TWI819043B - Photosensitive resin composition, cured film, laminated body, cured film manufacturing method, semiconductor element and thermal alkali generator - Google Patents

Abstract

The present invention provides a photosensitive resin composition excellent in curability and storage stability. Furthermore, a cured film, a laminated body, a cured film manufacturing method and a semiconductor element using the above-mentioned photosensitive resin composition are provided. The photosensitive resin composition contains a thermal base generator represented by formula (N1), and at least one precursor compound among a polyimide precursor and a polybenzoconazole precursor. ^{In the} formula ⁽ N1 ⁾ , A hydrocarbon group with 2 to 6 atoms in the chain.

Description

Photosensitive resin composition, cured film, laminated body, cured film manufacturing method, semiconductor element and thermal alkali generator

唑前驅物中的至少一種的感光性樹脂組成物、硬化膜、積層體、硬化膜的製造方法及半導體元件。又，本發明關於一種熱鹼產生劑。 The invention relates to a product containing a polyimide precursor and a polybenzo

A photosensitive resin composition, a cured film, a laminated body, a method for producing a cured film, and a semiconductor element containing at least one kind of azole precursor. Furthermore, the present invention relates to a thermal base generator.

唑樹脂等環化並硬化之樹脂的耐熱性及絕緣性優異，因此適用於各種用途。該用途並無特別限定，但若以實際安裝用半導體元件為例，則可舉出作為絕緣膜或密封材料的素材或保護膜的利用。(參考非專利文獻1及2等)。又，亦用作可撓性基板的基膜或蓋層等。 Polyimide resin, polybenzo

Cyclized and hardened resins such as azole resin have excellent heat resistance and insulation properties and are therefore suitable for various applications. The use is not particularly limited, but if a semiconductor element for actual mounting is taken as an example, the use as a material of an insulating film or a sealing material or a protective film can be cited. (Refer to Non-Patent Documents 1 and 2, etc.). In addition, it is also used as a base film or cover layer for flexible substrates.

唑前驅物的狀態溶解於溶劑中之方法。藉此，能夠實現優異的操作性，且在製造如上述那樣的各產品時能夠以各種形態塗佈於基板等並加工。然後，加熱並使聚合物前驅物環化，從而能夠形成已硬化之產品。除了聚醯亞胺樹脂等所具有之高性能以外，從此類製造上的適應性優異之觀點考慮，越來越期待其在產業上的應用發展。 Such polyimide resins generally have low solubility in solvents. Therefore, polymer precursors before cyclization reaction are often used, specifically, polyimide precursors or polybenzoyl

The azole precursor is dissolved in a solvent. Thereby, excellent workability can be achieved, and when manufacturing each product as mentioned above, it can be applied to a board|substrate etc. in various forms, and can be processed. The polymer precursor is then heated and cyclized to form a hardened product. In addition to the high performance of polyimide resins and the like, from the viewpoint of their excellent adaptability in manufacturing, their industrial application development is increasingly expected.

Conventionally, there is a technique using a base generator that generates a base by irradiation or heating of electromagnetic waves when cyclizing the polymer precursor as described above. For example, Patent Document 1 describes a technology that utilizes an ionic thermal base generator to perform cyclization of a polymer precursor as described above.

On the other hand, Patent Document 2 describes the use of a base generator having a urea bond as a polymerization initiator for polymerizing an epoxy group-containing compound.

[Prior technical literature]

[Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2013-139566

[Patent Document 2] Japanese Patent Application Publication No. 2013-068681

[Non-patent literature]

[Non-patent document 1] Science & technology Co., Ltd. "High-functionalization and application technology of polyimide" April 2008

[Non-patent document 2] Masaaki Kakimoto/Supervisor, CMC Technical Library "Basics and Development of Polyimide Materials" published in November 2011

The ionic thermal base generator described in Patent Document 1 has a problem that its reactivity is usually relatively high and the storage stability of the photosensitive resin composition is low. In addition, the ionic base generator is easily activated at normal semiconductor processing temperatures (for example, lower than 120° C.) in the previous process. As a result, there is also a problem that after the polymer precursor is cyclized, the generation efficiency of the base decreases during the process, and the polymer precursor cannot be sufficiently hardened.

The present invention was completed in view of the above-mentioned problems, and an object thereof is to provide a photosensitive resin composition excellent in curability and storage stability.

Moreover, an object of this invention is to provide the cured film and the laminated body formed using the said photosensitive resin composition. Furthermore, an object of the present invention is to provide a method for manufacturing a cured film using the above-mentioned photosensitive resin composition. Furthermore, an object of this invention is to provide the semiconductor element containing the said cured film or the said laminated body.

The above problems are solved by using a base generator having a specific structure. Specifically, the above problem is solved by the following method <1>, preferably <2> to <23>.

唑前驅物中的至少一種前驅物化合物；

式(N1)中，X^N表示羥基、羧基及磺酸基中的任一種，Z^N表示氧原子或硫原子，R^N1及R^N2分別獨立地表示氫原子或碳數1~20的烴基， L^N係從相鄰氮原子連結至X^N為止的3價烴基，且表示構成連結鏈之原子數為2~6之烴基，兩末端的*分別獨立表示氫原子或1價有機基團。 <1> A photosensitive resin composition including: a thermal base generator represented by the following formula (N1), a polyimide precursor and polybenzo

at least one precursor compound of an azole precursor;

^In the ^formula (N1 ^{) ,} L ^N is a 3 ^- valent hydrocarbon group connected from adjacent nitrogen atoms to

<2> The photosensitive resin composition according to <1>, wherein in the formula (N1), at least part of the connecting chain in L ^N is an aryl group.

式(N2)中，X^N1及X^N2分別獨立地表示羥基、羧基及磺酸基中的任一種，Z^N1表示氧原子或硫原子，R^N3及R^N4分別獨立地表示氫原子或碳數1~20的烴基，L^N1及L^N2分別獨立地表示碳數1~20的烴基，n1表示0或1，n2表示0~10的整數，n1及n2之和為1以上，n3表示1以上的整數， n1=1時，L^N1係從相鄰氮原子連結至X^N1為止的2價烴基，且為構成連結鏈之原子數為2~6的烴基，n2

1時，L^N2係從相鄰氮原子連結至X^N2為止的1+n2價烴基，且為構成連結鏈之原子數為2~6的烴基。 <3> The photosensitive resin composition according to <1>, wherein the thermal base generator is a compound represented by formula (N2);

In the formula ( ^{N2 ) ,} X ^{N1 and} A hydrocarbon group of 1 to 20, L ^N1 and L ^N2 each independently represent a hydrocarbon group with a carbon number of 1 to 20, n1 represents 0 or 1, n2 represents an integer of 0 to 10, the sum of n1 and n2 is more than 1, n3 represents more than 1 is an integer, when n1=1, L ^N1 is a divalent hydrocarbon group connected from adjacent nitrogen atoms to X ^N1 , and is a hydrocarbon group with 2 to 6 atoms constituting the connecting chain, n2

When 1, L ^N2 is a 1+n2-valent hydrocarbon group connected from the adjacent nitrogen atom to X ^N2 , and is a hydrocarbon group with 2 to 6 atoms constituting the connecting chain.

<4> The photosensitive resin composition according to <3>, wherein in the formula (N2), the total number of X ^N1 and X ^N2 is equal to the total number of Z ^N1 .

<5> The photosensitive resin composition according to <3> or <4>, wherein in the formula (N2), at least a part of the connecting chain in L ^N1 and L ^N2 is an aryl group.

式(N3)中，X^N3表示羥基、羧基及磺酸基中的任一種，Z^N2表示氧原子或硫原子，R^N5及R^N6分別獨立地表示氫原子或碳數1~20的烴基， L^N3係從相鄰氮原子連結至X^N3為止的3價烴基，且表示構成連結鏈之原子數為2~6的烴基。 <6> The photosensitive resin composition according to <1>, wherein the thermal base generator is a polymer compound containing a repeating unit represented by formula (N3);

^In the formula ( ^{N3 ) ,} L ^N3 is a trivalent hydrocarbon group connected from an adjacent nitrogen atom to X ^N3 , and represents a hydrocarbon group with 2 to 6 atoms constituting the connecting chain.

式(N4)中，X^N4分別獨立地表示羥基、羧基及磺酸基中的任一種，Z^N3與Z^N2獨立地表示氧原子或硫原子，R^N7及R^N8與R^N5及R^N6獨立地且分別獨立地表示氫原子或碳數1~20的烴基，L^N4係從相鄰氮原子連結至X^N4為止的4價烴基，且表示構成連結鏈之原子數為2~6的烴基。 <7> The photosensitive resin composition according to <6>, wherein the thermal base generator is a polymer compound containing a repeating unit represented by formula (N4);

^{In the formula ( N4 ) ,} independently and independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. L ^N4 is a tetravalent hydrocarbon group connected from an adjacent nitrogen atom to X ^N4 , and represents a hydrocarbon group having 2 to 6 atoms constituting the connecting chain.

L ^N5 represents a divalent organic group.

<8> The photosensitive resin composition according to <6> or <7>, wherein at least part of the connecting chain in L ^N4 is an aryl group.

<9> The photosensitive resin composition according to any one of <1> to <8>, wherein X N in the formula (N1), X ^N1 or X ^N2 in the formula (N2), or X ^N3 in the formula (N3 ) in X ^N3 or X ^N4 in formula (N4) is a hydroxyl group or a carboxyl group.

<10> The photosensitive resin composition according to any one of <1> to <9>, further comprising a photoradical polymerization initiator and a radical polymerizable compound.

<11> The photosensitive resin composition according to any one of <1> to <10>, wherein the precursor compound contains a polyimide precursor.

<12> The photosensitive resin composition according to <11>, wherein the polyimide precursor has a structural unit represented by the following formula (1);

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

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

<14> The photosensitive resin composition according to any one of <1> to <13>, which is used to form an interlayer insulating film for a rewiring layer.

<15> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <14>.

<16> A laminated body having two or more layers of the cured films described in <15> and having a metal layer between the cured films.

<17> A method for manufacturing a cured film, which includes a film formation process in which the photosensitive resin composition according to any one of <1> to <14> is applied to a substrate to form a film.

<18> The manufacturing method of the cured film according to <17>, which includes a process of heating the film at 50 to 450°C.

<19> A semiconductor element having the cured film according to <15> or the laminated body according to <16>.

式(N3)中，X^N3表示羥基、羧基及磺酸基中的任一種，Z^N2表示氧原子或硫原子，R^N5及R^N6分別獨立地表示氫原子或碳數1~20的烴基， L^N3係從相鄰氮原子連結至X^N3為止的3價烴基，且表示構成連結鏈之原子數為2~6的烴基。 <20> A thermal base generator including a polymer compound containing a repeating unit represented by formula (N3);

^In the formula ( ^{N3 ) ,} L ^N3 is a trivalent hydrocarbon group connected from an adjacent nitrogen atom to X ^N3 , and represents a hydrocarbon group with 2 to 6 atoms constituting the connecting chain.

式(N4)中，X^N4分別獨立地表示羥基、羧基及磺酸基中的任一種，Z^N3與Z^N2獨立地表示氧原子或硫原子，R^N7及R^N8與R^N5及R^N6獨立地且分別獨立地表示氫原子或碳數1~20的烴基，L^N4係從相鄰氮原子連結至X^N4為止的4價烴基，且表示構成連結鏈之原子數為2~6的烴基。 <21> The thermal base generator according to <20>, wherein the polymer compound contains a repeating unit represented by formula (N4);

^{In the formula ( N4 ) ,} independently and independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. L ^N4 is a tetravalent hydrocarbon group connected from an adjacent nitrogen atom to X ^N4 , and represents a hydrocarbon group having 2 to 6 atoms constituting the connecting chain.

L ^N5 represents a divalent organic group.

<22> The thermal base generator according to <20> or <21>, wherein at least part of the connecting chain in L ^N4 is an aryl group.

<23> The thermal base generator according to any one of <20> to <22>, wherein X ^N4 is a hydroxyl group or a carboxyl group.

According to the present invention, a photosensitive resin composition excellent in curability and storage stability can be obtained. Moreover, by using the photosensitive resin composition of this invention, the cured film, the laminated body, the manufacturing method of the cured film, and the semiconductor element of this invention can be provided.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the illustrated embodiments.

The numerical range represented by the "~" mark in this specification indicates the range including the numerical values before and after the "~" as the lower limit and the upper limit respectively.

The term "process" in this specification not only refers to an independent process, but also refers to a process that cannot be clearly distinguished from other processes as long as the expected effect of the process can be achieved.

Regarding the labels for groups (atomic groups) in this specification, labels that do not describe substituted or unsubstituted means that both those without a substituent and those with a substituent are included. For example, when simply described as "alkyl group", it means that both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group) are included. In addition, when simply described as "alkyl", it means that it may be a chain or a ring, and in the case of a chain, it means that it may be a linear or a branched chain. The same meanings apply to "alkenyl", "alkylene" and "alkenyl".

Unless otherwise specified, "exposure" in this specification means not only drawing using light but also drawing using particle beams such as electron beams and ion beams. Examples of energy rays used for drawing include the bright line spectrum of a mercury lamp, actinic rays such as far ultraviolet, extreme ultraviolet (EUV) and X-rays represented by excimer laser, and particles such as electron beams and ion beams. bundle.

In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid". Both or any one of them, "(meth)acrylyl group" means both or any one of "acrylyl group" and "methacrylyl group".

