JP7042353B2 - Photosensitive resin compositions, cured films, laminates, methods for manufacturing cured films, and semiconductor devices. - Google Patents

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.

Cyclized and cured resins such as polyimide resins and polybenzoxazole resins have excellent heat resistance and insulating properties, and are therefore applied to various applications. The application is not particularly limited, and examples thereof include semiconductor devices for mounting as materials for insulating films and encapsulants, or as protective films (see Non-Patent Documents 1 and 2 and the like). It is also used as a base film and coverlay for flexible substrates.

Such a polyimide resin or the like generally has low solubility in a solvent. Therefore, a method of dissolving in a solvent in the state of a polymer precursor before the cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor 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. The polymer precursor can then be heated to cyclize to form a cured product. In addition to the high performance of polyimide resins and the like, from the viewpoint of excellent manufacturing adaptability, the industrial application development is expected more and more.

Patent Document 1 describes an acidic compound that generates a base when heated to 40 ° C. or higher, and a thermosetting agent containing at least one selected from an ammonium salt having an anion having pKa1 of 0 to 4 and an ammonium cation. A thermosetting resin composition containing a thermosetting resin is disclosed.

Patent Document 2 discloses a resin composition containing a polyimide precursor having a specific structural unit, a compound that generates radicals by irradiation with active light, a compound having an oligopropyleneoxy structure, and a solvent. ing.

International Publication No. WO2015 / 199219 Pamphlet Japanese Unexamined Patent Publication No. 2014-201695

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

The techniques of Patent Documents 1 and 2 have made it possible to cyclize a polymer precursor at a low temperature to obtain a cured product. On the other hand, further research and development is required to meet the diversified technological demands of this type of resin in recent years.

Therefore, it is an object of the present invention to provide a novel thermal base generator and to enrich materials in the field of photosensitive resin compositions containing a precursor of a heterocyclic-containing polymer. Further, the photosensitive resin composition, the cured film, and the laminated body can realize excellent storage stability in the photosensitive resin composition and can increase the breaking elongation of the cured film formed from the photosensitive resin composition. , A method for manufacturing a cured film, and a semiconductor device.

As a result of studies by the present inventor based on the above problems, it has been found that a specific thermobase generator containing a site of a carboxyl group or an ester thereof and a site having an amide structure can solve the above problems. The invention was completed. Specifically, the above problems have been solved by the following means.

式（Ｎ１）中、Ｒ^N1およびＲ^N2はそれぞれ独立に１価の有機基を表し、Ｒ^C1は水素原子または保護基を表し、Ｌは２価の連結基を表す。

＜２＞上記式（Ｎ１）中のＬが連結鎖長１～５の２価の有機基である、＜１＞に記載の熱塩基発生剤。

＜３＞上記式（Ｎ１）中のＲ^N1およびＲ^N2が、それぞれ独立に、炭化水素基である、＜１＞または＜２＞に記載の熱塩基発生剤。

＜４＞上記式（Ｎ１）中のＲ^N1およびＲ^N2が、それぞれ独立に、脂肪族炭化水素基である、＜１＞～＜３＞のいずれか１つに記載の熱塩基発生剤。

＜５＞上記式（Ｎ１）中のＬが、１，２－エチレン基、１，３－プロパンジイル基、１，２－シクロヘキサンジイル基、シスビニレン基、１，２-フェニレン基、１，２－フェニレンメチレン基、または１，２－エチレンオキシ－１，２－エチレン基である、＜１＞～＜４＞のいずれか１つに記載の熱塩基発生剤。

＜６＞上記式（Ｎ１）中のＲ^C1が水素原子である、＜１＞～＜５＞のいずれか１つに記載の熱塩基発生剤。

＜７＞上記式（Ｎ１）で表される熱塩基発生剤が分解して発生する化合物が下記式（Ｎ２）で表される化合物であり、上記式（Ｎ２）で表される化合物の沸点が５０℃以上である、＜１＞～＜６＞のいずれか１つに記載の熱塩基発生剤；

式（Ｎ２）中、Ｒ^N1およびＲ^N2はそれぞれ独立に１価の有機基を表す。

＜８＞＜１＞～＜７＞のいずれか１つに記載の熱塩基発生剤と複素環含有ポリマーの前駆体とを含む、感光性樹脂組成物。

＜９＞さらに、光ラジカル重合開始剤およびラジカル重合性化合物を含む、＜８＞に記載の感光性樹脂組成物。

＜１０＞上記複素環含有ポリマーの前駆体がポリイミド前駆体またはポリベンゾオキサゾール前駆体を含む、＜８＞または＜９＞のいずれか１つに記載の感光性樹脂組成物。

＜１１＞上記複素環含有ポリマーの前駆体がポリイミド前駆体を含む、＜８＞～＜１０＞のいずれか１つに記載の感光性樹脂組成物。

＜１２＞上記複素環含有ポリマーの前駆体が下記式（１）で表される構成単位を有する、＜８＞～＜１０＞のいずれか１つ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価の連結基を表し、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。

＜１３＞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、＜１２＞に記載の感光性樹脂組成物。

＜１４＞再配線層用層間絶縁膜の形成に用いられる、＜８＞～＜１３＞のいずれか１つに記載の感光性樹脂組成物。

＜１５＞＜８＞～＜１４＞のいずれか１つに記載の感光性樹脂組成物を硬化してなる硬化膜。

＜１６＞＜１５＞に記載の硬化膜を２層以上有し、上記硬化膜の間に金属層を有する、積層体。

＜１７＞＜８＞～＜１６＞のいずれか１つ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。

＜１８＞上記膜を５０～４５０℃で加熱する工程を含む、＜１７＞に記載の硬化膜の製造方法。

＜１９＞＜１５＞記載の硬化膜または＜１６＞に記載の積層体を有する、半導体デバイス。

<1> Thermal base generator represented by the following formula (N1);

In formula ( ^N1 ), RN1 and ^RN2 each independently represent a monovalent organic group, ^RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

<2> The thermobase generator according to <1>, wherein L in the above formula (N1) is a divalent organic group having a chain length of 1 to 5.

<3> The thermal base generator according to <1> or <2>, wherein RN1 and ^RN2 in the above formula ( ^N1 ) are independently hydrocarbon groups.

<4> The thermobase generator according to any one of <1> to <3>, wherein RN1 and ^RN2 in the above formula ( ^N1 ) are independently aliphatic hydrocarbon groups.

<5> L in the above formula (N1) is a 1,2-ethylene group, a 1,3-propanediyl group, a 1,2-cyclohexanediyl group, a cisvinylene group, a 1,2-phenylene group, 1,2-. The thermal base generator according to any one of <1> to <4>, which is a phenylene methylene group or a 1,2-ethyleneoxy-1,2-ethylene group.

<6> The thermobase generator according to any one of <1> to <5>, wherein ^RC1 in the above formula (N1) is a hydrogen atom.

<7> The compound generated by decomposing the thermal base generator represented by the above formula (N1) is a compound represented by the following formula (N2), and the boiling point of the compound represented by the above formula (N2) is The thermobase generator according to any one of <1> to <6>, which has a temperature of 50 ° C. or higher;

In formula ( ^N2 ), RN1 and ^RN2 each independently represent a monovalent organic group.

<8> A photosensitive resin composition comprising the thermal base generator according to any one of <1> to <7> and a precursor of a heterocyclic-containing polymer.

<9> The photosensitive resin composition according to <8>, further comprising a photoradical polymerization initiator and a radically polymerizable compound.

<10> The photosensitive resin composition according to any one of <8> or <9>, wherein the precursor of the heterocyclic-containing polymer contains a polyimide precursor or a polybenzoxazole precursor.

<11> The photosensitive resin composition according to any one of <8> to <10>, wherein the precursor of the heterocyclic-containing polymer contains a polyimide precursor.

