 6 to 18 carbon atoms). More preferably, 6-10 is even more preferred), a heterocyclic group (containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom; preferably 1 to 30 carbon atoms, more preferably 2 to 24, 3 to 18 There further preferred; preferably contains a 5- or 6-membered ring), (meth) acryloyl group, (meth) acryloyloxy group, an imino group (= NR ^N), alkylidene groups (= C (R ^N) ₂₎ , Organic groups such as carboxy group.

Further, the substituent T includes a hydroxy group, an amino group (NH ₂ ), a sulfanyl group, a sulfo group, a sulfooxy group, a phosphono group, a phosphonooxy group and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom). , A group composed of an inorganic element such as an oxo group (= O) is included.

^RN is an alkyl group, an alkenyl group, an aryl group, an arylalkyl group, or a heterocyclic group, and specifically, it is selected from the alkyl group described in the substituent T described later.

The alkyl and alkenyl moieties contained in each substituent may be chain or cyclic, linear or branched. When the substituent T is a group capable of taking a substituent, it may further have a substituent T. For example, it may be a hydroxyalkyl group in which a hydroxy group is substituted with an alkyl group.

As the linking group L, an alkylene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms) and an alkenylene group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). 2-3 are more preferred), alkynylene groups (2-12 carbon atoms are preferred, 2-6 are more preferred, 2-3 are more preferred), (oligo) alkyleneoxy groups (alkylene groups in one building block. The number of carbon atoms is preferably 1-12, more preferably 1-6, still more preferably 1-3; the number of repetitions is preferably 1-50, more preferably 1-40, even more preferably 1-30; alkylene group and oxy. The orientation of the group in the compound does not matter; the terminal oxygen atom may be increased or decreased depending on the element to be linked), an arylene group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10). More preferred), oxygen atoms, sulfur atoms, sulfonyl groups, carbonyl groups, thiocarbonyl groups, -NH-, -NR ^N- , and linking groups for combinations thereof. The alkylene group, alkenylene group, and alkyleneoxy group may have the above-mentioned substituent T. For example, the alkylene group may have a hydroxy group.

The linking chain length of the linking group L is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6. The chain length means the number of atoms located in the shortest path of the atomic groups involved in the connection. For example, if -CH _2- (C = O) -O-, it becomes 3.

The alkylene group, alkaneylene group, and (oligo) alkyleneoxy group defined by the linking group L may be chain-like or cyclic, and may be linear or branched.

The atom constituting the linking group L preferably contains a carbon atom, 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 to 24, more preferably 1 to 12, and even more preferably 1 to 6. The hydrogen atom may be determined according to the number of carbon atoms and the like. The number of heteroatoms is preferably 0 to 12, more preferably 0 to 6, and even more preferably 0 to 3, independently of the oxygen atom, nitrogen atom, and sulfur atom.

<Polymer precursor>

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

Ａ¹およびＡ²は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ¹¹¹は、２価の有機基を表し、Ｒ¹¹⁵は、４価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴は、それぞれ独立に、水素原子または１価の有機基を表す。

<Polyimide precursor>

The polyimide precursor preferably contains a structural unit represented by the following formula (1). With such a configuration, a composition having more excellent film strength can be obtained.

A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ are independent, respectively. Represents a hydrogen atom or a monovalent organic group.

A ¹ and A ² are independently oxygen atoms or NH, and oxygen atoms are preferable.

<< R ¹¹¹ >>

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group consisting of a combination thereof, which have 2 to 20 carbon atoms. A linear aliphatic group, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. Preferably, an aromatic group having 6 to 20 carbon atoms is more preferable.

Examples of aromatic groups include the following AR-1 to AR-10.

In the formula, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, −O−, −C (= O) −, −S−, −S. (= O) _2- , -NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O- , -C (= O) -, - more preferably a group selected from, -CH ₂ - - S- and _{-SO 2, - O -, -} S -, - SO 2 -, - C ( It is more preferably a divalent group selected from the group consisting of CF ₃ ) ₂ − and −C (CH ₃ ) _{2 −.}

R ¹¹¹ is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.

Specifically, the diamine is derived from a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. It is preferably a diamine containing an aromatic group having 6 to 20 carbon atoms, and more preferably a diamine containing an aromatic group.

As the diamine, specifically, the compound described in paragraph 0032 of International Publication No. WO2015 / 199220 Pamphlet can be referred to, which is incorporated herein by reference.

R ¹¹¹ is preferably represented by ^{−Ar 0} −L ⁰ −Ar ⁰ − from the viewpoint of the flexibility of the obtained cured film. However, Ar ⁰ is independently an aromatic group, preferably an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and a phenylene group. More preferred. L ⁰ is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, −O−, −C (= O) −, −S−, −S (= O). ₂ -, - NHCO-, and represents a group selected from the combinations thereof. The preferred range is synonymous with A above.