In this specification, the concentration of the solid component in the composition is expressed as the mass percentage of other components except the solvent relative to the total mass of the composition.

In this specification, unless otherwise specified, the physical property values are values under the conditions of a temperature of 23°C and an air pressure of 101325 Pa (1 atmosphere).

In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are based on gel permeation chromatography (GPC measurement) and expressed as styrene-converted values. For example, HLC-8220 (manufactured by TOSOH CORPORATION) can be used as the weight average molecular weight (Mw) and number average molecular weight (Mn), and as the column, guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, and TSKgel Super HZ3000 can be used. and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). In addition, unless otherwise specified, those using THF (tetrahydrofuran) will be used as the eluent. In addition, unless otherwise specified, a detector with a wavelength of UV rays (ultraviolet) of 254 nm is used for detection in GPC measurement.

In this specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", other layers may exist above or below the reference layer among the plurality of layers of interest. That is, a third layer or a third element may be further sandwiched between the reference layer and the other layers, and the reference layer does not need to be in contact with the other layers. In addition, unless otherwise specified, the direction of the stacked layers of the base material is referred to as "up", or if there is In the case of the photosensitive layer, the direction from the substrate toward the photosensitive layer is called "upper", and the opposite direction is called "lower". In addition, the setting of the up and down directions is for convenience in this specification. In actual form, the "up" direction in this specification may also be different from the vertical upward direction.

[Photosensitive resin composition]

唑前驅物中的至少一種(以下，亦將此統稱為“含雜環聚合物的前驅物”。)、以及以下說明之特定的熱鹼產生劑。進而，本發明的感光性樹脂組成物含有光自由基聚合起始劑及自由基聚合性化合物為較佳。以下，對本發明的感光性樹脂組成物的各含有成分進行詳細說明。 The photosensitive resin composition of the present invention (hereinafter also simply referred to as the "composition of the present invention") contains a polyimide precursor and a polybenzo

At least one type of azole precursor (hereinafter, this is also collectively referred to as "heterocycle-containing polymer precursor"), and a specific thermal base generator described below. Furthermore, the photosensitive resin composition of the present invention preferably contains a photoradical polymerization initiator and a radical polymerizable compound. Hereinafter, each component contained in the photosensitive resin composition of the present invention will be described in detail.

<Precursor of heterocycle-containing polymer>

唑前驅物，聚醯亞胺前驅物為更佳。 In the present invention, the precursor of the heterocycle-containing polymer may be a polyimide precursor or a polybenzoide precursor.

Azole precursors and polyimide precursors are more preferred.

<<Polyimide precursor>>

The polyimide precursor preferably contains a structural unit represented by the following formula (1). By adopting this structure, a composition with more excellent film strength can be obtained.

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

A ¹ and A ² are independently oxygen atoms or NH, with oxygen atoms being preferred.

<<<R ¹¹¹ >>>

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group containing a combination thereof, and a linear aliphatic group having 2 to 20 carbon atoms. Preferably, a group including a family group, a branched chain 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 combination thereof, and carbon Aromatic groups with a number of 6 to 20 are more preferred.

R ¹¹¹ is preferably derived from a diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types of diamine may be used.

Specifically, the diamine includes a linear aliphatic group with 2 to 20 carbon atoms, a branched or cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 6 to 20 carbon atoms, or a group containing these combinations. Groups are preferred, and diamines containing aromatic groups with 6 to 20 carbon atoms are more preferred. Examples of the aromatic group include the following aromatic groups.

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

Specific examples of the diamine include those selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclopentane Cyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamine-3,3'-dimethyl Cyclohexylmethane and isophoronediamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4, 4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylsulfide and 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide and 3,3'-diaminodiphenylsulfide, 4 ,4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl (4,4'-diamine-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4'-dimethylbiphenyl Aminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-amine) phenyl)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 hydroxyphenyl)terine, bis(4-amino-3-hydroxyphenyl)terine, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl , bis[4-(4-aminophenoxy)phenyl]terine, bis[4-(3-aminophenoxy)phenyl]terine, bis[4-(2-aminophenoxy) Phenyl]benzene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'- Diaminodiphenyl terine, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene Phenyl)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)fluoride, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfide, 3,3',5,5'-tetramethyl- 4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzyloxy)ethyl methacrylate), 2,4-diaminocumene and 2, 5-Diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-tris Methyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluoride, 2,5-diaminopyridine, 1,2-bis(4 -Aminophenyl)ethane, diaminobenzoaniline, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-amine phenyl) 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-amino) Phenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4 -(4-Aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy) methyl)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy) )biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylbenzene, 4,4'-bis(3-amino-5-trifluoromethylbenzene) Oxy)diphenyl terine, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetrafluoropropane Methyl-4,4'-diaminobiphenyl, 4,4'-diamine-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6 At least one diamine selected from '-hexafluorobenzidine and 4,4'-diaminotetraphenyl.

In addition, the diamines (DA-1) to (DA-18) shown below are also preferred.

Furthermore, as a preferred example, a diamine having at least two alkylene glycol units in the main chain can also be cited. A diamine containing a total of two or more ethylene glycol chains or propylene glycol chains or both in one molecule is preferred, and a diamine containing no aromatic ring is more preferred. Specific examples include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR- 148. JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are product names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-amino Propoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc. , but are not limited to these.

The following shows JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) Registered Trademark) Structure of EDR-176.

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

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

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

R ⁵⁰ ~ R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ ~ R ⁵⁷ is a fluorine atom, methyl, fluoromethyl, difluoromethyl or trifluoromethyl .

Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Fluorinated alkyl groups (numbers 1 to 6), etc.

R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, fluoromethyl, difluoromethyl or trifluoromethyl.

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

<<<R ¹¹⁵ >>>

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

R ¹¹² has the same meaning as A, and the preferred range is also the same.

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

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

Specific examples of tetracarboxylic dianhydride include those selected from the group consisting of pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 3,3 ',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethyl Ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3 ,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2 ,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane- 3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3, 4,9,10-Perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10 -Phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1, At least one of 2,3,4-benzenetetracarboxylic dianhydride and such alkyl derivatives with 1 to 6 carbon atoms and alkoxy derivatives with 1 to 6 carbon atoms.

Moreover, tetracarboxylic dianhydride (DAA-1) - (DAA-5) shown below are also mentioned as a preferable example.

[Chemical 16]

<<<R ¹¹³ and R ¹¹⁴ >>>

In formula (1), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a radical polymerizable group, and it is more preferable that both of R 113 and R 114 contain a radical polymerizable group. The radically polymerizable group is a group capable of carrying out a crosslinking reaction by the action of radicals, and a preferred example thereof includes a group having an ethylenically unsaturated bond.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth)acrylyl group, a group represented by the following formula (III), and the like.

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

In formula (III), R ²⁰¹ represents an alkylene 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, carbon The numbers 1 to 12 are better, 1 to 6 are better, and 1 to 3 are particularly good; the repeated numbers 1 to 12 are better, 1 to 6 are better, and 1 to 3 are particularly good). Furthermore, (poly)oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.

Preferred examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, Hexamethylene, octamethylene, dodecylmethylene, -CH ₂ CH(OH)CH ₂ -, ethylidene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ - are Better.

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

As a preferred embodiment of the polyimide precursor in the present invention, examples of the monovalent organic group of R ¹¹³ or R ¹¹⁴ include 1, 2 or 3 acid groups, preferably 1 acid group. The aliphatic group, aromatic group, aralkyl group, etc. Specific examples include an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms. More specific examples include a phenyl group having an acidic group and a benzyl group having an acidic group. The acidic group is preferably a hydroxyl group. That is, it is preferable that R ¹¹³ or R ¹¹⁴ is a group having a hydroxyl group.

As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent that improves the solubility of the developer can preferably be used.

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

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

The carbon number of the alkyl group is preferably 1 to 30 (when it is cyclic, it is 3 or more). The alkyl group may be linear, branched, or cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, Alkyl, octadecyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, camphenyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl. Dihydryl, dicyclohexyl and pinenyl. Furthermore, as the alkyl group substituted by an aromatic group, a linear alkyl group substituted by an aromatic group described below is preferred.

環、三伸苯環等)或經取代或未經取代的芳香族雜環基(作為構成基團之環狀結構，茀環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、

唑環、噻唑環、吡啶環、吡

環、嘧啶環、噠

環、吲哚

環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹

環、喹啉環、酞

環、萘啶環、喹

啉環、喹唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環、色烯環、

環、啡

噻環、啡噻

環或啡

環)。 The aromatic group is specifically a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes benzene ring, naphthalene ring, biphenyl ring, fluorine ring, pentene ring, Indene ring, azulene ring, heptacene ring, indene ring, perylene ring, fused pentaphenyl ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring,

ring, triphenyl ring, etc.) or substituted or unsubstituted aromatic heterocyclic group (as the cyclic structure of the constituent group, fluorine ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring,

Azole ring, thiazole ring, pyridine ring, pyridine ring

ring, pyrimidine ring, da

ring, indole

ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinine

ring, quinoline ring, phthalein

ring, naphthyridine ring, quinine

Phenoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring,

ring, coffee

thiocycline, thiophene

ring or brown

ring).

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

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

The structural unit represented by formula (1) is preferably a structural unit represented by 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 group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, among R ¹¹³ and R ¹¹⁴ It is preferred that at least one of the groups contains a radically polymerizable group, and a radically polymerizable group is more preferred.

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same meaning as the preferred range of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1).

The preferred range of R ¹¹² has the same meaning as R ¹¹² in formula (5), among which oxygen atom is more preferred.

In formula (1-A), the bonding positions of the benzene ring to the carbonyl group in the formula are preferably 4, 5, 3’, and 4’. In formula (1-B), 1, 2, 4, and 5 are preferred.

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

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

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. Moreover, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

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

The polyimide precursor can be obtained by reacting dicarboxylic acid or dicarboxylic acid derivatives with diamine. It is preferably obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent and then reacting it with a diamine.

In the method for producing the polyimide precursor, it is preferable to use an organic solvent when carrying out the reaction. The number of organic solvents may be one type, or two or more types.

The organic solvent can be appropriately set depending on the raw material, and examples thereof include pyridine, diglyme, N-methylpyrrolidone, and N-ethylpyrrolidone.

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

唑前驅物>> <<polybenzo

Azole precursor>>

唑前驅物包含由下述式(2)表示之結構單元為較佳。 polybenzo

The azole 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 (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, 1 to 6 is particularly preferred) and aromatic group (carbon number 6 to 22 is preferred, 6 is preferred) ~14 is more preferred, 6~12 is particularly preferred) at least one group is preferred. Examples of the aromatic group constituting R ¹²¹ include R ¹¹¹ of the above formula (1). As the above-mentioned aliphatic group, a linear aliphatic group is preferred. R ¹²¹ is preferably derived from 4,4'-oxobenzoyl 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 preferred range is also the same. R ¹²² is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferred ranges are also the same.

唑前驅物還可以包含其他種類的結構單元。 In addition to the above structural units of formula (2), polybenzo

Azole precursors may also contain other types of structural units.

From the viewpoint of being able to suppress the occurrence of warpage of the cured film accompanying ring closure, it is preferable that the precursor contains a diamine residue represented by the following formula (SL) as another type of structural unit.

Z has a structure and b structure, R ^1s is a hydrogen atom or a hydrocarbon group with a carbon number of 1 to 10 (preferably a carbon number of 1 to 6, more preferably a carbon number of 1 to 3), R ^2s is a carbon number of 1 to 10 Hydrocarbon group (preferably having 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 an aromatic group (preferably having 6 to 22 carbon atoms, More preferably, it has a carbon number of 6 to 18, particularly preferably a carbon number of 6 to 10), and the remaining part is a hydrogen atom or a carbon number of 1 to 30 (more preferably, a carbon number of 1 to 18, more preferably a carbon number of 1 to 12, especially Preferably, they are organic groups having 1 to 6 carbon atoms, and they may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. In the Z part, it is preferable that the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a+b is 100 mol%.

唑前驅物的脫水閉環後的彈性率，且抑制翹曲之效果和提高溶解性之效果。 In the formula (SL), preferred examples of Z include those in which R ^5s and R ^6s in the b structure are phenyl groups. In addition, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by commonly used gel permeation chromatography. By setting the above molecular weight to the above range, it is possible to simultaneously reduce the polybenzo

The elastic modulus of the azole precursor after dehydration and ring closure, and the effect of inhibiting warpage and improving the solubility.

When the precursor contains a diamine residue represented by the formula (SL) as another type of structural unit, it also contains the tetracarboxylic acid remaining after removing the acid dianhydride from the tetracarboxylic dianhydride in order to improve the alkali solubility. Residues are preferred as structural units. Examples of these tetracarboxylic acid residues include R ¹¹⁵ in formula (1).

唑前驅物的重量平均分子量(Mw)較佳為2000~500000，更佳為5000~100000，進一步較佳為10000~50000。又，數平均分子量(Mn)較佳為800~250000，更佳為2000~50000，進一步較佳為4000~25000。 polybenzo

The weight average molecular weight (Mw) of the azole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. Moreover, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

唑前驅物的分子量的分散度係1.5~3.5為較佳，2~3為更佳。 polybenzo

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

The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 20 mass% or more, more preferably 30 mass% or more, and further preferably 40 mass% or more, based on the total solid content of the composition. It is further more preferable that it is 50 mass % or more, it is further more preferable that it is 60 mass % or more, and it is still more preferable that it is 70 mass % or more. Furthermore, the content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and further preferably 98% by mass or less relative to the total solid content of the composition. It is better, and 95 mass % or less is still more preferable, and 95 mass % or less is still more preferable.