<12> The photosensitive resin composition according to any one of <8> to <10>, wherein the precursor of the heterocyclic-containing polymer 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 linking group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ independently represents a hydrogen atom or a monovalent organic group.

<13> The photosensitive resin composition according to <12>, wherein at least one of R ¹¹³ and R ¹¹⁴ in the above formula (1) contains a radically polymerizable group.

<14> The photosensitive resin composition according to any one of <8> to <13>, which is used for forming an interlayer insulating film for a rewiring layer.

<15> A cured film obtained by curing the photosensitive resin composition according to any one of <8> to <14>.

<16> A laminated body having two or more cured films according to <15> and having a metal layer between the cured films.

<17> A method for producing a cured film, which comprises a film forming step of applying the photosensitive resin composition according to any one of <17> and <16> to a substrate to form a film.

<18> The method for producing a cured film according to <17>, which comprises a step of heating the film at 50 to 450 ° C.

<19> A semiconductor device having the cured film according to <15> or the laminate according to <16>.

INDUSTRIAL APPLICABILITY According to the present invention, a novel thermal base generator can be provided, and materials can be enriched in the field of photosensitive resin compositions containing a precursor of a heterocyclic-containing polymer. Further, according to the present invention, it is possible to realize excellent storage stability in the photosensitive resin composition and to increase the breaking elongation of the cured film formed from the photosensitive resin composition.

Hereinafter, the contents of the present invention will be described in detail. In addition, in this specification, "-" is used in the meaning which includes the numerical values described before and after it 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 the representative 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 not describing 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-shaped or cyclic, and the chain-shaped group may be linear or branched. These are also synonymous with the alkenyl group, the alkylene group, and the alkenylene group.

As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. The light used for exposure generally includes an 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.

As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. Representing either, "(meth) acrylic" represents both "acryloyl" and "methacrylic", 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 intended 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 measured by gel permeation chromatography (GPC measurement) and are defined as polystyrene-equivalent values unless otherwise specified. In the present specification, for example, HLC-8220 (manufactured by Tosoh Corporation) is used as the weight average molecular weight (Mw) and the number average molecular weight (Mn), 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). In this measurement, THF (tetrahydrofuran) is used as the eluent unless otherwise specified. Further, unless otherwise specified, a detector having a wavelength of 254 nm of UV rays (ultraviolet rays) is used for detection.

<Thermal base generator>

The thermal base generator of the present invention is represented by the following formula (N1). Hereinafter, this thermobase generator may be referred to as a "specific thermobase generator" to distinguish it from other thermobase generators.

式（Ｎ１）中、Ｒ^N1およびＲ^N2はそれぞれ独立に１価の有機基を表し、Ｒ^C1は水素原子または保護基を表し、Ｌは２価の連結基を表す。

In formula ( ^N1 ), RN1 and ^RN2 each independently represent a monovalent organic group, ^RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, and more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic arrangement that is the shortest route between the two carbonyl groups in the equation, and is required to link the linking group L and the two adjacent carbonyl carbons. It refers to the number of atoms. The linking chain length of Exemplified Compound B-1, which will be described later, is 2.

It is preferable that the specific thermobase generator is one in which the decomposition reaction proceeds in the molecule. Specifically, the reaction proceeds by heating or the like, and the carbonyl group of the amide structure (LC (= O) -N-) in the formula and the nitrogen atom are dissociated, and the amine (preferably the second) is dissociated. It is preferable to produce a secondary amine). From the viewpoint of rapidly advancing this decomposition reaction, the linking group L is preferably the above-mentioned linking chain length, but further, the linking group is configured within the range of the carbon number of each linking group exemplified below. Is preferable. In addition, from the viewpoint of the progress of the intramolecular decomposition reaction, when the linking group L is an alkenylene group, it is preferable that the carbonyl group bonded to both ends of L has a cis-type configuration with respect to L. However, the present invention is not particularly limited in this description.

Since the thermobase generator of the present invention is acidic or neutral at room temperature, it does not promote cyclization of the precursor of the heterocyclic-containing polymer. That is, the photosensitive resin composition containing the thermal base generator of the present invention maintains storage stability. After heating, the base generated from the thermal base generator effectively promotes the cyclization of the precursor of the heterocyclic-containing polymer, so that the obtained cured film has excellent elongation at break. In the present invention, when a base is generated from a specific thermal base generator, decomposition products other than the generated base are volatilized and can be configured so as not substantially remain in the membrane. Here, "substantially non-remaining" is preferably 1% by mass or less, and may be 0.5% by mass or less, or 0.1% by mass or less.

In the formula ( ^N1 ), RN1 and ^RN2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and a hydrocarbon group (preferably 3 to 12 carbon atoms). It is preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms), and specifically, an aliphatic hydrocarbon group (preferably 1 to 12 carbon atoms). Is more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and an aliphatic hydrocarbon can be mentioned. Groups are preferred. It is preferable to use an aliphatic hydrocarbon group as ^RN1 and ^RN2 because the basicity of the generated base is high. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are contained in the aliphatic hydrocarbon chain or the aromatic ring. It may have an oxygen atom in the substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

As the aliphatic hydrocarbon group constituting ^RN1 and ^RN2 , a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an oxygen atom are contained in the chain. Examples thereof include alkyl groups having.

The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. The linear or branched chain alkyl group includes, for example, 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, an undecyl group, a dodecyl group and the like. Can be mentioned.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.

The group related to the combination of the chain alkyl group and the cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Examples of the group related to the combination of the chain alkyl group and the cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, an ethylcyclohexylethyl group and the like.

The alkyl group having an oxygen atom in the chain is preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched.

Of these, alkyl groups having 5 to 12 carbon atoms are preferable for ^RN1 and ^RN2 from the viewpoint of increasing the boiling point of the decomposition-generated base described later. However, when a long-chain chain-like alkyl group is used in a photosensitive resin composition, the adhesion may be inferior when laminated with a metal (for example, copper) layer, and in a formulation that emphasizes this point, it may be poor. It is preferable to use a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms in that the group can suppress the above-mentioned problem and maintain good adhesion to the metal layer.

^RN1 and ^RN2 may be connected to each other to form an annular structure. In forming the cyclic structure, oxygen atoms or the like may be contained in the chain. The cyclic structure formed by ^RN1 and ^RN2 may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferable. As the cyclic structure to be formed, a 5-membered ring or a 6-membered ring containing a nitrogen atom in the formula (N1) is preferable, and for example, a pyrrol ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, and the like. Examples thereof include a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like are preferable.

^RC1 represents a hydrogen atom or a protecting group, and a hydrogen atom is preferable.

As the protecting group, a protecting group that decomposes by the action of an acid or a base is preferable, and a protecting group that decomposes by an acid is preferable.

Examples of the group desorbed by acid include -C (R ³⁶ ) (R ³⁷ ) (R ³⁸ ), -C (R ³⁶ ) (R ³⁷ ) (OR ³⁹ ), and -C (R ⁰¹ ) (R ⁰² ). ) (OR ³⁹ ) and the like.

In the above formula, R ³⁶ to R ³⁹ 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) and an aryl group (6 to 22 carbon atoms are preferable). Preferably, 6-18 is more preferred, 6-10 is more preferred), arylalkyl groups (7-23 carbons are preferred, 7-19 are more preferred, 7-11 are more preferred), or alkenyl groups (carbons are preferred). 2 to 12 is preferable, 2 to 6 is more preferable, and 2 to 3 is more preferable). At least two of R ³⁶ to R ³⁸ may be connected to each other to form a ring. Further, at least two of R ³⁶ , R ³⁷ , and R ³⁹ may be connected to each other to form a ring. The alkyl group is a linear, branched or cyclic alkyl group.

R ⁰¹ and R ⁰² are each independently a hydrogen atom, 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 aryl group (preferably 6 to 22 carbon atoms). , 6-18 is more preferred, 6-10 is even more preferred), arylalkyl groups (7-23 carbons are preferred, 7-19 are more preferred, 7-11 are even more preferred), or alkenyl groups (2 carbons). ~ 12 is preferable, 2 to 6 are more preferable, and 2 to 3 are more preferable). R ³⁹ and the carbon atom (C) in the formula may be linked to form a ring.