Ｒ⁵⁰〜Ｒ⁵⁷は、それぞれ独立に水素原子、フッ素原子または１価の有機基であり、Ｒ⁵⁰〜Ｒ⁵⁷の少なくとも１つはフッ素原子、メチル基、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。

Ｒ⁵⁰〜Ｒ⁵⁷の１価の有機基として、炭素数１〜１０（好ましくは炭素数１〜６）の無置換のアルキル基、炭素数１〜１０（好ましくは炭素数１〜６）のフッ化アルキル基等が挙げられる。

Ｒ⁵⁸およびＲ⁵⁹は、それぞれ独立にフッ素原子、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。

式（５１）または（６１）の構造を与えるジアミン化合物としては、ジメチル−４,４’−ジアミノビフェニル、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル、２，２’−ビス（フルオロ）−４，４’−ジアミノビフェニル、４，４’−ジアミノオクタフルオロビフェニル等が挙げられる。これらの１種を用いるか、２種以上を組み合わせて用いてもよい。

From the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.

R ^{50 to} R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 50 to} R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or It is a trifluoromethyl group.

As a ^{monovalent organic group of R 50 to} R ⁵⁷ , an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a hook having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkylated group.

R ⁵⁸ and R ⁵⁹ are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.

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

Ｒ¹¹²は、Ａと同義であり、好ましい範囲も同じである。

<< R ¹¹⁵ >>

^{R 115} in the formula (1) represents a tetravalent organic group. The tetravalent organic group is preferably a group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

R ¹¹² is synonymous with A and has the same preferred range.

Ｒ¹¹⁵は、４価の有機基を表す。Ｒ¹¹⁵は式（１）のＲ¹¹⁵と同義である。

^{Specific examples of the tetravalent organic group represented by R 115} in the formula (1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as R ¹¹⁵ in formula (1).

Specific examples of tetracarboxylic acid dianhydrides include pyromellitic acid, pyromellitic acid dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4. , 4'-diphenylsulfide tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dianoxide, 2,3,3', 4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1 , 4,5,7-naphthalenetetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propanedi Anhydrous, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenyl hexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1, 4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1, 2,4,5-Naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1- Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, In addition, at least one selected from these alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms is exemplified.

<< R ¹¹³ and R ¹¹⁴ >>

^{R 113} and R ¹¹⁴ in the formula (1) independently represent a hydrogen atom or a monovalent organic group. At ^{least one of R 113} and R ¹¹⁴ preferably contains a radically polymerizable group, and more preferably both contain a radically polymerizable group. Examples of the radically polymerizable group include a group capable of a cross-linking reaction by the action of a radical, and a preferable example thereof is 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, and a group represented by the following formula (III).

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, with a methyl group being more preferred.

In formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, −CH ₂ CH (OH) CH ₂ − or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom). ~ 12 is preferable, 1 to 6 is more preferable, and 1 to 3 are particularly preferable; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3). The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.

Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH ₂ CH (OH) CH _{2-, and} more preferably an ethylene group, a propylene group, a trimethylene group, and -CH ₂ CH (OH) CH _2-.

Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

As a preferred embodiment of the polyimide precursor in the present invention, an aliphatic group, an aromatic group and an aryl having one, two or three, preferably one acid group as the monovalent organic group of ^{R 113} or R ^114. Alkyl groups and the like can be mentioned. Specific examples thereof include an aromatic group having an acid group having 6 to 20 carbon atoms and an arylalkyl group having an acid group having 7 to 25 carbon atoms. 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 hydroxy group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxy group.

As the ^{monovalent organic group represented by R 113} or R ^114, a substituent that improves the solubility of the developing solution is preferably used.

It is more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.

The alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group). The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl group. , Isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable. In the present specification, the alkyl group defined here is referred to as "Alk".

Specific examples of the aromatic group include a substituted or unsubstituted aromatic hydrocarbon group (as a cyclic structure constituting the group, a benzene ring (the above formulas AR-1, AR-2, AR-3), Naphthalene ring, biphenyl ring (for example, the above formulas AR-5, AR-6, AR-7), bisphenyl ring (for example, the above formulas AR-8, AR-9, AR-10), fluorene ring, pentalene ring, Examples thereof include an inden ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaften ring, a phenylene ring, an anthracene ring, a naphthacene ring, a chrysen ring, and a triphenylene ring. The aromatic hydrocarbon group is referred to as "Ary") or a substituted or unsubstituted aromatic heterocyclic group (the cyclic structure constituting the group includes a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, and an oxazole ring. , Thiazol ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinoxazoline Rings, isoquinoline rings, carbazole rings, phenanthridin rings, aclydin rings, phenanthrolin rings, thiantolen rings, chromium rings, xanthene rings, phenoxatiin rings, phenothiazine rings or phenazine rings) The group heterocycle is called "Aro").

It is also preferable that the polyimide precursor has a fluorine atom in the constituent unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or less. There is no particular upper limit, but 50% by mass or less is practical.

Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the structural unit represented by the formula (1). Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.