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

<Thermal base generator>

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

在式(N1)中，X^N表示羥基、羧基及磺酸基中的任一種之親核性基，Z^N表示氧原子(O)或硫原子(S)，R^N1及R^N2分別 獨立地表示氫原子或碳數1~20的烴基，L^N係從相鄰氮原子連結至X^N為止的3價烴基，且表示構成連結鏈之原子數(連結鏈長)為2~6的烴基，兩末端的*分別獨立表示氫原子或1價有機基團。

In the formula ^{( N1 ) ,} Represents a hydrogen atom ^or a hydrocarbon group with 1 to 20 carbon atoms, L ^N is a trivalent hydrocarbon group connected from an adjacent nitrogen atom to The * at both ends independently represents a hydrogen atom or a monovalent organic group.

That is, the above-mentioned specific thermal base generator contains a urea bond (Z ^N =O, representing -NR ^N1 -C(=O)-NR ^N2 - bond.) or a thiourea bond (Z ^N =S, representing - NR ^N1 -C(=S)-NR ^N2 -bond.), and has a structure in which these bonds are connected to the nucleophilic group ^XN through the hydrocarbon group ^LN . Hereinafter, these bonds are also collectively referred to as "urea-type bonds".

In this specification, regarding the hydrocarbon group L connecting a nitrogen atom to When there are multiple X's, the shortest atomic chain among them is used as the "connecting chain". In addition, "X" is a general name for X ^N or X ^N1 mentioned later, etc. In addition, regarding the thermal base generator, "Z" may be similarly used as a general name for Z ^N or Z ^N1 described below, etc. For example, in the exemplary compound BE-1 described below, L ^N is composed of a phenylene group, the connecting chain is composed of two carbon atoms, and the number of atoms constituting the connecting chain (the length of the connecting chain) is 2.

The above-mentioned specific thermal base generator is acidic, weakly acidic or neutral at normal temperature and does not promote the cyclization of the heterocyclic polymer-containing precursor. Furthermore, the above-mentioned specific thermal base generator generates a base by heating, but it is chemically stable at 120°C and further below about 150°C and does not generate an alkali. Even if it is subjected to a normal semiconductor manufacturing process, it will hardly be generated as an alkali. inactivated by the agent. On the other hand, in the above-mentioned specific thermal base generator, for example, the nucleophilicity of the nucleophilic group is activated by heating at a temperature of 150° C. or higher, whereby, for example, according to the following reaction formula, the nucleophilic group in the nucleophilic group The oxygen atom bonds with the carbon atom in the urea-type bond, and the cyclization reaction rapidly proceeds within the molecule. As a result, the carbon atom located in the center of the urea-type bond and the nitrogen atom not adjacent to ^LN are rapidly dissociated, thereby efficiently producing an amine (preferably a secondary amine). Therefore, the cyclization of the heterocycle-containing polymer precursor is efficiently performed by the base generated from the specific thermal base generator after heating, so that the obtained cured film has excellent elongation at break. Furthermore, the photosensitive resin composition of the present invention containing the above-mentioned specific thermal base generator is also excellent in storage stability due to the above-mentioned chemical stability of the specific thermal base generator.

In the present invention, the number of carbon atoms in ^LN is preferably 3 to 24. The upper limit is 12 or less, which is more preferred, 10 or less, which is further preferred, and 8 or less, which is particularly preferred. The lower limit is 4 or more, which is more preferable, 5 or more, which is still more preferable, and 6 or more, which is extremely good. From the viewpoint of rapidly advancing the intramolecular cyclization reaction, in the present invention, the linking chain length is more preferably 2 to 4, further preferably 2 or 3, and 2 is particularly preferably.

L ^N is preferably a group including a linear or branched chain alkylene group, a cyclic alkylene group or an aryl group and a combination thereof, and more preferably a group containing at least a cyclic alkylene group or an aryl group, It is more preferable that it contains at least an aryl group. The cyclic alkylene group may be a single ring or a condensed ring. In addition, the cyclic alkylene group is preferably a 5- to 8-membered ring, and more preferably a 5- or 6-membered ring, such as cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, and cyclooctanediyl. Alkanediyl etc. The aryl group may be a single ring or a condensed ring. In addition, the carbon number of the aryl group is preferably 6 to 14, and more preferably 6 to 10, such as phenyl, naphthyl, anthracenediyl, phenanthrenediyl, biphenylene, and triphenylene. (terphenylene), etc., and phenylene, naphthylene or biphenylene, etc. are more preferred. L ^N may have the following substituent T in addition to X ^N. Furthermore, the substituent T may contain the same nucleophilic group as X (that is, at least one of a hydroxyl group, a carboxyl group, and a sulfonic acid group). In the present invention, from the viewpoint of making the above-mentioned intramolecular cyclization reaction proceed efficiently, the number of such nucleophilic groups as a whole including X and the substituent T is preferably close to the total number of Z, and is within the total number of Z ±2 Within the range of the total number of Z, it is better, within the range of the total number of Z ±1, it is even better, and it is particularly good if it is equal to the total number of Z. Furthermore, it is preferred that at least a part of the connecting chain in L ^N is an aryl group.

(Substituent T)

Examples of the substituent T include a halogen atom, a cyano group, a nitro group, a hydrocarbon group, a heterocyclic group, -ORt ¹ , -CORt ¹ , -COORt ¹ , -OCORt ¹ , -NRt ¹ Rt ² , -NHCORt ¹ , - CONRt ¹ Rt ² , -NHCONRt ¹ Rt ² , -NHCOORt ¹ , -SRt ¹ , -SO ₂ Rt ¹ , -SO ₂ ORt ¹ , -NHSO ₂ Rt ¹ or -SO ₂ NRt ¹ Rt ² . Rt ¹ and Rt ² each independently represent a hydrogen atom, a hydrocarbon group or a heterocyclic group. Rt ¹ and Rt ² may bond to form a ring.

Regarding the substituent T, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 15, and further preferably 1 to 8. The alkyl group may be any one of straight chain, branched chain, or cyclic. Straight chain or branched chain is preferred, and branched chain is more preferred. The carbon number of the alkenyl group is preferably 2 to 30, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be linear, branched, or cyclic, with linear or branched chains being preferred. The number of carbon atoms in the alkynyl group is preferably 2 to 30, and more preferably 2 to 25. The alkynyl group can be straight chain, Either branched chain or cyclic, with linear or branched chain being preferred. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. The heterocyclyl group may be a single ring or a condensed ring. The heterocyclyl group is preferably a single ring or a condensed ring with a condensation number of 2 to 4. The number of heteroatoms in the ring constituting the heterocyclyl group is preferably 1 to 3. The heteroatoms constituting the ring of the heterocyclyl group are preferably nitrogen atoms, oxygen atoms or sulfur atoms. The number of carbon atoms in the ring constituting the heterocyclyl group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.

The hydrocarbon group and the heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described for the substituent T described above.

From the viewpoint of rapidly advancing the intramolecular cyclization reaction, X ^N is preferably a hydroxyl group or a carboxyl group, and more preferably a hydroxyl group. Furthermore, it is preferable that the numbers of nucleophilic atoms (especially oxygen atoms in the nucleophilic group) and nucleophilic atoms (carbon atoms to which Z ^N is bonded) are the same. This reduces the steric hindrance during the nucleophilic reaction, allowing the intramolecular cyclization reaction to proceed efficiently.

R ^N1 and R ^N2 are preferably hydrogen atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, or aliphatic hydrocarbon groups having 1 to 20 carbon atoms. When R ^N1 and R ^N2 are aromatic hydrocarbon groups, the number of carbon atoms is more preferably 6 to 18, and further preferably 6 to 10. Examples of such aromatic hydrocarbon groups include phenyl and naphthyl. When R ^N1 and R ^N2 are aliphatic hydrocarbon groups, the number of carbon atoms is preferably 1 to 12, further preferably 1 to 8, and particularly preferably 1 to 6. The aliphatic hydrocarbon group may be a linear or branched chain alkyl group, or a cyclic alkyl group. Examples of such aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, cyclopentyl and cyclohexyl. Among them, the aromatic hydrocarbon group and the aliphatic hydrocarbon group may have a substituent T. R ^N1 and R ^N2 are particularly preferably hydrogen atoms.

The * sites at both ends are independently hydrogen atoms or monovalent organic groups. Regarding the * position, the univalent organic group is selected from linear or branched chain alkyl groups, cyclic alkyl groups, linear or branched chain alkenyl groups, cyclic alkenyl groups, and oxygen atoms in the chain. The hydrocarbon group composed of one or more combinations of alkyl groups and aryl groups is preferred. These may be linear or branched. As the monovalent organic group, the * site is preferably a cyclic alkyl group or an aryl group. In addition, regarding the * site, the monovalent organic group may contain a heteroatom-containing bond or substituent other than the hydrocarbon group. Examples of such bonds include ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, and amide bonds. Examples of such substituents include a hydroxyl group, a mercapto group, a cyano group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a nitro group, a carboxyl group, a hydroxyl group, a hydroxyl group, and a sulfinic acid group. , sulfo group, alkyl ether group, amine group, etc.

In the present invention, the compound represented by the formula (N1) has the various structures as described above as a monovalent organic group at the * sites at both ends, and becomes the formula (N1-a), formula (N2) to formula (N5 ) represents the compound.

The compound represented by formula (N1) may be a low molecular compound or a high molecular compound. When the above compound is a low molecular compound, its molecular weight is preferably 50 to 1000. The upper limit is 800 or less, which is more preferred, 600 or less, which is further preferred, and 500 or less, which is particularly preferred. The lower limit is 80 or more, which is more preferable, 100 or more, which is still more preferable, and 120 or more, which is extremely good. On the other hand, when the above compound is a polymer compound, the molecular weight is preferably 2,000 to 100,000. The upper limit is preferably 80,000 or less, further preferably 60,000 or less, and particularly preferably 40,000 or less. The lower limit is more preferably 3,000 or more, further preferably 5,000 or more, and particularly preferably 7,000 or more.

For example, the compound represented by formula (N1) is preferably a compound represented by formula (N1-a).

X ^N , Z ^N , ^RN1 and ^RN2 in the formula (N1-a) are the same as X ^N , Z ^N , ^RN1 and ^RN2 in the formula (N1). A ^N1 represents an aryl group, which may be a single ring or a condensed ring. In addition, the carbon number of the aryl group is preferably 6 to 14, more preferably 6 to 10, and examples include phenyl, naphthyl, biphenylene, and the like. A ^N2 represents an aryl group, which may be a single ring or a condensed ring. In addition, the carbon number of the aryl group is preferably 6 to 14, more preferably 6 to 10, such as phenyl, naphthyl, biphenyl, etc.

Furthermore, as the monovalent organic group, it is preferable that the * position at the terminal further has a group including a structure in which a urea-type bond and a nucleophilic group X are linked by a hydrocarbon group.

That is, in the present invention, it is preferable that the specific thermal base generator is a compound represented by formula (N2).

式(N2)中，按每一個對n1、n2或n3標註之括號獨立，X^N1及X^N2分別獨立地表示羥基、羧基及磺酸基中的任一種之親核 3基，Z^N1表示氧原子或硫原子，R^N3及R^N4分別獨立地表示氫原子或碳數1~20的烴基，L^N1及L^N2分別獨立地表示碳數1~20的烴基，n1表示0或1，n2表示0~10的整數，n1及n2之和為1以上，n3表示1以上的整數。又，n1=1時，L^N1係從相鄰氮原子連結至X^N1為止的2價烴基，且為構成連結鏈之原子數為2~6的烴基。或n2

1時，L^N2係從相鄰氮原子連結至X^N2為止的1+n2價烴基，且為構成連結鏈之原子數為2~6的烴基。

In the formula (N2), each parentheses marked for ⁿ¹ , n2 or n3 are independent, X ^{N1 and} Atom or sulfur atom, R ^N3 and R ^N4 respectively independently represent a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, L ^N1 and L ^N2 respectively independently represent a hydrocarbon group with 1 to 20 carbon atoms, n1 represents 0 or 1, and n2 represents Integers from 0 to 10, the sum of n1 and n2 is more than 1, and n3 represents an integer more than 1. When n1=1, L ^N1 is a divalent hydrocarbon group connected from an adjacent nitrogen atom to X ^N1 , and the number of atoms constituting the connecting chain is 2 to 6. or n2

When 1, L ^N2 is a 1+n2-valent hydrocarbon group connected from the adjacent nitrogen atom to X ^N2 , and is a hydrocarbon group with 2 to 6 atoms constituting the connecting chain.

Like L ^N in formula (N1), L ^N1 is preferably a group including a linear or branched alkylene group, a cyclic alkylene group or an aryl group, or a combination thereof, and at least contains a cyclic group. It is more preferable that it contains an alkylene group or an aryl group, and it is still more preferable that it contains at least an aryl group. L ^N1 may have the above-mentioned substituent T except X ^N1 . As in the case of L ^N , the substituent T may contain the same nucleophilic group as X. L ^N2 is also preferably a group including a linear or branched chain alkylene group, a cyclic alkylene group or an aryl group and a combination thereof, and more preferably a group including at least a cyclic alkylene group or an aryl group. , it is more preferred to contain at least an aryl group. Examples of the cyclic alkylene group include cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, cyclooctanediyl, and the like. Examples of the aryl group include phenylene group, naphthylene group, anthracendiyl group, phenanthrenediyl group, etc., with phenylene group or naphthylene group being more preferred. L ^N2 may have the above-mentioned substituent T except X ^N2 . As in the case of L ^N , the substituent T may contain the same nucleophilic group as X. Furthermore, it is preferable that at least a part of the connecting chain in L ^N1 is an aryl group, and it is preferable that at least a part of the connecting chain in L ^N2 is an aryl group.