The linear or branched alkyl group of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² is preferably an alkyl group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, or sec-. Butyl group, hexyl group, octyl group and the like can be mentioned.

The cycloalkyl groups of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² may be monocyclic or polycyclic. As the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferable, and for example, an adamantyl group, a norbornyl group, a camphanyl group, a dicyclopentyl group, an α-pinene group, a tricyclodecanyl group, a tetracyclododecyl group and Andros. Examples include a tanyl group. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

The aryl group of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group and an anthryl group.

The arylalkyl group of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² is preferably an arylalkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group and a naphthylmethyl group.

The alkenyl group of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group and a cyclohexenyl group.

The ring formed by bonding R ³⁶ and R ³⁷ is preferably a cycloalkyl group (monocyclic or polycyclic). As the cycloalkyl group, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group is preferable. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a monocyclic cycloalkyl group having 5 carbon atoms is particularly preferable.

Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. Examples of the chain or cyclic alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group and the like. Specific examples of the chain-like alkyl group having an oxygen atom in the chain include an alkyloxyalkyl group, and more specifically, a methyloxymethimethyl (MOM) group, an ethyloxyethyl (EE) group and the like. Can be mentioned. Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyranyl (THP) group and the like.

When ^RC1 is a hydrogen atom, the acid (carboxyl group) thereof is exposed when a specific thermal base generator is used in the photosensitive resin composition. As a result, a reaction other than the intended one may proceed, which may cause a decrease in stability. In such a case, it is preferable to introduce a protecting group as ^RC1 from the viewpoint of suppressing or preventing the progress of the reaction and maintaining good stability.

On the other hand, from the viewpoint of exerting the desired action of a specific thermobase generator, the protecting group is released at an appropriate time, and a carboxyl group (-COOH) or an anion thereof (-COOH) or an anion thereof (-COOH) is attached to the terminal of the specific thermobase generator. It is preferable that ^COO- ) is generated. The method for removing the protecting group in the system at a desired time is not particularly limited, and for example, (1) the photosensitive resin composition contains an acid, or an acid generator is contained to add an acid to the composition. Examples include a mode in which the protecting group of a specific thermobase generator is released by its action, and (2) a mode in which the photosensitive resin composition is heated and the protecting group of the specific thermobase generator is released at that time. Be done. Examples of the acid generator used for removing the protecting group according to the aspect (1) include a thermoacid generator. The heating temperature applied to the removal of the protecting group according to the aspect (2) is not particularly limited, but it is preferably in the range of the temperature at which the decomposition-generated base is generated by the decomposition of the following thermal base generator. In such an embodiment, the heat treatment of cyclizing and curing the precursor of the heterocyclic ring-containing polymer of the photosensitive resin composition simultaneously promotes the removal of the acid protecting group, so that a separate heat treatment or the like is required. It is preferable not only to improve efficiency and energy saving but also to maintain the stability of the photosensitive resin composition until it is cured.

The divalent linking group constituting L is not particularly specified, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent, or may have an atom of a type other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain. More preferably, a divalent aromatic hydrocarbon group, or a group relating to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group. A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferable. It is preferable that these groups do not have an oxygen atom.

The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The group (for example, an arylene alkyl group) relating to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and 7 to 18 carbon atoms. 10 is more preferable.

Specific examples of the linking group L include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain. , A linear or branched chain alkaneylene group, a cyclic alkaneylene group, an arylene group, or an arylene alkylene group is preferable.

The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The linear or branched chain alkylene group includes, for example, a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentandiyl group, a hexanediyl group, a heptandyl group, an octanediyl group, a nonandiyl group, a decandiyl group, an undecandyl group, and the like. Dodecandyl groups and the like can be mentioned.

The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Examples of the cyclic alkylene group include a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group and the like.

The group related to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms. Examples of the group related to the combination of the chain alkylene group and the cyclic alkylene group include a methylenecyclohexanediyl group, an ethylenecyclohexanediyl group, a propylenecyclohexanediyl group, a methylenecyclohexanediylmethylene group, an ethylenecyclohexanediylethylene group and the like.

The alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms. For example, a methyleneoxymethylene group, an ethyleneoxyethylene group, a propyleneoxypropylene group, a butyleneoxybutylene group and the like can be mentioned.

The linear or branched chain-like alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms. The linear or branched chain-like alkenylene group preferably has 1 to 10 C = C bonds, more preferably 1 to 6, and even more preferably 1 to 3. Examples of the linear or branched chain-like alkenylene group include a vinylene group, a propenylene group, a methylallylene group and the like.

The cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.

For the cyclic alkenylene group, the number of C = C bonds is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. Examples of the cyclic alkenylene group include a cyclopropenediyl group, a cyclobutendyl group, a cyclohexenediyl group and the like.

The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracene diyl group, a phenanthreneyl group and the like.

The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms. Examples of the arylene alkylene group include a phenylene methylene group, a phenylene ethylene group, a naphthylene methylene group, a naphthylene ethylene group, a xylene diyl group, an ethylene phenylene ethylene group and the like.

Among them, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propandiyl group (particularly 1, 3-Propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cisvinylene group), phenylene group (1,2-phenylene group), phenylene methylene group (especially 1,2-phenylene) Methylene group) and ethyleneoxyethylene group (particularly 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.

The specific thermal base generator represented by the above formula (N1) is decomposed by heating, and a compound represented by the following formula (N2) (hereinafter, this compound may be referred to as a "decomposition-generated base") is used. It is preferable to generate.

式（Ｎ２）中、Ｒ^N1およびＲ^N2はそれぞれ独立に１価の有機基を表す。Ｒ^N1およびＲ^N2の好ましい範囲は式（Ｎ１）で定義したものと同義であり、両者が連結して形成される環状構造の好ましいものも式（Ｎ１）で定義したものと同義である。

In formula ( ^N2 ), RN1 and ^RN2 each independently represent a monovalent organic group. The preferable range of RN1 and ^RN2 is synonymous with the one defined by the formula ( ^N1 ), and the preferable one of the annular structure formed by connecting the two is also the same as the one defined by the formula (N1).

The decomposition-generated base produced by the decomposition of a specific thermal base generator preferably has a boiling point (atmospheric pressure 101325 Pa) of 40 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 100 ° C. or higher. preferable. As an upper limit, it is practical that the temperature is 400 ° C. or lower. When the boiling point of the decomposition-generated base is equal to or higher than the above lower limit, scattering due to volatilization from the system is suppressed when used in the photosensitive resin composition, and the desired action of the decomposition-generated base (heterocyclic-containing polymer). (Catalytic action that promotes the cyclization of the precursor of the above) is more effectively exhibited, which is preferable.

From the viewpoint of realizing a moderately high boiling point range as described above, the total carbon number of ^RN1 and ^RN2 is preferably 2 or more, more preferably 3 or more, and 4 or more. Is even more preferable. It is practical that the upper limit is 24 or less. The preferable range of the number of carbon atoms based on the viewpoint of this action also applies to the formula (N1).

The specific thermobase generator is preferably contained in the photosensitive resin composition and used in combination with a precursor of a heterocyclic-containing polymer (further, it may be combined with a radically polymerizable compound and a photoradical polymerization initiator. More preferably), it is preferable that the polymer precursor is decomposed by heating to generate a base in the photosensitive resin composition to promote the cyclization reaction of the polymer precursor and effectively cure the resin composition. The decomposition temperature of the specific thermal base generator is not particularly limited, but is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 120 ° C. or higher, and 180 ° C. or higher. Is more preferable. As the upper limit, it is more preferably 450 ° C. or lower, more preferably 350 ° C. or lower, and further preferably 250 ° C. or lower. It is preferable to use a compound that decomposes at a lower temperature because the photosensitive resin composition can be cured with lower energy consumption when used in the photosensitive resin composition. On the other hand, when the decomposition temperature is set to the above lower limit or higher, it is preferable that the base is inadvertently generated and acts on when stored at room temperature, and the storage stability of the photosensitive resin composition is improved.