Ａ¹¹およびＡ¹²は、酸素原子またはＮＨを表し、Ｒ¹¹¹およびＲ¹¹²は、それぞれ独立に、２価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴は、それぞれ独立に、水素原子または１価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴の少なくとも一方は、ラジカル重合性基を含む基であることが好ましく、ラジカル重合性基であることがより好ましい。

The structural unit represented by the formula (1) is preferably a structural unit represented by the formula (1-A) or the formula (1-B).

A ¹¹ and A ¹² represent an oxygen atom or NH, R ¹¹¹ and R ¹¹² each independently represent a divalent organic radical, and R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or a monovalent. Representing an organic group, ^{at least one of R 113} and R ¹¹⁴ is preferably a group containing a radically polymerizable group, and more preferably a radically polymerizable group.

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ have independent preferred ranges, which are synonymous with the preferred ranges ^{of A 1} , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in equation (1). ..

A preferred range of R ¹¹² has the same meaning as R ¹¹² in formula (5), and more preferably an oxygen atom.

The bonding position of the carbonyl group to the benzene ring in the formula is preferably 4, 5, 3', 4'in the formula (1-A). In formula (1-B), it is preferably 1, 2, 4, 5.

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

As one embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the structural units is the structural unit represented by the formula (1). Is exemplified. The upper limit is practically 100 mol% or less.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000 to 500000, more preferably 5000 to 100,000, and even more preferably 1000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.

The degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.

In the method for producing a polyimide precursor, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.

The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.

In the production of the polyimide precursor, it is preferable to include a step of precipitating a solid. Specifically, the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.

Ｒ¹²¹は、２価の有機基を表し、Ｒ¹²²は、４価の有機基を表し、Ｒ¹²³およびＲ¹²⁴は、それぞれ独立に、水素原子または１価の有機基を表す。

<Polybenzoxazole precursor>

The polybenzoxazole precursor preferably contains a structural unit represented by the following formula (2).

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

R ¹²¹ represents a divalent organic group. The divalent organic group includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). Is more preferable, and a group containing at least one of (6 to 12 is particularly preferable) is preferable. Examples of the aromatic group constituting R ^{121 include R 111} of the above formula (1). As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably derived from 4,4'-oxydibenzoyl chloride.

In formula (2), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same ^{meaning as R 115} in the above formula (1), and the preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group, ^{which are synonymous with R 113} and R ¹¹⁴ in the above formula (1), and the preferable range is also the same.

The polybenzoxazole precursor may contain other types of structural units in addition to the structural units of the above formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2000 to 500000, more preferably 5000 to 100,000, and even more preferably 1000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.

The degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.5 to 3.5, 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, more preferably 30% by mass or more, and 40% by mass, based on the total solid content of the composition. The above is more preferable, 50% by mass or more is further preferable, 60% by mass or more is further preferable, and 70% by mass or more is further preferable. Further, the content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, based on the total solid content of the composition. It is more preferably 98% by mass or less, and even more preferably 95% by mass or less.

The photosensitive resin composition of the present invention may contain only one type of polymer precursor, or may contain two or more types of polymer precursors. When two or more kinds are included, the total amount is preferably in the above range.

<Polymerization initiator>

The photosensitive resin composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. Further, a thermal polymerization initiator (preferably a thermal radical polymerization initiator) may be used in combination as an initiator of the polymerization of the base generated from the thermal base generator.

<< Photopolymerization Initiator >>

The photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.

The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

When the photosensitive resin composition according to the preferred embodiment of the present invention contains a specific thermal base generator and a photopolymerization initiator, the following actions are 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 to cyclize a precursor of a heterocyclic-containing polymer and cure the composition (primary curing). can do. In this heat curing, the specific thermobase generator according to the present invention is useful. Next, the cured photosensitive resin composition layer is irradiated with light. As a result, curing caused by radicals generated by the action of the photopolymerization initiator occurs (secondary curing). At this time, when the polymer precursor has a polymerizable group, the polymerizable group or the polymerizable compound may be polymerized to be photocurable. As a result, the solubility in the light-irradiated portion can be reduced. There is an advantage that regions having different solubilitys can be easily prepared by utilizing this action. Specifically, the photosensitive resin composition layer is exposed through a photomask having a pattern that masks only the electrode portion. This makes it possible to prepare regions having different solubilitys according to the pattern of the electrodes.

As the photopolymerization initiator, a known compound can be arbitrarily used. For example, reference can be made to the description in paragraphs 0107 to 119 of Pamphlet WO 2015/199220, which is incorporated herein by reference.

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. Oxime-based photopolymerization initiators have a> C = N—O—C (= O) − linking group in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04, IRGACURE OXE 369 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-14502). The photoradical polymerization initiator 2) described in 1) is also preferably used. Further, TR-PBG-304 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831 and ADEKA ARCULDS NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.

When the photopolymerization initiator is contained, the content thereof is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention. It is preferably 1.0% by mass or more, and more preferably 1.0% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, and further preferably 10% by mass or less. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total is preferably in the above range.

<< Thermal Polymerization Initiator >>

In the present invention, a thermal polymerization initiator may be used. A thermal polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal polymerization initiator, it is possible to proceed with the polymerization reaction of the polymer precursor as well as the cyclization of the polymer precursor, so that a higher degree of heat resistance can be achieved.