Like X ^N in formula (N1), X ^N1 and X ^N2 are preferably hydroxyl or carboxyl groups, and more preferably hydroxyl groups. n1 and n2 represent the number of nucleophilic groups, and the total value of n1 and n2 is approximately the same as the total number of Z ^N1 . It is preferable that the total number of X ^N1 and X ^N2 is equal to the total number of Z ^N1 . That is, for all the brackets marked on n3, n1=1, and n2=0, for all the brackets marked on n3, n1=0, and n2=n3, and for every bracket marked on n3. Any case where the total of n1 and the sum of n2 is equal to n3 is preferred. Therefore, it is better for n2 to be an integer from 0 to n3, and it can also have the same value as n3. For n3, 1 to 10 is better, 1 to 4 is better, 1 to 3 is further better, and 2 or 3 is extremely good. In this way, by making the number of nucleophilic atoms and nucleophilic atoms the same as each other, the steric hindrance during the nucleophilic reaction is reduced, and the intramolecular cyclization reaction can be efficiently performed.

R ^N3 and R ^N4 have the same meanings as R ^N1 and R ^N2 in the formula (N1) respectively. A hydrogen atom, an aromatic hydrocarbon group with 6 to 20 carbon atoms or an aliphatic hydrocarbon group with 1 to 20 carbon atoms is preferred. The hydrogen atom is Better.

The molecular weight of the compound represented by formula (N2) is preferably 100 to 2000. The upper limit is preferably 1,800 or less, further preferably 1,500 or less, and particularly preferably 1,200 or less. The lower limit is 120 or more, which is more preferable, 150 or more, which is still more preferable, and 200 or more, which is particularly good.

Furthermore, in the present invention, it is also preferred that the specific thermal base generator is a polymer compound containing a repeating unit represented by formula (N3). Thermal base generators of polymer compounds have the advantage of being non-volatile.

式(N3)中，按每一個重複單元獨立，X^N3表示羥基、羧基及磺酸基中的任一種之親核性基，Z^N2表示氧原子或硫原子，R^N5及R^N6分別獨立地表示氫原子或碳數1~20的烴基，L^N3係從相鄰氮原子連結至X^N3為止的3價烴基，且表示構成連結鏈之原子數為2~6的烴基。 [Chemical 25]

In formula ( ^N3 ) ^, each ^repeating unit is independent ^. It represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms. L ^N3 is a trivalent hydrocarbon group connected from an adjacent nitrogen atom to X ^N3 , and represents a hydrocarbon group with 2 to 6 atoms constituting the connecting chain.

Like L ^N in formula (N1), L ^N3 is preferably a group including a linear or branched alkylene group, a cyclic alkylene group or an aryl group, or a combination thereof, and at least contains a cyclic group. It is more preferable that it contains an alkylene group or an aryl group, and it is still more preferable that it contains at least an aryl group. Examples of the aryl group include a phenylene group, a naphthylene group, a biphenylene group, and the like. L ^N3 may have substituents T other than X ^N3. As in the case of L ^N , the substituent T may contain the same nucleophilic group as X. It is preferred that at least part of the connecting chain in L ^N3 is an aryl group.

Like X ^N in formula (N1), X ^N3 is preferably a hydroxyl group or a carboxyl group, and more preferably a hydroxyl group. By making the total number of X ^N3 equal to the total number of Z ^N2 , that is, by making the number of nucleophilic atoms and nucleophilic atoms equal to each other, the steric hindrance during the nucleophilic reaction is reduced, and intramolecular cyclization reaction can be carried out. Do it efficiently.

R ^N5 and R ^N6 have the same meanings as R ^N1 and R ^N2 in formula (N1) respectively. A hydrogen atom, an aromatic hydrocarbon group with 6 to 20 carbon atoms or an aliphatic hydrocarbon group with 1 to 20 carbon atoms is preferred. The hydrogen atom is Better.

Furthermore, the polymer compound containing a repeating unit represented by formula (N3) is preferably a polymer compound containing a repeating unit represented by formula (N4).

式(N4)中，按每一個重複單元獨立，X^N4分別獨立地表示羥基、羧基及磺酸基中的任一種，Z^N3與Z^N2獨立地表示氧原子或硫原子，R^N7及R^N8與R^N5及R^N6獨立且分別獨立地表示氫原子或碳數1~20的烴基，L^N4係從相鄰氮原子連結至X^N4為止的4價烴基，且表示構成連結鏈之原子數為2~6的烴基，L^N5表示2價有機基團。式(N4)中，Z^N2、R^N5及R^N6與式(N3)中的Z^N2、R^N5及R^N6相同。

In formula (N4), each repeating unit is independent, X ^N4 independently represents any one of hydroxyl, carboxyl and sulfonic acid groups, Z ^N3 and Z ^N2 independently represent oxygen atoms or sulfur atoms, R ^N7 and R ^N8 R ^N5 and R ^N6 independently and independently represent a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms. L ^N4 is a tetravalent hydrocarbon group connected from an adjacent nitrogen atom to X ^N4 , and represents the number of atoms constituting the connecting chain. 2~6 hydrocarbon groups, L ^N5 represents a divalent organic group. In formula (N4), Z ^N2 , ^RN5 and ^RN6 are the same as Z ^N2 , ^RN5 and ^RN6 in formula (N3).

Like L ^N in formula (N1), L ^N4 is preferably a group including a linear or branched alkylene group, a cyclic alkylene group or an aryl group, or a combination thereof, and at least contains a cyclic group. It is more preferable that it contains an alkylene group or an aryl group, and it is still more preferable that it contains at least an aryl group. Examples of the aryl group include a phenylene group, a naphthylene group, a biphenylene group, and the like. L ^N4 may have substituents T other than X ^N4. As in the case of L ^N , the substituent T may contain the same nucleophilic group as X. It is preferred that at least part of the connecting chain in L ^N4 is an aryl group.

L ^N5 is selected from the group consisting of linear or branched chain alkylene groups, cyclic alkylene groups, alkylene groups with oxygen atoms in the chain, linear or branched chain alkenyl groups, cyclic The hydrocarbon group composed of one or a combination of two or more of the alkenylene and aryl groups is preferred. L ^N5 is preferably a group including a linear or branched chain alkylene group, a cyclic alkylene group or an aryl group and a combination thereof, and more preferably a group containing at least a cyclic alkylene group or an aryl group, It is more preferable that it contains at least an aryl group. Examples of the aryl group include a phenylene group, a naphthylene group, a biphenylene group, and the like. L ^N5 may have a substituent T.

Like X ^N in formula (N1), X ^N4 is preferably a hydroxyl group or a carboxyl group, and more preferably a hydroxyl group. ^{By making} the ^total number of The internal cyclization reaction proceeds efficiently.

R ^N7 and R ^N8 have the same meanings as R ^N1 and R ^N2 in formula (N1) respectively. A hydrogen atom, an aromatic hydrocarbon group with 6 to 20 carbon atoms or an aliphatic hydrocarbon group with 1 to 20 carbon atoms is preferred. The hydrogen atom is Better.

The weight average molecular weight of the polymer compound represented by formula (N3) or formula (N4) is preferably 2,000 to 100,000. The upper limit is preferably 8,000 or less, further preferably 6,000 or less, and particularly preferably 4,000 or less. The lower limit is more preferably 3,000 or more, further preferably 5,000 or more, and particularly preferably 7,000 or more.

The content of the thermal base generator containing the polymer compound of the repeating unit represented by the formula (N3) or the formula (N4) is 0.01~ with respect to the total solid content in the composition. 30% by mass is preferred. The upper limit is more preferably 25% by mass or less, and still more preferably 20% by mass or less. The lower limit is more preferably 0.1% by mass or more, and more preferably 0.3% by mass or more.

The polymer compound containing the repeating unit represented by Formula (N3) or Formula (N4) can be synthesized, for example, by polymerizing a dihydroxydiamine compound and a diisocyanate compound.

Furthermore, in the present invention, it is also preferable that the specific thermal base generator is a polymer compound containing a repeating unit represented by formula (N5).

In formula ( ^{N5 )} , ^each repeating unit is independent ^. Represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms. L ^N6 is a divalent hydrocarbon group connected from an adjacent nitrogen atom to X ^N5 and represents a hydrocarbon group with 2 to 6 atoms constituting the connecting chain. L ^N7 represents a divalent organic groups.

Like L ^N in formula (N1), L ^N6 is preferably a group including a linear or branched alkylene group, a cyclic alkylene group or an aryl group, and a combination thereof, and at least contains a cyclic group. It is more preferable that it contains an alkylene group or an aryl group, and it is still more preferable that it contains at least an aryl group. L ^N6 may have substituents T other than X ^N5. As in the case of L ^N , the substituent T may contain the same nucleophilic group as X. It is preferred that at least part of the connecting chain in L ^N6 is an aryl group. L ^N7 is selected from the group consisting of linear or branched chain alkylene groups, cyclic alkylene groups, alkylene groups with oxygen atoms in the chain, linear or branched chain alkenyl groups, cyclic The hydrocarbon group composed of one or a combination of two or more of the alkenylene and aryl groups is preferred. L ^N7 is more preferably a cyclic alkylene group or aryl group having 5 to 10 carbon atoms. L ^N7 may have a substituent T.

Like X ^N in formula (N1), X ^N5 is preferably a hydroxyl group or a carboxyl group, and more preferably a hydroxyl group. By making the total number of X ^N5 equal to the total number of Z ^N4 , that is, by making the number of nucleophilic atoms and nucleophilic atoms equal to each other, the steric hindrance during the nucleophilic reaction is reduced, enabling intramolecular cyclization reaction. Do it efficiently.

R ^N9 and R ^N10 have the same meanings as R ^N1 and R ^N2 in formula (N1) respectively. A hydrogen atom, an aromatic hydrocarbon group with 6 to 20 carbon atoms or an aliphatic hydrocarbon group with 1 to 20 carbon atoms is preferred. The hydrogen atom is Better.

The weight average molecular weight of the polymer compound containing the repeating unit represented by formula (N5) is preferably 2,000 to 100,000. The upper limit is preferably 80,000 or less, further preferably 60,000 or less, and particularly preferably 4,000 or less. The lower limit is preferably 5,000 or more, further preferably 8,000 or more, and particularly preferably 10,000 or more.

The content of the thermal base generator containing the polymer compound of the repeating unit represented by formula (N5) is preferably 0.01 to 30% by mass relative to the total solid content in the composition. The upper limit is more preferably 25% by mass or less, and still more preferably 20% by mass or less. The lower limit is more preferably 0.1% by mass or more, and more preferably 0.3% by mass or more.

Examples of the thermal base generator represented by formula (N1) include the following examples, but the present invention should not be construed in a limiting manner.

[Chemical 29]

Regarding the specific thermal base generator represented by the above formula (N1), the pKa of the conjugate acid of the generated base is preferably 8 or more, more preferably 9 or more, and 10 or more. Better still. There is no special limit on the upper limit, but it is actually below 14. By setting the pKa of the specific thermal base generator to the above range, the generated base can efficiently proceed with the cyclization reaction of the polymer precursor, and can increase the elongation at break of the cured film at low temperatures. From this point of view Better. The pKa here is a value determined by the following method.

The pKa described in this specification refers to the equilibrium constant Ka expressed by the negative common logarithm pKa, taking into account the dissociation reaction of releasing hydrogen ions from the acid. The smaller the pKa, the stronger the acid. Unless otherwise stated, pKa is a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, you can refer to the values recorded in "Chemistry Handbook, Basics, Revised 5th Edition" compiled by the Chemical Society of Japan.

The content of the specific thermal base generator is preferably 0.5 to 30% by mass relative to the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.1 mass % or more, further preferably 0.5 mass % or more, and particularly preferably 1.0 mass % or more. The upper limit is preferably 20 mass% or less, further preferably 15 mass% or less, and particularly preferably 10 mass% or less.

The content of the specific thermal base generator relative to 100 parts by mass of the polymer precursor is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and still more preferably 1.5 parts by mass or more. Better. For example, the upper limit is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, further preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less.

By setting the content of the specific thermal base generator to not less than the above-mentioned lower limit, it is preferable from the viewpoint of ensuring good storage stability in the photosensitive resin composition and achieving better mechanical properties of the cured film. . By setting it to the above upper limit value to This is preferable from the viewpoint of ensuring corrosion resistance of metal (for example, copper used for wiring, etc.).

One type or two or more types of specific thermal base generators can be used. When two or more types are used, the total amount is preferably within the above range.

The photosensitive resin composition of the present invention may or may not contain other thermal base generators other than the specific thermal base generator. When other thermal base generators are included, those described in WO2015/199219 and WO2015/199220 can be exemplified, and these contents are incorporated into this specification. Moreover, in the present invention, it is also possible to adopt a configuration that does not substantially include other thermal base generating agents other than the specific thermal base generating agent. Substantially not included means that the content of the specific thermal base generator contained in the photosensitive resin composition of the present invention is 5 mass % or less, preferably 3 mass % or less, and more preferably 1 mass %.