According to the specific thermobase generator according to the present invention, the photosensitivity is inhibited by reacting with a photoradical polymerization initiator or the like or a radically polymerizable compound which may be contained in the photosensitive resin composition. It is particularly preferable because the photosensitivity after curing can be effectively maintained and good exposure and development characteristics can be exhibited thereafter.

From the viewpoint of setting an effective decomposition temperature as described above and setting the boiling point of the decomposition-generated base in a suitable range, the specific thermobase generator preferably has a molecular weight of 100 or more, preferably 150. The above is more preferable, 200 or more is more preferable, and 250 or more is further preferable. It is practical that the upper limit is 1000 or less. In addition, this preferable range of the molecular weight also applies when the carboxyl group of a specific thermal base generator has a protecting group.

Examples of the thermobase generator represented by the formula (N1) include the following examples, but the present invention is not limited thereto.

The boiling point of the base (amine compound) generated from each of the above thermal base generators and the pKa of the conjugate acid are shown below.

Examples of the thermobase generator represented by the formula (N1) include the following examples, but the present invention is not limited thereto.

The thermal base generator represented by the above formula (N1) can be produced by a conventional method. In addition, commercially available reagents can be utilized.

The specific thermal base generator represented by the above formula (N1) preferably has a pKa of the conjugate acid of the generated base of 8 or more, more preferably 9 or more, and further preferably 10 or more. preferable. There is no particular upper limit, but it is practical that it is 14 or less. By setting the pKa of a specific thermal base generator in the above range, the generated base can efficiently proceed with the cyclization reaction of the polymer precursor, and the breaking elongation of the cured film can be increased at a low temperature. It is preferable in that it can be done. Here, pKa is a value specified by the following method.

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

The content of the specific thermal base generator is preferably 0.01 to 50% by mass with respect to the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.05% by mass or more, further preferably 0.1% by mass or more. The upper limit is more preferably 10% by mass or less, further preferably 5% by mass or less.

The content of the specific thermal base generator with respect to 100 parts by mass of the polymer precursor is preferably 0.015 parts by mass or more, more preferably 0.075 parts by mass or more, and 0.15 parts by mass or more. Is more preferable. As the upper limit, for example, it is preferably 15.0 parts by mass or less, more preferably 7.5 parts by mass or less, and further preferably 1.5 parts by mass or less.

By setting the content of the specific thermal base generator to the above lower limit value or more, it is preferable in that good storage stability can be ensured in the photosensitive resin composition and the mechanical properties of the cured film can be suitably realized.

By setting the value to the upper limit or less, it is preferable in that corrosion resistance of a metal (for example, copper used for wiring or the like) can be ensured.

As the specific thermobase generator, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.

The photosensitive resin composition of the present invention may or may not contain a thermal base generator other than the specific thermal base generator. When other thermobase generators are included, those described in WO2015 / 199219 and WO2015 / 199220 are exemplified, and the contents thereof are incorporated in the present specification. Further, in the present invention, it is possible to make the configuration substantially free of other thermobase generators other than the specific thermobase generator. The term "substantially free" means that the content of the specific thermal base generator contained in the photosensitive resin composition of the present invention is 5% by mass or less, preferably 3% by mass or less, and more preferably 1. It means that it is mass%.

Further, the photobase generator may or may not be contained together with the specific thermal base generator.

Photosensitive resin composition

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 precursor of a heterocyclic-containing polymer and the above-mentioned specific thermal base. Including with a generator. Further, the photosensitive resin composition of the present invention preferably contains a photoradical polymerization initiator and a radically polymerizable compound. Hereinafter, the components contained other than the specific thermal base generator will be described in detail.

<Polymer precursor>

As the precursor of the heterocyclic-containing polymer, at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor is exemplified, and a polyimide precursor is more 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価の連結基を表し、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 higher film strength can be obtained.

A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent linking 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 linking group, preferably 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 can be used. Preferably, an aromatic group having 6 to 20 carbon atoms is more preferable.

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. Examples of aromatic groups include:

In the formula, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be single-bonded or substituted with a fluorine atom, —O—, —C (= O) −, —S—, —S. (= O) _2- , -NHCO-, and preferably a group selected from a combination thereof, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O- , -C (= O)-, -S- and -SO _2-- , more preferably -CH _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 −.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-,1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; meta and paraphenylenediamine, diaminotoluene, 4,4'-and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-and 3,3'-diaminodiphenyl sulfone , 4,4'-and 3,3'-diaminodiphenylsulfide, 4,4'-and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-amino) Phenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxy) Phenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4'-diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) ) Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10- Bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) Nzen, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl- 4,4'-Diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] Hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether , 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl- 3,3'-Diaminodiphenylsulfone, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2- (3', 5'-diaminobenzoyloxy) ethyl methacrylate, 2,4- And 2,5-diaminocumen, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis ( 3-Aminopropyl) Tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5 -Diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) Decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2) -Aminophenoxy) Phenyl] Hexafluoropropane, 2,2-bis [4- (4-Aminophenoxy) -3,5-dimethylphenyl] Hexafluoropropane, 2,2-Bis [4- (4-Aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, parabis (4-amino-2-trifluoromethi) Ruphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'- Bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenyl sulfone, 2,2-bis [4- (4-amino-) 3-Trifluoromethylphenoxy) Phenyl] Hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoro) Included are at least one diamine selected from methyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotridin and 4,4'-diaminoquaterphenyl.

Further, the diamines (DA-1) to (DA-18) shown below are also preferable.

Further, a diamine having at least two or more alkylene glycol units in the main chain is also mentioned as a preferable example. A diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule is preferable, and a diamine containing no aromatic ring is more preferable. Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, and Jeffamine (registered trademark). ) EDR-148, Jeffamine® EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2) -Aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propane-2-amine, etc., but are limited to these. Not done.

Jeffamine® KH-511, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148, The structure of Jeffermin® EDR-176 is shown below.

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

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 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 is preferable. 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). Represents _2- , -NHCO-, and groups selected from these combinations. 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 independent 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. '-Bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like can be mentioned. 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 a group represented by the following formula (5) or formula (6) is more preferable.

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 acid 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 is synonymous with R ¹¹⁵ in equation (1).

Specific examples of the tetracarboxylic acid dianhydride 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'-diphenylsulfone tetracarboxylic 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'-benzophenonetetracarboxylic 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-diphenylhexafluoropropane-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-phenanthrentetracarboxylic 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.

Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also mentioned as preferable examples.

<<< R ¹¹³ and R ¹¹⁴ >>>

R ¹¹³ and R ¹¹⁴ in the formula (1) independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a radically polymerizable group, and it is more preferable that both of them contain a radically polymerizable group. Examples of the radically polymerizable group include a group capable of 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, and a methyl group is more preferable.

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 (as an alkylene group having 1 carbon atom). ~ 12 is preferable, 1 to 6 is more preferable, 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, 1 to 6 is more preferable, and 1 to 3 is particularly preferable). 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-butanediyl 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 a monovalent organic group of R ¹¹³ or R ¹¹⁴ . Examples include an alkyl group. 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 hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group.

As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent that improves the solubility of the 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 cyclic alkyl group of the monocycle 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.

Specific examples of the aromatic group include a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and azulene. Rings, heptalene rings, indacenes rings, perylene rings, pentacene rings, acenaphthene rings, phenanthrene rings, anthracene rings, naphthalene rings, chrysen rings, triphenylene rings, etc.) or substituted or unsubstituted aromatic heterocyclic groups (groups). The cyclic structure constituting the ring includes a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indridin ring, an indole ring, and a benzofuran ring. Benzofuran ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, aclysine ring, phenanthrene ring, thiantolen ring, chromene ring, xanthene. Ring, phenoxatiin ring, phenothiazine ring or phenazine ring).