Specific examples of the thermal polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.

When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the photosensitive resin composition of the present invention. It is more preferably 5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, the total is preferably in the above range.

<Polymerizable compound>

The photosensitive resin composition of the present invention contains a polymerizable compound, and preferably contains a radically polymerizable compound. Examples of the polymerizable group include the above-mentioned polymerizable group Ps, and among them, examples of a group Et having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group can be mentioned. Be done. The polymerizable group contained in the polymerizable compound is particularly preferably a (meth) acryloyl group.

The number of polymerizable groups contained in the polymerizable compound may be one or two or more, but the polymerizable compound preferably has two or more polymerizable groups, and more preferably three or more. 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 even more preferably 900 or less. The lower limit of the molecular weight of the polymerizable compound is preferably 100 or more.

From the viewpoint of developability, the photosensitive resin composition of the present invention preferably contains at least one bifunctional or higher polymerizable compound containing two or more polymerizable groups (preferably radical polymerizable groups), and is trifunctional. It is more preferable to contain at least one of the above polymerizable compounds. Further, it may be a mixture of a bifunctional polymerizable compound and a trifunctional or higher functional polymerizable compound. The number of functional groups of the polymerizable compound means the number of polymerizable groups in one molecule.

As a specific example of the polymerizable compound, the compounds described in paragraphs 0056 to 0100 of International Publication No. WO2015 / 199220 Pamphlet can be referred to, which are incorporated herein by reference.

As polymerizable compounds, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (As a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are bonded via an ethylene glycol residue or a propylene glycol residue. The structure is preferable. These oligomer types can also be used.

Commercially available products of the polymerizable compound include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209, which is a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartmer. 231 and 239, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, and urethane oligomer UAS-10. , UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Japan) Chemicals (manufactured by 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 Nichiyu Co., Ltd.), etc. Can be mentioned.

The content of the polymerizable compound is preferably 1% by mass or more, more preferably 3% by mass or more, and 5% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention. It is more preferable to have. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 30% by mass or less.

It is preferable to use the polymerizable compound at the above lower limit value or more because it has an advantage from the viewpoint of pattern formation. Further, it is preferable to use the polymerizable compound at the above upper limit value or less because there is an advantage in terms of the elongation at break.

One type of the polymerizable compound may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.

<Solvent>

The photosensitive resin composition of the present invention preferably contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone. , Δ-Valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-alkyloxypropionic acid alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-). Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) Etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy-2-methylpropion Methyl acetate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvin Suitable examples include propyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutate and the like.

Examples of ethers 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, and propylene glycol. Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.

As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene and the like are preferable.

As the sulfoxides, for example, dimethyl sulfoxide is preferable.

As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like are preferable.

As the solvent, a form in which two or more kinds are mixed is also preferable from the viewpoint of improving the coating surface properties.

In the present invention, 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- Consists of one solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more. The mixed solvent to be mixed is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the photosensitive resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and more preferably 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness and coating method.

Only one type of solvent may be contained, or two or more types may be contained. When two or more kinds of solvents are contained, the total is preferably in the above 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 movement of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer.

The migration inhibitor is not particularly limited, but a heterocycle (pyran ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc. Pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, piperazine ring, morpholin ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and mercapto group compounds, hindered phenolic compounds , Salicylic acid derivative compound, hydrazide derivative compound and the like. 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.

It is also possible to use an ion trap agent that traps anions such as halogen ions.

Examples of other migration inhibitors include rust preventives described in paragraphs 0094 of JP2013-15701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-59656A. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520 can be used.

Specific examples of the migration inhibitor include the following compounds.

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the photosensitive resin composition, and is 0. .05 to 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is further preferable.

The migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.

<Polymerization inhibitor>

The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'. -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 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 shall be 0.01 to 5% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Is more preferable, 0.02 to 3% by mass is more preferable, and 0.05 to 2.5% by mass is further preferable.

The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.

<Metal adhesion improver>

The photosensitive resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesiveness improving agent include a silane coupling agent.

Examples of the silane coupling agent include the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, the compounds described in paragraphs 0063-0071 of International Publication WO2011 / 080992A1, JP-A-2014-191252. Examples thereof include the compounds described in paragraphs 0060 to 0061, the compounds described in paragraphs 0045 to 0052 of JP-A-2014-41264, and the compounds described in paragraph 0055 of International Publication WO2014 / 0975994. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

Further, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used.

When the photosensitive resin composition of the present invention has a metal adhesion improver, the content thereof is 0.1 to 30% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. It is preferably in the range of 0.5 to 15% by mass, and more preferably in the range of 0.5 to 5% by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are good. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.