<Photosensitizer>

The photosensitive resin composition of the present invention preferably contains a photosensitizer. Examples of the photosensitizer include a photoradical polymerization initiator. In addition, for example, a photocuring accelerator, a thermal radical polymerization initiator, and a thermal acid generator may also be included.

<<Photopolymerization initiator>>

The photopolymerization initiator that can be used as the photosensitizer is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited, and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light from an ultraviolet region to a visible region is preferred. In addition, it can be an active agent that interacts with the sensitizer excited by light and generates active free radicals.

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

骨架之化合物、具有

二唑骨架之化合物、具有三鹵甲基之化合物等)、醯基氧化膦等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮化合物、羥基苯乙酮、偶氮系化合物、疊氮化合物、茂金屬化合物、有機硼化合物、鐵芳烴錯合物等。關於該等的詳細內容，能夠參閱日本特開2016-027357號公報的0165~0182段、國際公開WO2015/199219號的0138~0151段的記載，該內容編入本說明書中。 As the photoradical polymerization initiator, any known compound can be used. For example, halogenated hydrocarbon derivatives (for example, having three

A compound with a skeleton

Compounds with an oxadiazole skeleton, compounds with trihalomethyl groups, etc.), acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbisimidazole, oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, Aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic hydrocarbon complexes, etc. For details, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. WO 2015/199219, which contents are incorporated into this specification.

Examples of the ketone compound include compounds described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611, and this content is incorporated into this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can be preferably used.

As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be preferably used. More specifically, for example, aminoacetophenone described in Japanese Patent Application Laid-Open No. 10-291969 can also be used. The initiator is the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898.

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

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

As the aminoacetophenone-based initiator, compounds described in Japanese Patent Application Laid-Open No. 2009-191179 whose maximum absorption wavelength matches a light source with a wavelength of 365 nm or 405 nm can also be used.

Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. In addition, commercially available IRGACURE-819 or IRGACURE-TPO (trade name: both manufactured by BASF Corporation) can be used.

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

As a photoradical polymerization initiator, an oxime compound is more preferable. By using oxime compounds, the exposure latitude can be further effectively increased. Among oxime compounds, they are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photohardening accelerator.

As specific examples of the oxime compound, compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166 can be used. .

Preferred oxime compounds include, for example, compounds with the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetyloxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetyloxyiminopentan-3-one, 2-acetyloxyiminobutan-1-phenylpropane-1- ketone, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. In the photosensitive resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime photopolymerization initiator has a >C=N-O-C(=O)- linking group in the molecule.

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF), ADEKA OPTOMER N-1919 (ADEKA Photo radical polymerization initiator 2) manufactured by CORPORATION and described in Japanese Patent Application Publication No. 2012-014052. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), ADEKAARKLS NCI-831, and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of these oxime compounds include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and Japanese Patent Application Publication No. 2014-500852. Compound (C-3) described in paragraph 0101 of Japanese Patent Application Publication No. 2013-164471, etc.

Preferred oxime compounds include oxime compounds having specific substituents shown in Japanese Patent Application Laid-Open No. 2007-269779 or oxime compounds having a thioaryl group shown in Japanese Patent Application Laid-Open No. 2009-191061. Compounds etc.

化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓鹽化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯基-苯-鐵錯合物及其鹽、鹵甲基

二唑化合物、3-芳基取代香豆素化合物之群組中之化合物。 From the perspective of exposure sensitivity, the photoradical polymerization initiator is selected from the group consisting of trihalomethyltri

Compounds, benzyldimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds , benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyl

Compounds in the group of oxadiazole compounds and 3-aryl substituted coumarin compounds.

化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟 化合物、三芳基咪唑二聚體、鎓鹽化合物、二苯甲酮化合物、苯乙酮化合物，選自包括三鹵甲基三

化合物、α-胺基酮化合物、肟化合物、三芳基咪唑二聚體、二苯甲酮化合物之群組中之至少一種化合物為進一步較佳，使用茂金屬化合物或肟化合物為更進一步較佳，肟化合物為更進一步較佳。 A better photoradical polymerization initiator is trihalomethyltri

Compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, selected from the group consisting of Trihalomethyltri

It is further preferred to use at least one compound from the group consisting of a compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound, and it is further preferred to use a metallocene compound or an oxime compound, Oxime compounds are further preferred.

In addition, as the photoradical polymerization initiator, N, such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone) can also be used. N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, Aromatic ketones such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1, quinones such as alkyl anthraquinones and other quinones formed by ring condensation with aromatic rings, Benzoin ether compounds such as benzoin alkyl ether, benzoin, benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyldimethyl ketal, etc. Moreover, the compound represented by the following formula (I) can also be used.

In formula (I), R ^I00 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 alkoxy group having 1 to 12 carbon atoms, or a phenyl group. , consisting of an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, and an alkenyl group with 2 to 12 carbon atoms, interrupted by one or more oxygen atoms. The alkyl group having 2 to 18 carbon atoms and the alkyl group having 1 to 4 carbon atoms is at least one substituted phenyl group or biphenyl group, R ^I01 is a group represented by formula (II), or is the same as R ^I00 The group, R ^I02 ~ R ^I04 are each independently an alkyl group with 1 to 12 carbon atoms, an alkoxy group with 1 to 12 carbon atoms, or a halogen.

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 of the above formula (I).

In addition, the compounds described in paragraphs 0048 to 0055 of International Publication No. WO2015/125469 can also be used as the photoradical polymerization initiator.

When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 0.5% to 30% by mass relative to the total solid content of the photosensitive resin composition of the present invention. 15% by mass, more preferably 1.0~10% by mass. The photopolymerization initiator may contain only one type, or two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

<<Thermal polymerization initiator>>

As the photosensitizer, a thermal polymerization initiator can be used, especially a thermal radical polymerization initiator can be used. Thermal radical polymerization initiator is a compound that generates free radicals by heat energy and starts or promotes the polymerization reaction of a polymerizable compound. By adding Heating the radical polymerization initiator can cyclize the polymer precursor and proceed with the polymerization reaction of the polymer precursor, thereby achieving a higher degree of heat resistance.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-063554.

When a thermal radical polymerization initiator is contained, its content is preferably 0.1 to 30 mass%, more preferably 0.1 to 20 mass%, and further preferably 0.1 to 30 mass% relative to the total solid content of the photosensitive resin composition of the present invention. 5~15% by mass. Thermal radical polymerization initiator may contain only one type or two or more types. When two or more thermal radical polymerization initiators are contained, the total amount is preferably within the above range.

<Polymerizable compound>

<<Radically polymerizable compound>>

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

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

The molecular weight of the radically polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, and 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 radically polymerizable compound containing two or more polymerizable groups, and at least one trifunctional or higher radically polymerizable compound. Sexual compounds are better. Moreover, it may be a mixture of a bifunctional radically polymerizable compound and a trifunctional or higher radically polymerizable compound. In addition, the number of functional groups of a radically polymerizable compound represents the number of radically polymerizable groups in one molecule.

Specific examples of radically polymerizable compounds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides. , preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, the addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amine group, or a mercapto group, and a monofunctional or polyfunctional isocyanate or epoxy can be preferably used. , dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. In addition, the addition reaction product of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, thiols, and halogen groups or toluene Substitution reactants of unsaturated carboxylic acid esters or amides with releasable substituents such as sulfonyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. As another example, instead of the unsaturated carboxylic acid, a group of compounds substituted by unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. can be used. As a specific example, refer to Japanese Patent Application Laid-Open The records in paragraphs 0113~0122 of Public Notice No. 2016-027357 are incorporated into this manual.

In addition, the radically polymerizable compound is also preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and neopenterythritol triacrylate. (Meth)acrylate, neopenterythritol tetra(meth)acrylate, dineopenterythritol penta(meth)acrylate, dineopenterythritol hexa(meth)acrylate, hexanediol (meth)acrylate acrylate, trimethylolpropane tris(acrylyloxypropyl) ether, tris(acrylyloxyethyl)isocyanurate, glycerin or trimethylolethane, etc. in multifunctional alcohols Compounds that are (meth)acrylated after adding ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. 51-037193 (Meth)acrylic urethanes described in the publication, polyester acrylics described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490 Esters include polyfunctional acrylates or methacrylates such as epoxy acrylates which are the reaction product of epoxy resin and (meth)acrylic acid, and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also suitable. Furthermore, polyfunctional (meth)acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate and the like can also be cited.

In addition, as preferred radical polymerizable compounds other than the above, Japanese Patent Application Laid-Open No. 2010-160418 and Japanese Patent Application Laid-Open No. 2010-129825 can also be used. Compounds having a fluorine ring and two or more groups containing ethylenically unsaturated bonds or cardo resins described in the publication, Japanese Patent No. 4364216, etc.

Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 1-040337, Japanese Patent Publication No. 1-040336, Japanese Patent Publication No. 1-040336, and Japanese Patent Publication No. 2 - Vinylphosphonic acid-based compounds described in Publication No. 025493, etc. In addition, compounds containing a perfluoroalkyl group described in Japanese Patent Application Publication No. Sho 61-022048 can also be used. Furthermore, those introduced as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. WO 2015/199219 can also be preferably used, and these contents are incorporated in this manual.

In addition, the following compounds described as formula (1) and formula (2) together with specific examples in Japanese Patent Application Laid-Open No. 10-062986 can also be used as radical polymerizable compounds. These compounds are added to a polyfunctional alcohol. A compound formed by (meth)acrylation into ethylene oxide or propylene oxide.

Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as other radical polymerizable compounds, and these contents are incorporated in this specification.

As the radical polymerizable compound, dipenterythritol triacrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipenterythritol tetraacrylate (commercially available product: KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipenterythritol penta(meth)acrylate (commercially available as KAYARAD D -310; manufactured by Nippon Kayaku Co., Ltd.), dipenterythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and the structure in which the (meth)acrylyl group is bonded via an ethylene glycol residue or a propylene glycol residue is preferred. These oligomer types can also be used.

Examples of commercially available radically polymerizable compounds include SR-494, a tetrafunctional acrylate having four ethoxyl chains, and SR-494, a tetrafunctional acrylate having four vinyloxy chains, manufactured by Sartomer Company, Inc. Functional methyl acrylate SR-209, 231, 239 manufactured by Sartomer Company, Inc., Nippon Kayaku Co., Ltd. DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains, and DPCA-60 having 3 pentyleneoxy chains TPA-330, trifunctional acrylate of isobutoxy chain, urethane oligomer UAS-10, urethane oligomer UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.) , NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd. ), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

Examples of radically polymerizable compounds include those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 2-032293, and Japanese Patent Publication No. 2-016765. Urethane acrylates, environmentally friendly products described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 Urethane compounds having an oxyethane-based skeleton are also preferred. Furthermore, as the radically polymerizable compound, compounds having an amine group structure in the molecule described in Japanese Patent Application Laid-Open Nos. 63-277653, 63-260909, and 105238 can also be used. Or compounds with sulfide structure.

The radical polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxyl group or a phosphate group. Among the radically polymerizable compounds having acidic groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, and those having acidic groups are obtained by reacting unreacted hydroxyl groups of the aliphatic polyhydroxy compounds with non-aromatic carboxylic acid anhydrides. Radically polymerizable compounds are more preferred. Particularly preferred are radically polymerizable compounds having acidic groups by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic acid anhydrides. The aliphatic polyhydroxy compounds are neopentyl erythritol and/or dineopenterythritol. of compounds. As commercially available products, for example, polybasic acid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd. include M-510, M-520, and the like.

The preferred acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. As long as the acid value of the radically polymerizable compound is within the above range, the production and workability will be excellent, and the developability will be excellent. In addition, the polymerizability is good.

From the viewpoint of suppressing warpage accompanying elastic modulus control of the cured film, the photosensitive resin composition of the present invention can preferably use a monofunctional radical polymerizable compound as the radical polymerizable compound. As the monofunctional radical polymerizable compound, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy acrylate can be preferably used. Ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and other (meth)acrylates Derivatives, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate Allyl compounds such as esters, etc. As the monofunctional radical polymerizable compound, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or higher under normal pressure is also preferred.

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

化合物。 The photosensitive resin composition of the present invention may contain polymerizable compounds other than the radically polymerizable compounds described above. Examples of polymerizable compounds other than the above-mentioned radically polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group, or a hydroxymethyl group; epoxy compounds; oxetane compounds; and benzo compounds.

compound.

<<<Compounds with hydroxymethyl, alkoxymethyl or acyloxymethyl>>>

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

In the formula, t represents an integer from 1 to 20, R ¹⁰⁴ represents a t-valent organic group with a carbon number of 1 to 200, R ¹⁰⁵ represents a group represented by -OR ¹⁰⁶ or -OCO-R ¹⁰⁷ , R ¹⁰⁶ represents a hydrogen atom or An organic group having 1 to 10 carbon atoms. R ¹⁰⁷ represents an organic group having 1 to 10 carbon atoms.

In the formula, R ⁴⁰⁴ represents a divalent organic group with 1 to 200 carbon atoms, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , and R ⁴⁰⁶ represents a hydrogen atom or an organic group with 1 to 10 carbon atoms. group, R ⁴⁰⁷ represents an organic group with 1 to 10 carbon atoms.

In the formula, u represents an integer from 3 to 8, R ⁵⁰⁴ represents a u-valent organic group with a carbon number of 1 to 200, R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ , and R ⁵⁰⁶ represents a hydrogen atom. Or an organic group with 1 to 10 carbon atoms. R ⁵⁰⁷ represents an organic group with 1 to 10 carbon atoms.