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 a 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 the structural unit represented by the formula (1-A) or (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 their respective preferred ranges synonymous with the preferred ranges of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1). ..

The preferred range of R ¹¹² is synonymous with R ¹¹² in the 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, but may be two or more kinds. Further, it may contain a structural isomer of a structural unit represented by the formula (1). 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, 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the constituent units is the polyimide precursor represented by the formula (1). Is exemplified. As an upper limit, 100 mol% or less is practical.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. 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, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting 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 each 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). 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, and have the same meaning as R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferred 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 precursor preferably contains a diamine residue represented by the following formula (SL) as another type of structural unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.

Ｚは、ａ構造とｂ構造を有し、Ｒ^1sは水素原子または炭素数１～１０の炭化水素基（好ましくは炭素数１～６、より好ましくは炭素数１～３）であり、Ｒ^2sは炭素数１～１０の炭化水素基（好ましくは炭素数１～６、より好ましくは炭素数１～３）であり、Ｒ^3s、Ｒ^4s、Ｒ^5s、Ｒ^6sのうち少なくとも１つは芳香族基（好ましくは炭素数６～２２、より好ましくは炭素数６～１８、特に好ましくは炭素数６～１０）で、残りは水素原子または炭素数１～３０（好ましくは炭素数１～１８、より好ましくは炭素数１～１２、特に好ましくは炭素数１～６）の有機基で、それぞれ同一でも異なっていてもよい。ａ構造およびｂ構造の重合は、ブロック重合でもランダム重合でもよい。Ｚ部分において、好ましくは、ａ構造は５～９５モル％、ｂ構造は９５～５モル％であり、ａ＋ｂは１００モル％である。

Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R ^2s . Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of R ^3s , R ^4s , R ^5s , and R ^6s is aromatic. It is a group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and the rest is a hydrogen atom or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms). It is preferably an organic group having 1 to 12 carbon atoms, particularly preferably 1 to 6) carbon atoms, and may be the same or different from each other. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z portion, the a structure is preferably 5 to 95 mol%, the b structure is 95 to 5 mol%, and a + b is 100 mol%.

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. The molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be lowered, and the effect of suppressing warpage and the effect of improving solubility can be achieved at the same time.

When the precursor contains a diamine residue represented by the formula (SL) as another type of building block, further removal of the acid dianhydride group from the tetracarboxylic acid dianhydride in terms of improving alkali solubility. It is preferable to include a tetracarboxylic acid residue remaining later as a constituent unit. Examples of such tetracarboxylic acid residues include the example of R ¹¹⁵ in the formula (1).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. 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, further preferably 95% 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 kind of polymer precursor, or may contain two or more kinds of polymer precursors. When two or more kinds are contained, it is preferable that the total amount is within the above range.

The photosensitive resin composition of the present invention may contain other components in addition to the above. Specific examples thereof include a photopolymerization initiator, a photocuring accelerator, a thermal radical polymerization initiator, and a thermal acid generator.

<Photopolymerization initiator>

The photopolymerization initiator that can be used as the photosensitive agent is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization 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 active agent that causes some action with a photoexcited sensitizer and generates an active radical.

The photoradical polymerization 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).

As the photoradical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azido compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description in paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication WO2015 / 199219 can be referred to, and the contents thereof are incorporated in the present specification.

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

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.

As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, the compound described in JP-A-2009-191179, in which the maximum absorption wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.

Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

市販品ではＩＲＧＡＣＵＲＥ ＯＸＥ ０１、ＩＲＧＡＣＵＲＥ ＯＸＥ ０２、ＩＲＧＡＣＵＲＥ ＯＸＥ ０３、ＩＲＧＡＣＵＲＥ ＯＸＥ ０４（以上、ＢＡＳＦ社製）、アデカオプトマーＮ－１９１９（ＡＤＥＫＡ社製、特開２０１２－１４０５２号公報に記載の光ラジカル重合開始剤２）も好適に用いられる。また、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカアークルズＮＣＩ－８３１およびアデカアークルズＮＣＩ－９３０（ＡＤＥＫＡ社製）も用いることができる。また、ＤＦＩ－０９１（ダイトーケミックス株式会社製）を用いることができる。

さらに、また、フッ素原子を有するオキシム化合物を用いることも可能である。そのようなオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載されている化合物、特表２０１４－５００８５２号公報の段落０３４５に記載されている化合物２４、３６～４０、特開２０１３－１６４４７１号公報の段落０１０１に記載されている化合物（Ｃ－３）などが挙げられる。

最も好ましいオキシム化合物としては、特開２００７－２６９７７９号公報に示される特定置換基を有するオキシム化合物や、特開２００９－１９１０６１号公報に示されるチオアリール基を有するオキシム化合物などが挙げられる。

The photoradical polymerization initiator is more preferably an oxime compound. By using the oxime compound, it becomes possible to improve the exposure latitude more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, and the compound described in JP-A-2006-342166 can be used.

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzooxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxy. Iminopentan-3-one, 2-acetoxyimimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. In the photosensitive resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. The oxime-based photopolymerization initiator has 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 (above, manufactured by BASF), and ADEKA PTOMER N-1919 (manufactured by ADEKA, JP-A-2012-14052). The initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), ADEKA Arklus NCI-831 and ADEKA Arklus NCI-930 (manufactured by ADEKA) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.

Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include the compounds described in JP-A-2010-262028, the compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.

The most preferable oxime compound includes an oxime compound having a specific substituent shown in JP-A-2007-269779, an oxime compound having a thioaryl group shown in JP-A-2009-191061, and the like.

式（Ｉ）中、Ｒ^I00は、炭素数１～２０のアルキル基、１個以上の酸素原子によって中断された炭素数２～２０のアルキル基、炭素数１～１２のアルコキシル基、フェニル基、炭素数１～２０のアルキル基、炭素数１～１２のアルコキシル基、ハロゲン原子、シクロペンチル基、シクロヘキシル基、炭素数２～１２のアルケニル基、１個以上の酸素原子によって中断された炭素数２～１８のアルキル基および炭素数１～４のアルキル基の少なくとも１つで置換されたフェニル基、またはビフェニルであり、Ｒ^I01は、式（ＩＩ）で表される基であるか、Ｒ^I00と同じ基であり、Ｒ^I02～Ｒ^I04は各々独立に炭素数１～１２のアルキル、炭素数１～１２のアルコキシまたはハロゲンである。

式中、Ｒ^I05～Ｒ^I07は、上記式（Ｉ）のＲ^I02～Ｒ^I04と同じである。

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator includes a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, and a triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxadiazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.

Further preferable photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds. At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, a metallocene compound or an oxime compound is further preferable, and an oxime compound is further preferable. Is even more preferable.

The photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). -Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanol-1, alkylanthraquinone, etc. It is also possible to use quinones fused to the aromatic ring of the above, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. Further, a compound represented by the following formula (I) can also be used.

In formula (I), ^RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxyl group having 1 to 12 carbon atoms, a phenyl group, and the like. An alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms. It is a phenyl group or biphenyl substituted with at least one of 18 alkyl groups and an alkyl group having 1 to 4 carbon atoms, and ^RI01 is a group represented by the formula (II) or the same as ^RI00 . The groups, R ^I02 to R ^{I 04} , are each independently an alkyl having 1 to 12 carbon atoms and an alkoxy or halogen having 1 to 12 carbon atoms.

In the formula, R ^I05 to R I ⁰⁷ are the same as R I ⁰² to R I ⁰⁴ in the above formula (I).

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

When the photopolymerization 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 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. 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 thereof is preferably in the above range.