<Other additives>

The photosensitive resin composition of the present invention contains various additives such as a photocuring accelerator, a sensitizing dye, a chain transfer agent, a surfactant, and a higher grade, if necessary, as long as the effects of the present invention are not impaired. A fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an antioxidant and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

<< Sensitive Dye >>

The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electron-excited state. The sensitizing dye in the electron-excited state comes into contact with a thermal curing accelerator, a thermal polymerization initiator, a photopolymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermosetting accelerator, the thermal polymerization initiator, and the photopolymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases. For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP2016-027357A can be referred to, and this content is incorporated in the present specification.

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

<< Chain Transfer Agent >>

The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazol, etc.) can be preferably used.

When the photosensitive resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. Preferably, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable. The chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.

<< Surfactant >>

Each type of surfactant may be added to the photosensitive resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferable.

When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is 0.001 to 2.0% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass. The surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.

<< Higher fatty acid derivatives >>

In the photosensitive resin composition of the present invention, in order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added, and the surface of the composition is dried in the process of drying after application. It may be unevenly distributed in.

When the photosensitive resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative shall be 0.1 to 10% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Is preferable. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.

<Restrictions on other contained substances>

The water content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties.

From the viewpoint of insulating properties, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.

Further, as a method for reducing metal impurities unintentionally contained in the photosensitive resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the photosensitive resin composition of the present invention. Methods such as filtering the raw materials constituting the photosensitive resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.

Considering the use as a semiconductor material, 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 more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.

A conventionally known storage container can be used as the storage container for the photosensitive resin composition of the present invention. In addition, as the storage container, for the purpose of suppressing impurities from being mixed into the raw materials and compositions, the inner wall of the container is made of a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resin are formed into a 7-layer structure. It is also preferable to use a bottle of plastic. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

<Preparation of composition>

The photosensitive resin composition of the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited, and a conventionally known method can be used.

Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the composition. 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 filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.

In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

<Cured film, laminate, semiconductor device, and their manufacturing method>

Next, a cured film, a laminate, a semiconductor device, and a method for manufacturing them will be described.

The cured film of the present invention is obtained by curing the photosensitive resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, or 1 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.

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

Examples of applicable fields of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008, Masaaki Kakimoto / supervision, CMC technical library "Basics and development of polyimide materials" published in November 2011 , Japan Polyimide / Aromatic Polymer Study Group / ed., "Latest Polyimide Basics and Applications" NTS, August 2010, etc. can be referred to.

The cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially microelectronics.

The method for producing a cured film of the present invention includes using the photosensitive resin composition of the present invention. Specifically, it preferably contains at least the following (a), preferably includes (a) and (d), and more preferably includes the steps (a) to (d).

(A) A film forming step of applying a photosensitive resin composition to a substrate to form a film.

(B) Exposure step of exposing the film after the film forming step

(C) A developing step of developing an exposed photosensitive resin composition layer.

(D) Heating step of heating the developed photosensitive resin composition at 80 to 450 ° C.

As in this embodiment, the exposed resin layer can be further cured by heating after development. In this heating step, the thermobase generator of the present invention acts to obtain sufficient curability.

The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention. The method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after forming the cured film according to the above-mentioned method for producing the cured film. )-(D). In particular, it is preferable to carry out each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, between the cured films, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to (d). ) Can be performed a plurality of times to obtain a laminated body of the cured film.

These details will be described below.

<< Membrane formation process (layer formation process) >>

The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the photosensitive resin composition is applied to a substrate to form a film (layered).

The type of substrate can be appropriately determined depending on the application, but semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, polysilicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, thin film, and magnetic film. , Reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like are not particularly limited. In the present invention, a semiconductor-made substrate is particularly preferable, and a silicon substrate is more preferable.

Further, 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 serves as a substrate.

Coating is preferable as a means for applying the photosensitive resin composition to the substrate.

Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. The coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, the spin coating method, spray coating method, inkjet method, etc. are preferable, and for rectangular substrates, the slit coating method, spray coating method, inkjet, etc. The method or the like is 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 process >>

The production method of the present invention may include a step of forming the photosensitive resin composition layer, followed by a film forming step (layer forming step), and then drying to remove the solvent. The preferred drying temperature is 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<< Exposure process >>

The production method of the present invention may include an exposure step of exposing the photosensitive resin composition layer. Exposure is not particularly limited so long as it can be cured photosensitive resin composition, for example, it is preferable to irradiate 100~10000mJ / cm ² at an exposure energy conversion at a wavelength 365nm, 200~8000mJ / cm ² irradiated Is more preferable.

The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, preferably 240 to 550 nm.

The exposure wavelengths are as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), and (6) electron beam. Regarding the photosensitive resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferable, and exposure with an i-line is particularly preferable. As a result, particularly high exposure sensitivity can be obtained.

<< Development process >>

The production method of the present invention may include a development treatment step of performing a development treatment on the exposed photosensitive resin composition layer. By developing, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.

Development is performed using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed. The developer preferably contains an organic solvent, and more preferably the developer contains 90% or more of the organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of −1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.

As the organic solvent, those exemplified in the above <solvent> section can be preferably used.

In the present invention, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable.

The developing solution preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Further, the developing solution may be an organic solvent in an amount of 100% by mass.