Specific examples of the compound represented by formula (AM4) include 46DMOC, 46DMOEP (the above are trade names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, and DML-PC. , DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol (2,6-dimethoxymethyl-4-tertiary butylphenol) , 2,6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-dacethoxymethyl-p-cresol (2,6-diethoxymethyl-p-cresol) Cresol) etc.

Specific examples of the compound represented by formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML- TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade names, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.).

<<<Epoxy compounds (compounds with epoxy groups)>>>

As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. Epoxy cross-links at temperatures below 200°C and does not cause dehydration reactions due to cross-linking, making it difficult to shrink the film. Therefore, by containing an epoxy compound, low-temperature hardening and warpage of the composition can be effectively suppressed.

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

Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polypropylene glycol diglycidyl ether and other polypropylene glycol type epoxy resins; Alkylene glycol type epoxy resin; polymethyl (glycidyloxypropyl) siloxane and the like contain epoxy silicone, but are not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) Trademark) EXA-4850-150, EPICLONEXA-4850-1000, EPICLON (Registered Trademark) EXA-4816, EPICLON (Registered Trademark) EXA-4822 (the above are trade names, manufactured by DIC Corporation), RIKARESIN (Registered Trademark) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above are trade names, manufactured by ADEKA CORPORATION), etc. Among these, excellent in terms of warpage suppression and heat resistance Considering different aspects, epoxy resin containing polyethylene oxide group is better. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E are preferred because they contain polyethylene oxide groups.

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

Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxetane, 1,4-bis{ [(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzene dicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl] ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone, or both of them can be mixed. More than one species.

化合物(具有聚苯并

唑基之化合物)>>> <<<Benzo

Compounds (with polybenzo

Azole-based compounds)>>>

化合物因源自開環加成反應之交聯反應而於硬化時不產生脫氣，進而減少熱收縮而抑制產生翹曲，因此為較佳。 Benzo

The compound is preferable because it does not produce outgassing during hardening due to the cross-linking reaction derived from the ring-opening addition reaction, thereby reducing thermal shrinkage and suppressing warpage.

化合物的較佳的例，可舉出B-a型苯并

、B-m型苯并

(以上為商品名，Shikoku Chemicals Corporation製)、聚羥基苯乙烯樹脂的苯并

加成物、酚醛清漆型二氫苯并

化合物。該等可以單獨使用，或者可以混合兩種以上。 as benzo

Preferable examples of the compound include Ba-type benzo

, Bm type benzo

(the above are trade names, manufactured by Shikoku Chemicals Corporation), polyhydroxystyrene resin benzo

Adduct, novolak type dihydrobenzo

compound. These may be used alone, or two or more types may be mixed.

When a polymerizable compound is contained, its content is preferably more than 0% by mass and 60% by mass or less based on 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 mass% or less, and further preferably 30 mass% or less.

One type of other polymerizable compounds may be used alone, or two or more types may be mixed and used. When two or more types are used at the same time, the total amount is preferably within the above range.

<Solvent>

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

Examples of preferred esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, Alkoxyethyl acetate, alkoxybutyl acetate (e.g., methyl methoxyacetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate etc.)), 3-alkoxypropionic acid alkyl esters (for example, 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxypropionic acid methyl ester , ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid alkyl esters (for example, 2- Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2-methoxypropionic acid propyl ester, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester)), 2-alkoxy-2-methylpropionic acid methyl ester and 2- Ethyl alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate ester, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetyl acetate, ethyl acetyl acetate, 2-oxo Methyl butyrate, ethyl 2-oxobutyrate, etc.

Examples of preferred ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve. Acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropylene Ether acetate, etc.

Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and the like.

Preferable aromatic hydrocarbons include toluene, xylene, anisole, limonene, and the like.

Preferable examples of the sericene include dimethyl serotonin.

Preferred examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Dimethylformamide, etc.

Regarding the solvent, from the viewpoint of improving the coating surface, etc., it is also preferable to mix two or more forms.

In the present invention, it is selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, and butyl acetate. , methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, ethyl carbitol acetate, butyl carbitol Acetate, N-methyl-2-pyrrolidone, propyl One solvent of glycol methyl ether and propylene glycol methyl ether acetate or a mixed solvent composed of two or more is preferred. It is particularly good to use dimethylsulfoxide and γ-butyrolactone at the same time.

Regarding the content of the solvent, from the viewpoint of coatability, the total solid content concentration of the photosensitive resin composition of the present invention is preferably 5 to 80 mass %, and is preferably 5 to 75 mass %. To be more preferable, the amount is 10 to 70 mass %, and the amount is 40 to 70 mass %, which is still more preferable. The content of the solvent can be adjusted according to the desired thickness and coating method.

The solvent may contain only one type or two or more types. When two or more solvents are contained, the total amount is preferably within the above range.

<Migration inhibitor>

The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, it is possible to effectively suppress metal ions originating from the metal layer (metal wiring) from being transferred into the photosensitive resin composition layer.

唑環、噻唑環、吡唑環、異

唑環、異噻唑環、四唑環、吡啶環、噠

環、嘧啶環、吡

環、哌啶環、哌

環、嗎啉環、2H-吡喃環及6H-吡喃環、三

環)之化合物、具有硫脲類及巰基之化合物、受阻酚系化合物、水楊酸衍生物系化合物、醯肼衍生物系化合物。尤其，能夠較佳地使用1,2,4-三唑、苯并三唑等三唑系化合物、1H-四唑、5-苯基四唑等四唑系化合物。 The migration inhibitor is not particularly limited, and examples thereof include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring,

Azole ring, thiazole ring, pyrazole ring, iso

Azole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridine ring

ring, pyrimidine ring, pyridine

ring, piperidine ring, piperazine

Ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, tri

ring) compounds, compounds having thioureas and mercapto groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazine derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be suitably used.

In addition, an ion scavenger that captures anions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitors described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, and the compounds described in Japanese Patent Application Laid-Open No. 2011 can be used. - Compounds described in paragraph 0052 of Publication No. 059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, compounds described in paragraph 0166 of International Publication No. WO2015/199219, etc. .

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 mass %, more preferably 0.05 to 2.0 mass %, and 0.1 to 1.0 mass % relative to the total solid content of the photosensitive resin composition. Mass % is more preferable.

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

<Polymerization inhibitor>

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

、N-亞硝基二苯胺、N-苯基萘胺、伸乙基二胺四乙酸、1,2-環己二胺四乙酸、乙二醇醚二胺四乙酸、2,6-二-三級丁基-4-甲基苯酚、5-亞硝基-8-羥基喹啉、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5-(N-乙基-N-磺基丙基胺)苯酚、N-亞硝基-N-(1-萘基)羥胺銨鹽、雙(4-羥基-3,5-三級丁基)苯基甲烷等。又，亦能夠使用日本特開2015-127817號公報的0060段中所記載之聚合抑制劑及國際公開WO2015/125469號的0031~0046段中所記載之化合物。 As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, p-tertiary butylcatechol, 1 ,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl -6-tertiary butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiophene

, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-diaminetetraacetic acid Tertiary butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso -5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tertiary butyl base) phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Laid-Open No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. WO2015/125469 can also be used.

Furthermore, the following compounds (Me is methyl) can also be used.

When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass %, and 0.02 to 3 mass % relative to the total solid content of the photosensitive resin composition of the present invention. More preferably, 0.05~2.5% by mass is still more preferably.

There may be only one type of polymerization inhibitor, or two or more types of polymerization inhibitors may be used. When there are two or more polymerization inhibitors, the total amount is preferably within the above range.

<Metal adhesion improver>

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

Examples of the silane coupling agent include the compounds described in paragraph 0167 of International Publication No. WO2015/199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, and the compounds described in International Publication No. WO2011/080992A1. Compounds described in paragraphs 0063 to 0071 of Japanese Patent Application Laid-Open No. 2014-191252, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-041264, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, The compound described in paragraph 0055 of International Publication No. WO2014/097594. In addition, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358. In addition, it is also preferable to use the following compounds as a silane coupling agent. In the following formula, Et represents an ethyl group.

Moreover, the compound described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186, and the sulfide described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can also be used as the metal adhesion improver.

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 0.5 to 5 parts by mass relative to 100 parts by mass of the polymer precursor. By setting the value above the lower limit, the adhesion between the cured film and the metal layer after the curing process becomes good, and by setting it below the upper limit, the heat resistance and mechanical properties of the cured film after the curing process become good. The number of metal adhesion improvers may be only one type, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

<Other additives>

The photosensitive resin composition of the present invention can contain various additives as necessary, such as thermal acid generators, sensitizing dyes, chain transfer agents, surfactants, and higher fatty acid derivatives, within the scope that does not impair the effects of the present invention. , inorganic particles, hardener, hardening catalyst, filler, antioxidant, ultraviolet absorber, aggregation inhibitor, etc. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

<<sensitizing pigment>>

The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and enters an electronically excited state. The sensitizing dye in the electronically excited state comes into contact with the thermal hardening accelerator, thermal radical polymerization initiator, photo radical polymerization initiator, etc., resulting in electron transfer, energy transfer, heat generation and other effects. Take this, heat The hardening accelerator, thermal radical polymerization initiator, and photo radical polymerization initiator undergo chemical changes and decompose, and generate free radicals, acids, or bases. For details of the sensitizing dye, please refer to the description in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and this content is incorporated into this specification.

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

<<Chain transfer agent>>

The photosensitive resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined in, for example, pages 683-684 of the Polymer Dictionary, third edition (edited by The Society of Polymer Science, Japan, 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These can generate free radicals by donating hydrogen to low-activity free radicals, or by deprotonating them after oxidation. In particular, thiol compounds can be preferably used.

In addition, the compounds described in paragraphs 0152 to 0153 of International Publication No. WO2015/199219 can also be used as the chain transfer agent.

When the photosensitive resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention, and 1 to 10 parts by mass. Parts by mass are more preferred, and 1 to 5 parts by mass are still more preferred. There may be only one type of chain transfer agent, or two or more types of chain transfer agents may be used. When there are two or more chain transfer agents, the total range is preferably within the above range.

<<Surfactant>>

From the viewpoint of further improving coatability, various surfactants can be added to the photosensitive resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. In addition, the following surfactants are also preferred.

In addition, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International Publication No. WO2015/199219 can also be used.

When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass relative to the total solid content of the photosensitive resin composition of the present invention. Mass %. There may be only one type of surfactant, or two or more types of surfactants may be used. When there are two or more surfactants, the total range is preferably within the above range.

<<Higher fatty acid derivatives>>

In order to prevent inhibition of polymerization due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the photosensitive resin composition of the present invention to be locally present in the drying process after coating. surface of the composition.

In addition, compounds described in paragraph 0155 of International Publication No. WO2015/199219 can also be used as the higher fatty acid derivatives.

When the photosensitive resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the photosensitive resin composition of the present invention. The number of higher fatty acid derivatives may be only one type or two or more types. When there are two or more types of higher fatty acid derivatives, the total range is preferably within the above range.

<Restrictions on other contained substances>

From the viewpoint of coating surface shape, the moisture content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and still more preferably less than 0.6% by mass.

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

Furthermore, as a method of reducing metal impurities unintentionally contained in the photosensitive resin composition of the present invention, a raw material constituting the photosensitive resin composition of the present invention is selected and a raw material with a small metal content is selected. The raw materials of the photosensitive resin composition are filtered through a filter, the inside of the device is lined with polytetrafluoroethylene, and distillation is performed under conditions that suppress contamination as much as possible.

Considering the use as a semiconductor material and from the viewpoint of wiring corrosion, the content of halogen atoms in the photosensitive resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm. ppm is more preferably. Among them, those in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total number of chlorine atoms and bromine atoms or chlorine ions and bromide ions is within the above range.

As a container for storing the photosensitive resin composition of the present invention, a conventionally known container can be used. In addition, as a storage container, in order to prevent impurities from being mixed into raw materials or compositions, it is also preferable to use a multi-layer bottle with an inner wall of six types of six-layer resins or a bottle with six types of resins formed into a seven-layer structure. Examples of such containers include those 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 the above-mentioned components. The mixing method is not particularly limited and can be performed by conventionally known methods.

In addition, for the purpose of removing foreign matter such as garbage and particles in the composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. Filters can be pre-cleaned with organic solvents. In the filtration process of the filter, multiple types of filters can be used in parallel or in series. When using multiple types of filters, filters with different pore sizes or materials can be used in combination. Also, yes to filter various materials multiple times. When filtering multiple times, cyclic filtering can be used. In addition, filtration may be performed after pressurization. When filtration is performed after pressurization, the pressurization pressure is preferably 0.05 MPa or more and 0.3 MPa or less.

In addition to filtration using filters, impurity removal using adsorbent materials can also be performed. It is also possible to combine filter filtration and impurity removal using adsorbent materials. As the adsorbent material, known adsorbent materials can be used. Examples include inorganic adsorbent materials such as silica gel and zeolite, and organic adsorbent materials such as activated carbon.

<Cured film, laminated body, semiconductor element, and manufacturing method of the same>

Next, the cured film, the laminated body, the semiconductor element, and the manufacturing method of these are demonstrated.

The cured film of the present invention is formed by curing the photosensitive resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Moreover, as an upper limit, it can be 100 micrometers or less, and can also be 30 micrometers or less.