<Thermal polymerization initiator>

A thermal polymerization initiator may be used as the photosensitive agent, and in particular, a thermal radical polymerization initiator may be used. The thermal radical 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 radical 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 higher heat resistance can be achieved.

Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-6554.

When the thermal radical 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. %, More preferably 5 to 15% by mass. Only one type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal radical polymerization initiators are contained, the total thereof is preferably in the above range.

<Polymerizable compound>

<< Radical Polymerizable Compound >>

The photosensitive resin composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, a radically polymerizable compound can be used. The radically polymerizable compound is a compound having a radically polymerizable group. Examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group and a (meth) acryloyl group. The radically polymerizable group is preferably a (meth) acryloyl group.

The number of radically polymerizable groups contained in the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups and preferably three or more radically polymerizable groups. More preferred. 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 radically polymerizable compound is preferably 2000 or less, more preferably 1500 or less, still more preferably 900 or less. The lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.

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

Specific examples of the radically polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and preferred examples thereof. Esters of unsaturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyhydric amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polymorphic acid. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a polyelectron substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and a halogen group. Substitution reaction products of unsaturated carboxylic acid esters or amides having a desorbing substituent such as or tosyloxy group with monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which the above-mentioned unsaturated carboxylic acid is replaced with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.

Further, as the radically polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropanetri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Application Laid-Open No. 51-37193. Urethane (meth) acrylates such as those described in JP-A-48-64183, JP-A-49-43191, and JP-B-52-30490, polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.

Further, as preferred radically polymerizable compounds other than the above, those described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like have a fluorene ring and have an ethylenically unsaturated bond. It is also possible to use a compound having two or more groups having the above, or a cardo resin.

Further, as other examples, the specific unsaturated compound described in Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1-4039, Japanese Patent Publication No. 1-4536, and Japanese Patent Application Laid-Open No. 2-25493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-22048 can also be used. Furthermore, the journal of the Japan Adhesive Association vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication WO2015 / 199219 can also be preferably used, and the contents thereof are described in the present specification. Will be incorporated into.

Further, the compound described in JP-A No. 10-62986 together with specific examples as the formulas (1) and (2) after addition of ethylene oxide or propylene oxide to the polyfunctional alcohol is also (meth) acrylated. It can be used as a radically polymerizable compound.

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

Examples of the radically polymerizable compound include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku). A-TMMT Co., Ltd .: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) Acrylate (KAYARAD DPHA as a commercial product; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups via ethylene glycol residues or propylene glycol residues. Bonded structures are preferred. These oligomer types can also be used.

Commercially available products of the radically 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. , 231, 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, 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 ( Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.

Examples of the radically polymerizable compound include urethane acrylates as described in JP-A-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. , Urethane compounds having an ethylene oxide-based skeleton described in JP-A-58-49860, JP-B-56--17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, as the radically polymerizable compound, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. It can also be used.

The radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxyl group or a phosphoric acid group. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid is obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A radically polymerizable compound having a group is more preferable. Particularly preferably, in a radically polymerizable compound in which a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipenta. It is a compound that is erythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The acid value of the radically polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radically polymerizable compound is within the above range, it is excellent in manufacturing and handling, and further excellent in developability. Moreover, the polymerizability is good.

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

<< Polymerizable compounds other than the radically polymerizable compounds mentioned above >>

The photosensitive resin composition of the present invention may further contain a polymerizable compound other than the radically polymerizable compound described above. Examples of the polymerizable compound other than the above-mentioned radically polymerizable compound include a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.

<<< Compound with hydroxymethyl group, alkoxymethyl group or acyloxymethyl group >>>

As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferable.

（式中、ｔは、１～２０の整数を示し、Ｒ¹⁰⁴は炭素数１～２００のｔ価の有機基を示し、Ｒ¹⁰⁵は、－ＯＲ¹⁰⁶または、－ＯＣＯ－Ｒ¹⁰⁷で示される基を示し、Ｒ¹⁰⁶は、水素原子または炭素数１～１０の有機基を示し、Ｒ¹⁰⁷は、炭素数１～１０の有機基を示す。）

(In the formula, t represents an integer of 1 to 20, R ¹⁰⁴ represents an organic group having a t-valence of 1 to 200 carbon atoms, and R ¹⁰⁵ is a group represented by -OR ¹⁰⁶ or -OCO-R ¹⁰⁷ . , R ¹⁰⁶ indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ¹⁰⁷ indicates an organic group having 1 to 10 carbon atoms.)

（式中、Ｒ⁴⁰⁴は炭素数１～２００の２価の有機基を示し、Ｒ⁴⁰⁵は、－ＯＲ⁴⁰⁶または、－ＯＣＯ－Ｒ⁴⁰⁷で示される基を示し、Ｒ⁴⁰⁶は、水素原子または炭素数１～１０の有機基を示し、Ｒ⁴⁰⁷は、炭素数１～１０の有機基を示す。）

(In the formula, R ⁴⁰⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , and R ⁴⁰⁶ is a hydrogen atom or carbon. An organic group having a number of 1 to 10 is indicated, and R ⁴⁰⁷ indicates an organic group having 1 to 10 carbon atoms.)

（式中ｕは３～８の整数を示し、Ｒ⁵⁰⁴は炭素数１～２００のｕ価の有機基を示し、Ｒ⁵⁰⁵は、－ＯＲ⁵⁰⁶または、－ＯＣＯ－Ｒ⁵⁰⁷で示される基を示し、Ｒ⁵⁰⁶は、水素原子または炭素数１～１０の有機基を示し、Ｒ⁵⁰⁷は、炭素数１～１０の有機基を示す。）

(U in the formula indicates an integer of 3 to 8, R ⁵⁰⁴ indicates an organic group having a u-valence of 1 to 200 carbon atoms, and R ⁵⁰⁵ indicates a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ . , R ⁵⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁵⁰⁷ indicates an organic group having 1 to 10 carbon atoms.)

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMEEP (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML. -PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKARAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-buthylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diastoxymethyl-p-cresol, etc. Be done.

Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, and the like. HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Material Industry Co., Ltd.), NIKALAC MX-280, Examples thereof include NIKALAC MX-270 and NIKALAC MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).

<<< Epoxy compound (compound having an epoxy group) >>>

The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low temperature curing and warpage of the composition.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and warpage can be suppressed. The polyethylene oxide group means that the number of constituent units of ethylene oxide is 2 or more, and the number of constituent units is preferably 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidi). Examples include, but are not limited to, epoxy group-containing silicones such as loxypropyl) siloxane. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trademark, manufactured by Dainippon Ink and Chemicals Co., Ltd.), Rica Resin (registered trademark) ) BEO-60E (trade name, Shin Nihon Rika Co., Ltd.), EP-4003S, EP-4000S (trade name, manufactured by ADEKA) and the like. Among these, an epoxy resin containing a polyethylene oxide group is preferable because it suppresses warpage and is excellent in heat resistance. For example, Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain a polyethylene oxide group.

<<< Oxetane compound (compound having an oxetanyl group) >>>

Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and the like. Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like. As a specific example, the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or individually. Two or more kinds may be mixed.

<<< Benzoxazine compound (compound having a benzoxazolyl group) >>>

Since the benzoxazine compound is a cross-linking reaction derived from the ring-opening addition reaction, degassing does not occur at the time of curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.

Preferred examples of the benzoxazine compound include B-a type benzoxazine, Bm type benzoxazine (hereinafter, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, and phenol novolac type dihydrobenzo. Examples include oxazine compounds. These may be used alone or in combination of two or more.

When the polymerizable compound is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

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 within 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-Alkyloxypropionate 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-alkyloxypropionate 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-methylpropionate, etc. Methyl acid 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 thereof include propyl acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate 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 properties of the coated surface.

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 solvent content 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 preferably 10 to 70% by mass, and even 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 has a heterocyclic ring (pyrrole 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, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and sulfanyl 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 captures anions such as halogen ions.