The development time is preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly specified, but is usually 20 to 40 ° C.

After the treatment with the developing solution, further rinsing may be performed. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with a solvent contained in the photosensitive resin composition. The rinsing time is preferably 5 seconds to 1 minute.

<< Heating process >>

The production method of the present invention preferably includes a step of heating after a film forming step (layer forming step), a drying step, or a developing step. In the heating step, the cyclization reaction of the polymer precursor proceeds. At this time, good exposure developability can be realized without the specific thermobase generator impairing the photosensitivity. Then, by heating the resin pattern left after development, a specific thermal base generator releases the base, and rapid and sufficient curing by cyclization of the resin proceeds.

The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. It is even more preferable, and it is even more preferable that the temperature is 200 ° C. or lower.

The heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of the base while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, the cured film can be prevented. Residual stress can be relaxed.

The temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the photosensitive resin composition is applied onto a substrate and then dried, the temperature of the film (layer) after drying is, for example, 30 higher than the boiling point of the solvent contained in the photosensitive resin composition. It is preferable to gradually raise the temperature from a temperature as low as about 200 ° C.

The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.

In particular, when forming a multi-layered laminate, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the polymer precursors between the layers are undergoing a cross-linking reaction at this temperature.

Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed. The heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. 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.

Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

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

<< Metal layer forming process >>

The production method of the present invention preferably includes (e) a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment.

As the metal layer, existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. More preferred.

The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination method thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.

The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm at the thickest portion.

<< Laminating process >>

The production method of the present invention preferably further includes a laminating step.

The laminating step is a step of (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing process step, and (d) a heating step again on the surface of the cured film (resin layer) or the metal layer. Is a series of steps including performing in this order. However, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated photosensitive resin composition layers all at once. Further, the (c) developing step may be followed by the (e) metal layer forming step, and even if the heating is performed each time (d), the (d) is collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the drying step, the heating step, and the like as appropriate.

When the laminating step is further performed after the laminating step, the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. An example of the surface activation treatment is plasma treatment.

The laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.

For example, a structure such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer is preferable, and the resin layer is preferably 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 a cured film (resin layer) of the photosensitive resin composition so as to cover the metal layer after providing the metal layer. Specifically, a mode in which (a) a film forming step, (b) an exposure step, (c) a developing step, (e) a metal layer forming step, and (d) a heating step are repeated in this order, or (a) film forming. Examples thereof include an embodiment in which (b) an exposure step, (c) a development step, and (e) a metal layer forming step are repeated in this order, and (d) a heating step is collectively provided 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 laminated alternately.

The present invention also discloses a semiconductor device having the cured film or laminate of the present invention. As specific examples of the semiconductor device in which the photosensitive resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 and the description in FIG. 1 of JP-A-2016-0273557 are taken into consideration. Yes, these contents are incorporated herein.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<Synthesis example 1>

[Synthesis of polyimide precursor (A-1: polyimide precursor having no radical polymerizable group) from pyromeritic acid dianhydride, 4,4'-diaminodiphenyl ether and benzyl alcohol]

14.06 g (64.5 mmol) of pyromeritic acid dianhydride (dried at 140 ° C. for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N-methylpyrrolidone. It was dried in a molecular sieve. The suspension was heated at 100 ° C. for 3 hours. A clear solution was obtained a few minutes after heating. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL ₂ was added over 10 minutes while keeping the temperature at −10 ± 4 ° C. Viscosity increased while adding SOCL _2. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution prepared by dissolving 11.08 g (58.7 mmol) of 4,4′-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at −5 to 0 ° C. over 20 minutes. Then, the reaction mixture was reacted at 0 ° C. for 1 hour, 70 g of ethanol was added, and the mixture was stirred at room temperature overnight. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polyimide precursor was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. The obtained polyimide precursor was then dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of this polyimide precursor was 18,000.

A-1

<Synthesis example 2>

[Synthesis of Polyimide Precursor (A-2: Polyimide Precursor with Radical Polymerizable Group) from Pyromeric Acid Dianhydride, 4,4'-Diaminodiphenyl Ether and 2-Hydroxyethyl Methacrylate]

14.06 g (64.5 mmol) of pyromeritic dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 20. 4 g of pyridine (258 mmol) and 100 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromeritic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester is _{chlorinated with SOCL 2} , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the polyimide precursor is converted into a polyimide precursor in the same manner as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 19,000.

A-2

<Synthesis example 3>

[Synthesis of polyimide precursor (A-3: polyimide precursor having radical polymerizable group) from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone. , 20.4 g of pyridine (258 mmol) of pyridine, and 100 g of diglyme are mixed and stirred at a temperature of 60 ° C. for 18 hours to obtain a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Manufactured. Next, the obtained diester is _{chlorinated with SOCL 2} , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the polyimide precursor is converted into a polyimide precursor in the same manner as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 18,000.