The cured film of the present invention can be laminated in two or more layers and further in 3 to 7 layers to form a laminated body. A laminate system having two or more layers of the cured film of the present invention is preferably one in which a metal layer is provided between the cured films. These metal layers can be preferably used as metal wiring such as rewiring layers.

Examples of fields to which the cured film of the present invention can be applied include insulating films for semiconductor elements, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition, examples include sealing films, substrate materials (base films or cover layers of flexible printed circuit boards, interlayer insulating films), or insulating films for actual mounting purposes as described above by etching. Pattern formation, etc. Regarding such uses, for example, you can refer to Science & Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Masaaki Kakimoto/Supervisor, CMC Technical Library "Polyimide Materials" "Basic and Development" released in November 2011, Japan Polyimide. Aromatic Polymer Research Society/edited "Latest Polyimide Fundamentals and Applications" NTS, August 2010, etc.

Furthermore, the cured film in the present invention can also be used in the production of offset printing plates or screen plates, use of molded parts, production of protective paints and dielectric layers in electronics, especially microelectronics, and the like.

The manufacturing method of the cured film of this invention includes the case of using the photosensitive resin composition of this invention. Specifically, processes including the following (a) to (d) are preferred.

(a) Film formation process of applying a photosensitive resin composition to a substrate to form a film

(b) After the film formation process, the exposure process of the exposed film

(c) The development process of developing the exposed photosensitive resin composition layer

(d) Heating process of heating the developed photosensitive resin composition at 80~450℃

As in this embodiment, the exposed resin layer can be further hardened by heating after development. In this heating process, the thermal base generator of the present invention acts to obtain sufficient curability.

The manufacturing method of the laminated body in the preferred embodiment of this invention includes the manufacturing method of the cured film of this invention. The manufacturing method of the laminated body of this embodiment is as described above. In the method of manufacturing a cured film, after the cured film is formed, the process of (a), the processes of (a) to (c), or the processes of (a) to (d) are further performed. In particular, it is preferable to perform each of the above processes in sequence a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured films in this way, a laminated body can be formed. In the present invention, it is particularly preferred to provide a metal layer on the upper side of the portion where the cured film is provided, between the cured films, or both. In addition, in the production of the laminated body, it is not necessary to repeat all the processes (a) to (d). As mentioned above, it is possible to perform at least (a), preferably (a) to (c) or (a) a plurality of times. ~ (d) process to obtain a laminated body of the cured film.

<<Film formation process (layer formation process)>>

A manufacturing method according to a preferred embodiment of the present invention includes a film formation process (layer formation process) in which a photosensitive resin composition is applied to a substrate to form a film (layered).

The type of substrate can be appropriately set according to the application, but is not particularly limited. Examples include semiconductor manufacturing substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, and evaporated films. , magnetic film, reflective film, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, electrode plate of plasma display panel (PDP), etc. In the present invention, a semiconductor manufacturing substrate is particularly preferred, and a silicon substrate is even more preferred.

Furthermore, when the photosensitive resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as the substrate.

As a method of applying the photosensitive resin composition to a substrate, coating is preferred.

Specifically, examples of applicable methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, and spin coating. Slit coating method and inkjet method, etc. From the viewpoint of thickness uniformity of the photosensitive resin composition layer, spin coating, slit coating, spray coating, and inkjet are more preferred. By adjusting the appropriate solid content concentration or coating conditions according to the method, a resin layer with a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferable. If it is a rectangular substrate, slit coating is preferable. Or spraying method, inkjet method, etc. are better. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

<<Drying process>>

The manufacturing method of the present invention may further include a drying process in order to remove the solvent after forming the photosensitive resin composition layer and after the film formation process (layer formation process). The preferred drying temperature is 50~150°C, 70~130°C is more preferred, and 90~110°C is even more preferred. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<<Exposure Process>>

The manufacturing method of the present invention may include an exposure process to expose the above-mentioned photosensitive resin composition layer. The amount of exposure is not particularly limited within a range that can harden the photosensitive resin composition. For example, it is preferably 100 to 10000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, and more preferably 200 to 8000 mJ/cm ² .

The exposure wavelength can be appropriately set within the range of 190~1000nm, with 240~550nm being preferred.

Regarding the exposure wavelength, if described in relation to the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, etc. Regarding the photosensitive resin composition in the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and exposure by i-rays is particularly preferred. As a result, particularly high exposure sensitivity can be achieved.

<<Development Process>>

The manufacturing method of the present invention may include a development process to develop the exposed photosensitive resin composition layer. By performing development, the unexposed portion (non-exposed portion) is removed. The development method is not particularly limited as long as a desired pattern can be formed. For example, development methods such as spin immersion, spray, immersion, and ultrasonic waves can be used.

Development is performed using a developer. The developer can be used without particular limitation as long as it can remove the unexposed portion (non-exposed portion). It is preferred that the developer contains an organic solvent, and it is even more preferred that the developer contains more than 90% organic solvent. In the present invention, it is preferable that the developer contains an organic solvent with a ClogP value of -1 to 5, and it is even more preferable that the developer contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be calculated as a calculated value by inputting the structural formula into ChemBioDraw.

Regarding the organic solvent, suitable examples of esters include ethyl acetate, n-butyl acetate, amyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyric acid. Ethyl ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (example: methyl alkoxyacetate , ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyethyl acetate esters, etc.)), 3-alkoxypropionic acid alkyl esters (for example: 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxypropionic acid methyl ester) Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid alkyl esters (example: 2 -Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate ester, 2-methoxypropylpropionate, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester)), 2-alkoxy-2-methylpropionic acid methyl ester and 2 -Ethyl alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate Esters, ethyl pyruvate, propyl pyruvate, methyl acetyl acetate, ethyl acetate acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, for example, Suitable examples include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethylene glycol monoethyl ether. Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones Suitable examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrole. Suitable examples of the aromatic hydrocarbons include toluene, xylene, anisole, limonene, etc., and suitable examples of the sericene hydrocarbons include dimethyl styrene.

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

It is preferable that 50% by mass or more of the developer is an organic solvent, more preferably 70% by mass or more is an organic solvent, and still more preferably 90% by mass or more is an organic solvent. In addition, 100% by mass of the developer may be an organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but it can usually be performed at 20 to 40°C.

After using the developer, it can then be rinsed. It is better to use a different solvent from the developer for rinsing. For example, the solvent contained in the photosensitive resin composition can be used for flushing. The optimal flushing time is 5 seconds to 1 minute.

<<Heating process>>

The manufacturing method of the present invention preferably includes a heating process after the film formation process (layer formation process), drying process or development process. During the heating process, a cyclization reaction of the polymer precursor is performed. Furthermore, the composition of the present invention may contain a radically polymerizable compound other than the polymer precursor, and the radically polymerizable compound other than the unreacted polymer precursor may be cured during the process. As for the heating temperature (maximum heating temperature) of the middle layer in the heating process, 50°C or above is preferred, 80°C or above is even better, 140°C or above is further preferred, 150°C or above is further preferred, and 160°C or above is still further preferred. Preferable, and above 170°C 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 still further preferably 220°C or lower.

Regarding heating, it is preferable to conduct the heating at a temperature rising rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the temperature rise rate to 1°C/min or more, excessive volatilization of amine can be prevented while ensuring productivity, and by setting the temperature rise rate to 12°C/min or less, the residual stress of the cured film 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 still more preferably 25°C to 120°C. The temperature at the start of heating represents the temperature at which the process starts to be heated to the highest heating temperature. For example, when the photosensitive resin composition is applied to a substrate and then dried, the temperature of the dried film (layer) is, for example, from 30 to 200 degrees lower than the boiling point of the solvent contained in the photosensitive resin composition. It is better to gradually increase the temperature to ℃.

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

In particular, when forming a multilayer laminated body, from the viewpoint of interlayer adhesion of the cured film, heating is preferably performed at a heating temperature of 180°C to 320°C, and more preferably 180°C to 260°C. The reason for this is not certain, but it is considered that the reason is that by setting this temperature, the ethynyl groups of the polymer precursor between the layers undergo a cross-linking reaction.

Heating can be done in stages. As an example, the temperature can be raised from 25°C to 180°C at 3°C/min and held at 180°C for 60 minutes. The temperature can be raised from 180°C to 200°C at 2°C/minute and held at 200°C for 120 minutes before processing. . As a pretreatment process, the heating temperature is preferably 100~200℃, 110~190℃ is better, and 120℃ ~185℃ is further preferred. In this pretreatment process, it is also preferable to perform the treatment while irradiating ultraviolet rays as described in U.S. Patent No. 9159547. The characteristics of the membrane can be improved through these pre-treatment processes. The pretreatment process can be carried out in a short time of about 10 seconds to 2 hours, and 15 seconds to 30 minutes is better. Pretreatment can be a two-stage or more process. For example, pretreatment process 1 can be performed in the range of 100~150℃, and then pretreatment process 2 can be performed in the range of 150~200℃.

Furthermore, cooling may be performed after heating. In this case, the cooling rate is preferably 1 to 5° C./minute.

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

<<Metal layer formation process>>

The manufacturing method of the present invention preferably includes a metal layer forming process of forming a metal layer on the surface of the photosensitive resin composition layer after development.

The metal layer is not particularly limited, and existing metal types can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferred, and copper is even more preferred.

The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Laid-Open Nos. 2007-157879, 2001-521288, 2004-214501, and 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless Electrolytic plating, etching, printing and methods of combining these, etc. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating can be cited.

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

<<Layered Process>>

The manufacturing method of the present invention preferably further includes a lamination process.

The lamination process includes performing (a) film formation process (layer formation process), (b) exposure process, (c) development process, and (d) heating process on the surface of the cured film (resin layer) or metal layer. A series of processes. However, the film forming process of (a) may be repeated only. Alternatively, (d) the heating process may be performed collectively at the end or in the middle of the lamination process. That is, it is also possible to adopt an aspect in which the processes (a) to (c) are repeated a predetermined number of times, and then the heating in (d) is performed to collectively harden the laminated photosensitive resin composition layers. In addition, the (c) development process may be followed by the (e) metal layer forming process. In this case, the heating of (d) may be performed each time, or the heating of (d) may be performed collectively after laminating a predetermined number of times. There is no doubt that the lamination process can also appropriately include the above-mentioned drying process and heating process.

When the lamination process is performed after the lamination process, the surface activation treatment process may be performed after the above-mentioned heating process, and after the above-mentioned exposure process or after the above-mentioned metal layer forming process. As surface activation treatment, plasma treatment is exemplified.

It is better to carry out the above-mentioned lamination process 2 to 5 times, and even more preferably 3 to 5 times.

For example, a structure in which the resin layer has three to seven layers is preferable, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, and more preferably three to five layers.

In the present invention, it is particularly preferred 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, the method of sequentially repeating (a) the film formation process, (b) the exposure process, (c) the development process, (e) the metal layer formation process, (d) the heating process, or sequentially repeating (a) ) film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, and (d) heating process is integrated at the end or in the middle. By alternately performing a lamination process for laminating a photosensitive resin composition layer (resin) and a metal layer forming process, the photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses a semiconductor element having the cured film or laminate of the present invention. As a specific example of a semiconductor element using the photosensitive resin composition of the present invention in the formation of an interlayer insulating film for a rewiring layer, refer to the descriptions in paragraphs 0213 to 0218 of Japanese Patent Application Laid-Open No. 2016-027357 and FIG. 1 records, these contents are incorporated into this manual.

[Example]

Hereinafter, the present invention will be described in further detail with reference to examples. The materials, usage amounts, proportions, treatment contents, treatment processes, etc. shown in the following examples can be appropriately changed within the scope that does not deviate from the gist of the present invention. Therefore, this invention The scope of explanation is not limited to the specific examples shown below. Unless otherwise stated, "parts" and "%" are based on mass.

<Synthesis Example 1: Synthesis of Thermal Base Generator BE-1>

In a flask equipped with a condenser, 6.00 g of 2-aminephenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 35.0 g of N-methylpyrrolidone (manufactured by KANTO CHEMICAL CO., INC.), and the mixture was cooled. to 0℃. Next, 5.96 g of phenyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 10.0 g of N-methylpyrrolidone (manufactured by KANTO CHEMICAL CO., INC.), and the mixture was dropped over 1 hour. add. After the dropwise addition, stir at room temperature for 2 hours, pour 300 mL of 0.5N hydrochloric acid water, filter the precipitate, wash with 100 mL of water, wash with acetone/methanol mixture, and dry at 40°C for 8 hours to obtain 7.2g of thermal base generator BE-1 with the following structure.

<Synthesis Example 2: Synthesis of Thermal Base Generator BE-2>

In a flask equipped with a condenser, 7.20 g of 2-aminephenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 41.0 g of N-methylpyrrolidone (manufactured by KANTO CHEMICAL CO., INC.), and the mixture was cooled. to 0℃. Next, 6.67 g of isophorone isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. After dropwise addition, stir at room temperature for 2 hours, filter the precipitate, and moisten with 50 mL of N-methylpyrrolidone. Washed, reslurry-washed with 400 mL of acetone for 1 hour, and filtered. After drying at 40° C. for 8 hours, 6.8 g of the thermal base generator BE-2 having the following structure was obtained.