Examples of other migration inhibitors include the rust preventive agent described in paragraph 0094 of JP2013-15701, the compound described in paragraphs 0073 to 0076 of JP2009-283711, and JP-A-2011-59656. The compound described in paragraph 0052, the compound described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compound described in paragraph 0166 of International Publication WO2015 / 199219, and the like 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. It is more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.

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

本発明の感光性樹脂組成物が重合禁止剤を有する場合、重合禁止剤の含有量は、本発明の感光性樹脂組成物の全固形分に対して、０．０１～５質量％であることが好ましく、０．０２～３質量％であることがより好ましく、０．０５～２．５質量％であることがさらに好ましい。

重合禁止剤は１種のみでもよいし、２種以上であってもよい。重合禁止剤が２種以上の場合は、その合計が上記範囲であることが好ましい。

<Polymerization inhibitor>

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

Examples of the polymerization inhibitor include hydroquinone, p-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.

In addition, the following compounds can be used (Me is a methyl group).

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 compound described in paragraph 0167 of International Publication WO2015 / 199219, the compound described in paragraphs 0062 to 0073 of JP-A-2014-191002, and paragraph 0063-of International Publication WO2011 / 080992A1. The compound described in 0071, the compound described in paragraphs 0060 to 0061 of JP-A-2014-191252, the compound described in paragraphs 0045-0052 of JP-A-2014-41264, paragraph 0055 of International Publication WO2014 / 097594. The described compounds are mentioned. Further, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. 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 adhesiveness improving agent, 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.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0 with respect to 100 parts by mass of the polymer precursor. It is in the range of .5 to 5 parts 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, it is preferable that the total is in the above range.

<Other additives>

The photosensitive resin composition of the present invention contains various additives such as a thermoacid generator, 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, an inorganic particle, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an antiaggregating agent 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.

<< Thermal acid generator >>

The photosensitive resin composition of the present invention may contain a thermal acid generator. The thermoacid generator is used to remove the protecting group when the specific thermobase generating agent has a protecting group.

The content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the polymer precursor. By containing 0.01 part by mass or more of the thermal acid generator, the crosslinking reaction and the cyclization of the polymer precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. The content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, from the viewpoint of electrical insulation of the cured film.

The thermal acid generator may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total amount is within the above range.

<< 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 electronically excited state. The sensitizing dye in the electron-excited state comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid, or a base. For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027355 can be referred to, and the content thereof 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 can be preferably used.

Further, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication WO2015 / 199219 can also be 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 kind 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.

Further, as the surfactant, the compound described in paragraphs 0159 to 0165 of International Publication WO2015 / 199219 can also be used.

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 derivative >>

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

Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication WO2015 / 199219 can also be used.

When the photosensitive resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is 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, still 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, still 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, it is preferable that the total of these metals is 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 the 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 are 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 by mass, 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 amount 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 a storage container, a multi-layer bottle composed of 6 types and 6 layers of resin and a 7-layer structure of 6 types of resin are used for the inner wall of the container for the purpose of suppressing impurities from being mixed into raw materials and compositions. 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 hole diameter is preferably 1 μm or less, more preferably 0.5 μm or less, still 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. In addition, various materials may be filtered a plurality of times. When filtering multiple 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 manufacturing method thereof>

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, and can be 1 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.

Two or more layers of the cured film of the present invention may be laminated, and further, 3 to 7 layers may be laminated to form a 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 the applicable field 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 a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, and manufacturing a protective lacquer and a dielectric layer in electronics, particularly microelectronics.

The method for producing a cured film of the present invention includes using the photosensitive resin composition of the present invention. Specifically, it is preferable to include the following steps (a) to (d).

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

(B) An exposure step of exposing the film after the film forming step.

(C) A developing step of performing a developing process on the 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 thermal base 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. In the method for producing the laminated body of the present embodiment, after forming the cured film according to the above-mentioned method for producing the cured film, the steps (a), the steps (a) to (c), or (a) are further performed. )-(D). In particular, it is preferable to perform 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 laminated body, 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.

<< 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, silicon 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.

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. Further, the coating method can be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method, a spray coating method, an inkjet method, 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, 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. The exposure amount is not particularly determined as long as the photosensitive resin composition can be cured, but for example, it is preferable to irradiate 100 to 10000 mJ / cm ² in terms of exposure energy at a wavelength of 365 nm, and to irradiate 200 to 8000 mJ / cm ² . 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 (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam and the like. For 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 performing the development, 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 developer. 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.

Examples of the organic solvent include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., as well as As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene. Etc., Dimethyl sulfoxide is preferably mentioned as the sulfoxides.

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

The developer preferably has 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 developer may be 100% by mass of an organic solvent.

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

After the treatment with the developer, 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. Further, the composition of the present invention may contain a radically polymerizable compound other than the polymer precursor, but the curing of the radically polymerizable compound other than the unreacted polymer precursor can also proceed in this step. 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. Even more preferable.

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, still 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 amine while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, the cured membrane can be prevented from excessive volatilization. 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 the 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 crosslinking 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 the temperature is kept at 200 ° C. for 120 minutes. , Such as a pretreatment step 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 may be 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, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

The heating step is preferably performed in an 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 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 electrolytic plating 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 a cured film (resin layer) or a metal layer. Is a series of steps including performing in this order. However, it may be an embodiment in which only the film forming step (a) is repeated. Further, (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 include (e) a 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, the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. Plasma treatment is exemplified as the surface activation 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.

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 the metal layer is provided. Specifically, an embodiment 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 alternately laminated.

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 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>

[Polyimide precursor A-1: Synthesis of polyimide precursor having no radically polymerizable group]

Polyimide precursor A-1 was synthesized using pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and benzyl alcohol.

14.06 g (64.5 mmol) of pyromellitic 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. , Dryed in a molecular sieve. The suspension was heated at 100 ° C. for 3 hours. 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 SOCL ₂ was added. 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 overnight at room temperature. 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 precipitated polyimide precursor was filtered, then stirred again in 4 liters of water for 30 minutes and filtered again. The obtained filtrate was dried under reduced pressure at 45 ° C. for 3 days to obtain a polyimide precursor A-1. The weight average molecular weight of this polyimide precursor was 18,000.

A-1

<Synthesis example 2>

[Polyimide precursor A-2: Synthesis of a polyimide precursor having a radically polymerizable group]

Polyimide precursor A-2 was synthesized using pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate.

14.06 g (64.5 mmol) of pyromellitic 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 pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester is chlorinated with SOCL ₂ , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and the polyimide precursor A is converted by the same method as in Synthesis Example 1. I got -2. The weight average molecular weight of this polyimide precursor was 19,000.

A-2

<Synthesis example 3>

[Polyimide precursor A-3: Synthesis of a polyimide precursor having a radically polymerizable group]

Polyimide precursor A-3 was synthesized using 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) and 100 g of diglyme 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 is chlorinated with SOCL ₂ , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and the polyimide precursor A is converted by the same method as in Synthesis Example 1. I got -3. The weight average molecular weight of this polyimide precursor was 18,000.

A-3

<Synthesis example 4>

[Polyimide precursor A-4: Synthesis of a polyimide precursor having a radically polymerizable group]

Polyimide precursor A-4 was synthesized using 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotridin) 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) and 100 g of diglyme 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 by the same method as in Synthesis Example 1, and the same as in Synthesis Example 1. A polyimide precursor A-4 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]

Polybenzoxazole precursor A-5 was synthesized using 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 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 precipitated polybenzoxazole precursor was filtered, then stirred again in 6 liters of water for 30 minutes and filtered again. The obtained filtrate was dried under reduced pressure at 45 ° C. for 3 days to obtain a polybenzoxazole precursor A-5. The weight average molecular weight of this polybenzoxazole precursor was 15,000.

A-5

<Examples and comparative examples>

The components listed in the table 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.