A-3

<Synthesis example 4>

Polyimide precursor from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotrizine) and 2-hydroxyethyl methacrylate (A-4: having radical polymerizable group) Synthesis of polyimide precursor)]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone. , 20.4 g of pyridine (258 mmol) and 100 g of diglime were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. .. Next, the obtained diester was _{chlorinated with SOCL 2} and then converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 1, and the same as in Synthesis Example 1. A polyimide precursor was obtained by the above method. The weight average molecular weight of this polyimide precursor was 19,000.

A-4

<Synthesis example 5>

[Synthesis of polybenzoxazole precursor (A-5) from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4,4'-oxydibenzoyl chloride]

To 100 mL of N-methyl-2-pyrrolidone, 13.92 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added and dissolved by stirring. Subsequently, 11.21 g of 4,4'-oxydibenzoyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5 ° C., and then stirring was continued for 60 minutes. The polybenzoxazole precursor was then precipitated in 6 liters of water and the water-polybenzoxazole precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polybenzoxazole precursor was filtered off and stirred again in 6 liters of water for 30 minutes and filtered again. The resulting polybenzoxazole precursor was then dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of this polybenzoxazole precursor was 15,000.

A-5

Examples and Comparative Examples

<Preparation of photosensitive resin composition>

The components shown in Table 2 below were mixed to obtain each photosensitive resin composition. The obtained photosensitive resin composition was pressure-filtered through a filter having a pore width of 0.8 μm. Details such as the names and structures of the compounds listed in the table are given as notes below the table.

The following evaluation tests were conducted on each of the prepared photosensitive resin compositions. The results are shown in Table 3.

<Storage stability>

The viscosity (0 days) of the photosensitive resin composition after the filtration was measured using an E-type viscometer. The photosensitive resin composition was allowed to stand in a closed container at 25 ° C. for 14 days, and then the viscosity (14 days) was measured again using an E-type viscometer. The viscosity volatility was calculated from the following formula. The lower the viscosity volatility, the higher the storage stability.

Viscosity volatility = | 100 × {1- (viscosity (14 days) / viscosity (0 days))} |

The viscosity was measured at 25 ° C., and the others were in accordance with JIS Z 8803: 2011.

A: Viscosity volatility is 5% or less

B: Viscosity volatility exceeds 5% and 10% or less

C: Viscosity volatility exceeds 10% and 15% or less

D: Viscosity volatility exceeds 15% and 20% or less

E: Viscosity volatility exceeds 20%

<Breaking elongation>

Each of the photosensitive resin compositions after filtration was applied in layers 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 a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 20 μm on the silicon wafer. ^{The photosensitive resin composition layer on the silicon wafer was exposed to an exposure energy of 500 mJ / cm 2} using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was exposed to a nitrogen atmosphere. Underneath, the temperature was raised at a heating rate of 10 ° C./min, and after reaching 180 ° C., this temperature was maintained for 3 hours. The cured resin layer was immersed in a 4.9% hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a resin film 1.

The elongation at break of the resin film 1 was measured using a tensile tester (Tencilon). Specifically, the crosshead speed is 300 mm / min, the width is 10 mm, and the sample length is 50 mm. Then, the elongation at break was measured. The elongation at break is E _b (%) = (L _{b −} L ₀ ) / L ₀ (E _b : elongation at cutting, L ₀ : length of the test piece before the test, L _b : when the test piece is cut. Calculated based on the length of the test piece). For the evaluation, the elongation at break in each of the longitudinal direction and the width direction was measured 5 times each, and the average value in the longitudinal direction and the width direction was used.

A: Break elongation exceeded 85%

B: Break elongation exceeds 80% and 85% or less

C: Break elongation exceeds 75% and 80% or less

D: Break elongation exceeds 70% and 75% or less

E: Break elongation is 70% or less

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

(B) Thermal base generator, etc.

Regarding the thermobase generator, the relationship between the example numbers in the above examples and the numbers of the compounds exemplified above in the general description is shown in Table 4 below.

Comparative example compound

(C) Photopolymerization initiator

C-1: IRGACURE OXE 01 (manufactured by BASF)

C-2: IRGACURE OXE 02 (manufactured by BASF)

C-3: IRGACURE 369 (manufactured by BASF)

Ｄ−３：Ａ−ＴＭＭＴ（新中村化学工業社製）

(D) Polymerizable compound

D-1: A-DPH (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

D-2: SR-209 (manufactured by Sartmer)

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

(E) Polymerization inhibitor

E-1: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

E-2: Parabenzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)

E-3: Paramethoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

(F) Migration inhibitor

F-1: Compound M-1 exemplified above

F-2: Compound M-2 exemplified above

F-3: Compound M-3 exemplified above

F-4: Compound M-4 exemplified above

(G) Metal Adhesive Improvement Agent

G-1: Compound SC-1 exemplified above

G-2: Compound SC-2 exemplified above

G-3: Compound SC-3 exemplified above

(I) Solvent

I-1: γ-Butyrolactone (manufactured by Sanwa Yuka Co., Ltd.)

I-2: Dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.)