<Synthesis Example 3: Synthesis of Thermal Base Generator BE-3>

In a flask equipped with a condenser, 6.48 g of 3,3'-dihydroxybenzidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in N-methylpyrrolidone (manufactured by KANTO CHEMICAL CO., INC.) 40.0g and cool to 0°C. Next, 7.65 g of cyclohexyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. After the dropwise addition, the mixture was stirred at room temperature for 2 hours, and the precipitate was filtered, washed with 50 mL of N-methylpyrrolidone, reslurry-washed with 400 mL of acetone for 1 hour, and filtered. After drying at 40° C. for 8 hours, 9.8 g of thermal base generator BE-3 having the following structure was obtained.

<Synthesis Example 4: Synthesis of Thermal Base Generator BE-4>

In a flask equipped with a condenser, 3.15 g of 3,3'-dihydroxybenzidine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.02 g of cyclohexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in N,N-dimethylacetamide (manufactured by KANTO CHEMICAL CO., INC.) 35.0 g. Next, 2.91 g of 1.3-bis(methyl isocyanate)cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. After the dropwise addition, the mixture was stirred at room temperature for 1 hour, and 15 mL of methanol was added and dissolved. This was poured into a mixture of 400 mL of methanol and 400 mL of water, and the precipitate was filtered, rinsed with 100 mL of water and 100 mL of methanol in sequence, and filtered. After drying at 40° C. for 8 hours, 5.2 g of thermal base generator (resin) BE-4 having the following structure was obtained. The weight average molecular weight of the above resin is 20,300.

<Synthetic Example 5: Combination of oxydiphthalic anhydride, 4,4'-diphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether Synthesis of polyimide precursor resin A-1>

In a dry reactor equipped with a stirrer, a condenser, and a flat-bottomed joint with an internal thermometer, 10.0 g (32.25 mmol) of oxydiphthalic anhydride was suspended in 140 mL of diglylene dimethyl ether while removing water. middle. Then add 16.8g (129mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone and 10.7g of pyridine. (135 mmol) and stirred at a temperature of 60°C for 18 hours. Next, the mixture was cooled to -20°C, and then 16.1 g (135.5 mmol) of thionite chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was warmed to room temperature and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise to the obtained transparent liquid over 1 hour. Next, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tertiary butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried under reduced pressure at 45° C. for 3 days. The polyimide precursor resin (A-1) has Mw=24800 and Mn=10500.

<Synthesis Example 6: Synthesis of polyimide precursor resin A-2 using oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether >

In a dry reactor equipped with a stirrer, a condenser, and a flat-bottom joint with an internal thermometer, 20.0 g (64.5 mmol) of oxydiphthalic anhydride was suspended in 140 mL of diglylene dimethyl ether while removing water. Next, 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 10.7 g (135 mmol) of pyridine were added, and the mixture was stirred at a temperature of 60° C. for 18 hours. Next, the mixture was cooled to -20°C, and then 16.1 g (135.5 mmol) of thionite chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was warmed to room temperature and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise to the obtained transparent liquid over 1 hour. Next, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tertiary butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried under reduced pressure at 45° C. for 3 days. The polyimide precursor resin (A-2) has Mw=23500 and Mn=8800.

<Examples and Comparative Examples>

The components described in the following tables were mixed to obtain each photosensitive resin composition. The obtained photosensitive resin composition was filtered under pressure through a filter with a pore width of 0.8 μm. Furthermore, each photosensitive resin composition was evaluated for elongation at break and storage stability.

<Components of photosensitive resin composition>

Details of the components constituting each photosensitive resin composition are as follows.

(A) Polymer precursor: A-1 and A-2 synthesized above

(B) Specific thermal base generator: BE-1~BE-4 synthesized above

Base generator used in comparative examples: the following compounds

(C)Solvent

DMSO: dimethylsulfoxide

GBL: gamma-butyrolactone

The mixing ratio of DMSO and GBL is 20:80 in terms of mass ratio.

(D) Photopolymerization initiator (all are trade names)

OXE-01: IRGACURE OXE 01 (made by BASF)

OXE-02: IRGACURE OXE 02 (made by BASF)

(E) Polymerizable compound (all are trade names)

SR-209: SR-209 (manufactured by Sartomer Company, Inc.)

SR-231: SR-231 (manufactured by Sartomer Company, Inc.)

SR-239: SR-239 (manufactured by Sartomer Company, Inc.)

(F)Polymerization inhibitor

F-1: 1,4-benzoquinone

F-2: 4-methoxyphenol

F-3: 1,4-dihydroxybenzene

(G) Metal adhesion improver

G-1: The following compound

G-2: The following compounds

G-3: The following compounds

Et represents ethyl.

(H)Migration inhibitor

H-1: 1H-tetrazole

H-2: 1,2,4-triazole

H-3: 5-phenyltetrazole

(I) Other thermal base generators

I-1:

[Chemical 47]

<Evaluation of elongation at break (film strength measurement)>

Each of the photosensitive resin compositions described in the above table was applied on the silicon wafer by spin coating to form a photosensitive resin composition layer. The silicon wafer on which the obtained photosensitive resin composition layer was formed was dried on a hot plate at 100° C. for 5 minutes, thereby obtaining a photosensitive resin composition layer with a uniform thickness of approximately 15 μm on the silicon wafer. The obtained thermophotosensitive resin composition layer (resin layer) was heated at a temperature increasing rate of 10° C./min in a nitrogen atmosphere. After reaching 250° C., it was heated for 3 hours. The hardened resin layer (cured film) was immersed in a 4.9% hydrofluoric acid solution, and the cured film was peeled off from the silicon wafer. The peeled cured film was used to produce a test piece with a width of 3 mm and a sample length of 30 mm using a punching machine. Using a tensile testing machine (TENSILON) at a crosshead speed of 300 mm/min, in an environment of 25°C and 65% RH (relative humidity), in compliance with JIS-K6251, the obtained test piece was tested in the longitudinal direction of the film. measured. The evaluation was performed five times each, and the average value was used for the elongation at break of the film (elongation at break).

A More than 60%

B More than 55% and less than 60%

C More than 50% and less than 55%

D is less than 50%

<Evaluation of storage stability (film thickness change rate measurement)>

<<Premenstrual membrane thickness>>

Each of the photosensitive resin compositions described in the above table was applied on the silicon wafer by spin coating to form a photosensitive resin composition layer. The silicon wafer on which the obtained photosensitive resin composition layer was formed was dried on a hot plate at 100° C. for 5 minutes, thereby obtaining a photosensitive resin composition layer with a uniform thickness of approximately 15 μm on the silicon wafer. This value was regarded as the film thickness before time.

<<Film thickness after time>>

Each photosensitive resin composition described in the above table was put into a glass container and sealed. After leaving it standing in an environment of 25°C for 14 days, it was coated by spin coating using the same rotation speed as when determining the film thickness before time. The photosensitive resin composition layer is formed on the silicon wafer. The silicon wafer on which the obtained photosensitive resin composition layer was formed was dried on a hot plate at 100° C. for 5 minutes, thereby obtaining a uniform photosensitive resin composition layer on the silicon wafer. The film thickness of the obtained photosensitive resin composition layer was measured in the same manner as above, and the value was used as the film thickness after time.

<<Film thickness change rate>>

The film thickness change rate was calculated by the following equation.

Film thickness change rate [%] = | Film thickness before time - Film thickness after time | / Film thickness before time × 100

Evaluation level and film thickness change rate

A: Less than 10%

B: More than 10% and less than 15%

C: more than 15% and less than 20%

D: More than 20%

From the above results, it is known that the photosensitive resin composition containing a specific thermal base generator and a heterocyclic-containing polymer precursor has excellent curing properties and storage stability.

<Example 100>

The photosensitive resin composition of Example 1 was pressure-filtered through a filter with a pore width of 1.0 μm, and then spin-molded (3500 rpm, 30 seconds) on the surface of a resin substrate on which a copper thin layer was formed. 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). Exposure was performed at a wavelength of 365 nm with an exposure dose of ²⁰⁰ mJ/cm via a mask. After exposure, it was baked, developed with cyclopentanone for 30 seconds, and rinsed with PGMEA for 20 seconds to obtain a pattern.

Next, it was heated at 230° C. for 3 hours to form an interlayer insulating film for a rewiring layer. This interlayer insulating film for rewiring layers has excellent insulation properties.

Claims (26)

A photosensitive resin composition containing: a thermal base generator represented by the following formula (N1), a polyimide precursor and polybenzo

at least one precursor compound of an azole precursor;

^In the ^formula (N1 ^{) ,} L ^N is a trivalent hydrocarbon group connected ^from adjacent nitrogen atoms to The content of the base generator is 0.5 to 30% by mass relative to the total solid content of the photosensitive resin composition. The photosensitive resin composition described in claim 1, wherein in the formula (N1), at least part of the connecting chain in L ^N is an aryl group. The photosensitive resin composition described in item 1 of the patent application, wherein the thermal base generator is a compound represented by formula (N2),

In the formula ( ^{N2 ) ,} X ^{N1 and} A hydrocarbon group of 1 to 20, L ^N1 and L ^N2 each independently represent a hydrocarbon group with a carbon number of 1 to 20, n1 represents 0 or 1, n2 represents an integer of 0 to 10, the sum of n1 and n2 is more than 1, n3 represents more than 1 is an integer, when n1=1, L ^N1 is a divalent hydrocarbon group connected from adjacent nitrogen atoms to X ^N1 , and is a hydrocarbon group with 2 to 6 atoms constituting the connecting chain, n2

When 1, L ^N2 is a 1+n2-valent hydrocarbon group connected from the adjacent nitrogen atom to X ^N2 , and is a hydrocarbon group with 2 to 6 atoms constituting the connecting chain. The photosensitive resin composition described in item 3 of the patent application, wherein in the formula (N2), the total number of X ^N1 and X ^N2 is equal to the total number of Z ^N1 . The photosensitive resin composition described in claim 3, wherein in the formula (N2), at least part of the connecting chains in L ^N1 and L ^N2 is an aryl group. The photosensitive resin composition described in item 1 of the patent application, wherein the thermal base generator is a polymer compound containing a repeating unit represented by formula (N3),

^In the formula ( ^{N3 ) ,} L ^N3 is a trivalent hydrocarbon group connected from an adjacent nitrogen atom to X ^N3 , and represents a hydrocarbon group with 2 to 6 atoms constituting the connecting chain. The photosensitive resin composition described in item 6 of the patent application, wherein the thermal base generator is a polymer compound containing a repeating unit represented by formula (N4),

^{In the formula ( N4 ) ,} Represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, L ^N4 is a tetravalent hydrocarbon group connected from an adjacent nitrogen atom to X ^N4 , and represents a hydrocarbon group with 2 to 6 atoms constituting the connecting chain, L ^N5 represents a divalent organic group. The photosensitive resin composition described in claim 7, wherein at least part of the connecting chain in L ^N4 is an aryl group. The photosensitive resin composition as described in any one of items 1 to 8 of the patent application, wherein X ^N in the formula (N1) is a hydroxyl group or a carboxyl group. The photosensitive resin composition described in any one of items 3 to 5 of the patent application, wherein X ^N1 or X ^N2 in the formula (N2) is a hydroxyl group or a carboxyl group. The photosensitive resin composition described in any one of items 6 to 8 of the patent application, wherein X ^N3 in the formula (N3) is a hydroxyl group or a carboxyl group. The photosensitive resin composition described in Item 7 or Item 8 of the patent application, wherein X ^N4 in the formula (N4) is a hydroxyl group or a carboxyl group. The photosensitive resin composition described in any one of items 1 to 8 of the patent application further includes a photoradical polymerization initiator and a radical polymerizable compound. Photosensitivity as described in any one of items 1 to 8 of the patent application scope A resin composition, wherein the precursor compound includes a polyimide precursor. The photosensitive resin composition described in item 14 of the patent application, wherein the polyimide precursor has a structural unit represented by the following formula (1),

In formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or 1-valent organic group. The photosensitive resin composition described in claim 15, wherein at least one of R ¹¹³ and R ¹¹⁴ in the formula (1) contains a radical polymerizable group. The photosensitive resin composition described in any one of items 1 to 8 of the patent application is used to form an interlayer insulating film for a rewiring layer. A cured film formed by curing the photosensitive resin composition described in any one of claims 1 to 17. A laminated body having two or more layers of cured films as described in claim 18, and having a metal layer between the cured films. A method for manufacturing a cured film, which includes a film formation process in which the photosensitive resin composition described in any one of claims 1 to 17 is applied to a substrate to form a film. The manufacturing method of the cured film described in item 20 of the patent application includes a process of heating the film at 50 to 450°C. A semiconductor element having a cured film as described in claim 18 or a laminated body as described in claim 19. A thermal base generator comprising a polymer compound containing a repeating unit represented by formula (N3);

^In the formula ( ^{N3 ) ,} L ^N3 is a trivalent hydrocarbon group connected from an adjacent nitrogen atom to X ^N3 , and represents a hydrocarbon group with 2 to 6 atoms constituting the connecting chain. The thermal base generator as described in item 23 of the patent application, wherein the polymer compound contains a repeating unit represented by formula (N4);

^{In the formula ( N4 ) ,} Represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, L ^N4 is a tetravalent hydrocarbon group connected from an adjacent nitrogen atom to X ^N4 , and represents a hydrocarbon group with 2 to 6 atoms constituting the connecting chain, L ^N5 represents a divalent organic group. The thermal base generator described in Item 23 or 24 of the patent application, wherein at least part of the connecting chain in L ^N4 is an aryl group. The thermal base generator described in item 23 or 24 of the patent application, wherein X ^N4 is a hydroxyl group or a carboxyl group.