＜感光性樹脂組成物の組成＞

（Ａ）複素環含有ポリマーの前駆体 ：上記で合成したＡ－１～Ａ－５

（Ｂ）特定の熱塩基発生剤：先に記載の例示化合物Ｂ－１～Ｂ－１９

比較例のための熱塩基発生剤：下記の化合物

<Composition of photosensitive resin composition>

(A) Heterocycle-containing polymer precursor: A-1 to A-5 synthesized above

(B) Specific thermal base generator: Exemplified compounds B-1 to B-19 described above.

Thermal base generators for comparative examples: the following compounds

The boiling point of the base (amine compound) generated from the thermal base generator of the above comparative example and the pKa of the conjugate acid are shown below.

(C) Photoradical polymerization 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) Radical polymerizable compound

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

D-2: SR-209 (manufactured by Sartmer, the following compound)

D-3: A-TMMT (Pentaerythritol tetraacrylate 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: p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)

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

(F) Migration inhibitor

F-1: The following compounds

F-2: The following compounds

F-3: The following compounds

F-4: The following compounds

(G) Metal adhesion improver

G-1: The following compounds

G-2: The following compounds

G-3: The following compounds

(H) Solvent

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

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

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

<Storage stability>

The viscosity (0 days) of the photosensitive resin composition after 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 is 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 to which the obtained photosensitive resin composition layer was applied 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.

Using a tensile tester (Tencilon), the breaking elongation of the resin film 1 was set to a crosshead speed of 300 mm / min, a width of 10 mm, and a sample length of 50 mm. The elongation at break was measured in accordance with JIS-K6251: 2017 under the environment. The breaking elongation is Eb = (L _b −L ₀ ) / L ₀ (E _b : elongation at cutting, L ₀ : length of the test piece before the test, L _b : length of the test piece when the test piece is cut. It was calculated by. For the evaluation, the breaking elongation 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 60%

B: Break elongation exceeds 55% and 60% or less

C: Break elongation exceeds 50% and 55% or less

D: Break elongation exceeds 40% and 50% or less

E: Break elongation is 40% or less

<Evaluation of resolution of minimum line width pattern>

Each of the photosensitive resin compositions after filtration was spin-coated on a silicon wafer. The silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a film thickness of 20 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). Exposure was performed at a wavelength of 365 nm with exposure energies of 200, 300, 400, 500, 600, 700, 800 mJ / cm ² using a line-and-space photomask from 5 μm to 25 μm in 1 μm increments. To obtain a resin layer.

The resin layer was developed with cyclopentanone for 60 seconds. The smaller the line width of the obtained resin layer (line pattern), the finer the pattern can be formed, which is a preferable result. Further, the more the minimum line width that can be formed is less likely to change with respect to the fluctuation of the exposure amount, the more the arbitraryness of the exposure amount in forming the fine pattern increases, and the preferable result is obtained. The measurement limit is 5 μm.

A: It was 5 μm or more and 8 μm or less.

B: It was more than 8 μm and less than 10 μm.

C: It was more than 10 μm and less than 15 μm.

D: It was more than 15 μm and less than 20 μm.

E: Exceeded 20 μm

F: A pattern having a line width with sharp edges could not be obtained.

<Evaluation conditions for copper adhesion>

Each of the photosensitive resin compositions after filtration was applied in layers on a copper substrate by a spin coating method to form a photosensitive resin composition layer. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 20 μm on the silicon wafer. The photosensitive resin composition layer on a silicon wafer is exposed with a stepper (Nikon NSR 2005 i9C) at an exposure energy of 500 mJ / cm ² using a 100 μm square photomask, followed by cyclopentanone for 60 seconds. Development was performed to obtain a 100 μm square resin layer. Further, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 250 ° C., this temperature was maintained for 3 hours to obtain a resin film 2.

Shear force was measured on a 100 μm square resin film 2 on a copper substrate in an environment of 25 ° C. and 65% relative humidity (RH) using a bond tester (CondorSigma, manufactured by XYZTEC). The larger the shearing force, the greater the adhesion force, which is a preferable result.

A: Shear force exceeds 40 gf

B: Shear force exceeds 35 gf and 40 gf or less

C: Shear force exceeds 30 gf and 35 gf or less

D: Shear force exceeds 25 gf and is 30 gf or less

E: Shear force is 25 gf or less

「最小線幅パターンの解像性評価」の数値は露光エネルギーであり単位はｍＪ／ｃｍ²のである。各露光エネルギーにおけるパターンの解像性の評価結果を示している。

The numerical value of "evaluation of resolution of the minimum line width pattern" is the exposure energy, and the unit is mJ / cm ² . The evaluation result of the resolvability of the pattern at each exposure energy is shown.

From the above results, it was found that the photosensitive resin composition containing the specific thermal base generator according to the present invention and the precursor of the heterocyclic-containing polymer is excellent in storage stability. Further, if required, a photosensitive resin can be obtained by using ^RN1 and RN2 of the formula ( ^N1 ) as an alkyl group having a relatively large number of carbon atoms (particularly an alkyl group having a cyclic structure) for a specific thermal base generator. It was found that the cured film of the composition can be excellent in elongation at break. Further, if necessary, by combining with a polymer precursor having a radically polymerizable group, the obtained photosensitive cured film has excellent pattern resolution and good adhesion to copper. It turns out that it can be a radical.

<Example 100>

The photosensitive resin composition of Example 1 is 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 is formed. did. The photosensitive resin composition applied to the resin substrate was dried at 100 ° C. for 2 minutes and then exposed using a stepper (NSR1505 i6, 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 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 property.

Claims (19)

Thermal base generator represented by the following formula (N1);

In formula ( ^N1 ), RN1 and ^RN2 each independently represent a monovalent organic group, ^RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

The thermal base generator according to claim 1, wherein L in the formula (N1) is a divalent organic group having a chain length of 1 to 5.

The thermobase generator according to claim 1 or 2, wherein RN1 and ^RN2 in the formula ( ^N1 ) are independently hydrocarbon groups.

The thermobase generator according to any one of claims 1 to 3, wherein RN1 and ^RN2 in the formula ( ^N1 ) are independently aliphatic hydrocarbon groups.

L in the formula (N1) is a 1,2-ethylene group, a 1,3-propanediyl group, a 1,2-cyclohexanediyl group, a cisvinylene group, a 1,2-phenylene group, and a 1,2-phenylene methylene group. , Or the thermal base generator according to any one of claims 1 to 4, which is a 1,2-ethyleneoxy-1,2-ethylene group.

The thermobase generator according to any one of claims 1 to 5, wherein ^RC1 in the formula (N1) is a hydrogen atom.

The compound generated by the decomposition of the thermal base generator represented by the formula (N1) is the compound represented by the following formula (N2), and the boiling point of the compound represented by the formula (N2) is 50 ° C. or higher. The thermobase generator according to any one of claims 1 to 6;

In formula ( ^N2 ), RN1 and ^RN2 each independently represent a monovalent organic group.

A photosensitive resin composition comprising the thermal base generator according to any one of claims 1 to 7 and a precursor of a heterocyclic-containing polymer.

The photosensitive resin composition according to claim 8, further comprising a photoradical polymerization initiator and a radically polymerizable compound.

The photosensitive resin composition according to any one of claims 8 or 9, wherein the precursor of the heterocyclic-containing polymer contains a polyimide precursor or a polybenzoxazole precursor.

The photosensitive resin composition according to any one of claims 8 to 10, wherein the precursor of the heterocyclic-containing polymer contains a polyimide precursor.

The photosensitive resin composition according to any one of claims 8 to 10, wherein the precursor of the heterocyclic-containing polymer 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 linking 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 12, 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 8 to 13, 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 8 to 14.

A laminated body having two or more cured films according to claim 15, 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 8 to 14 to a substrate to form a film.

The method for producing a cured film according to claim 17, which comprises a step of heating the film at 50 to 450 ° C.

A semiconductor device having the cured film according to claim 15 or the laminate according to claim 16.