I-3: N-methyl-2-pyrrolidone (manufactured by Ashland)

As can be seen from the above results, in the photosensitive resin composition of the example using the thermal base generator having a polymerizable group in the portion to be the base to be generated, all the cured films have good elongation at break (80%). The above) was shown (Examples 1 to 25). The fact that the cured film exhibits a high elongation at break means that the thermosetting of the photosensitive resin composition has sufficiently progressed, and the thermobase generators B-1 to B-20 have a film curing temperature of 180. It is considered that the base was effectively generated at ° C and the volatilization of the generated base was suppressed. Further, if necessary, the photosensitive resin composition can be made excellent in storage stability (Examples 1, 3 to 7, 9, 11 to 24), where the basicity before heating is low. It was understood that the polymer precursor was suppressed and the curing of the polymer precursor over time was suppressed.

On the other hand, in the photosensitive resin compositions of Comparative Examples using the thermobase generator having no polymerizable group, it is considered that the curing reaction of the thermosetting resin did not proceed sufficiently, and as a result, the cured film was formed. The breaking elongation was significantly inferior. In addition, the storage stability of Comparative Examples 1 and 2 was extremely low.

<Example 100>

The photosensitive resin composition 1 of Example 1 was pressure-filtered through a filter having a pore width of 1.0 μm, and then spun (3500 rpm, 30 seconds) on the surface of a resin substrate on which a thin copper layer was formed. Applied. The photosensitive resin composition applied to the resin substrate was dried at 100 ° C. for 2 minutes and then exposed using a stepper (NSR1505i6 manufactured by Nikon Corporation). The exposure was carried out through a mask at a wavelength of 365 nm and an exposure amount of ^{200 mJ / cm 2.} After exposure, baking was performed, developed with cyclopentanone for 30 seconds, and rinsed with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds to obtain a pattern.

Then, it was heated at 230 ° C. for 3 hours to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating properties.

Further, the compounds X-4 and X-5 described in Patent Document 3 (Japanese Unexamined Patent Publication No. 2006-228880) generate bases by light irradiation, but no bases are generated at 200 ° C. or lower. ..

Claims (13)

With a thermobase generator

Polymer precursors selected from polyimide precursors and polybenzoxazole precursors,

Photopolymerization initiator and

With polymerizable compounds

A photosensitive resin composition containing

A photosensitive resin composition in which the thermal base generator generates a base at 200 ° C. or lower and has a polymerizable group at a site where the base is generated.

The photosensitive resin composition according to claim 1, wherein the thermobase generator has a structure represented by any of the following formulas (N1) to (N3);

In formula (N1), X is a single bond or a divalent linking group, R ¹ independently represents a hydrogen atom or an organic group, n1 and n2 are 1 or 2, n1 + n2 is 3, and n3. Is 0 or 1, X is not a single bond when n3 is 1, and the groups in the two [] are the same or different when n1 is 2, and when n2 is 2. two R ¹ may be the same or different, two R ¹ may form a cyclic structure via connection to each other, 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 in parentheses. groups may be the same as or different from each other, n5 is or different and the two R ² when 2 identical to each other, the two R ² may be linked to each other to form a cyclic structure, R ^At least one of 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, and R ^{7 to} R ⁹ each independently represent a hydrocarbon group. A represents an m-valent acid anion, m is an integer of 1 to 4, n7 is an integer of 1 to 12, n8 and n9 are integers of 1 to 12, n8 = n9, and R ⁵ And R ⁶ may be connected to form an annular structure, and ^{two or more of R 7 to} R ⁹ may be connected to form an annular structure, and at least one of ^{R 7 to} R ^{9 may be connected to form an annular structure.} It has a polymerizable group.

The photosensitive group according to claim 1 or 2, wherein the polymerizable group of the generated base site is an epoxy group, an oxetane group, an ethylenically unsaturated group, or a group represented by the following formula (Z). Resin composition;

In formula (Z), Rc represents an oxygen atom, a nitrogen atom or a (n + 2) -valent aromatic group, Ra and Rb independently represent a hydrogen atom or an organic group, and n represents an integer of 0 to 6. When Rc is an oxygen atom, n is 0, when Rc is a nitrogen atom, n is 1, and * represents a bond.

The photosensitive resin composition according to any one of claims 1 to 3, wherein the polymer precursor contains a polyimide precursor.

The photosensitive resin composition according to claim 4, wherein the polyimide precursor has a structural unit represented by the following formula (1).

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

The photosensitive resin composition according to any one of claims 1 to 6, which is used for forming an interlayer insulating film for a rewiring layer.

A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 7.

A laminate having the cured film according to claim 8 having 2 or more layers and 7 or less layers, and having a metal layer between the cured films.

A method for producing a cured film, which comprises a film forming step of applying the photosensitive resin composition according to any one of claims 1 to 7 to a substrate to form a film.

The method for producing a cured film according to claim 10, further comprising a heating step of heating the film at 80 to 450 ° C.

The method for producing a cured film according to claim 10, further comprising an exposure step for exposing the film and a developing step for developing the film.

A semiconductor device having the cured film according to claim 8 or the laminate according to claim 9.