TW202146527A - Photosensitive resin composition, method for producing pattern, photosensitive film, cured product, laminate, and device - Google Patents

Abstract

Provided are: a photosensitive resin composition containing at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and polybenzoxazole, an organic metal complex, and a sensitizer having a condensed ring structure; a method for producing a pattern made of the photosensitive resin composition; a photosensitive film formed from the photosensitive resin composition; a cured product of the photosensitive film; a laminate containing a layer made of the cured product; and a device including the cured product or the laminate.

Description

Photosensitive resin composition, method for producing pattern, photosensitive film, cured product, laminate, and element

The present invention relates to a photosensitive resin composition, a method for producing a pattern, a photosensitive film, a cured product, a laminate, and an element.

Polyimide or polybenzoxazole is excellent in heat resistance and insulating properties, and thus can be used in various applications. Although it does not specifically limit as said use, if the semiconductor element for actual mounting is taken as an example, the use as a material of an insulating film, a sealing material, or a protective film is mentioned. Moreover, it can also be used as a base film, a coverlay film, etc. of a flexible substrate.

For example, in the above applications, the polyimide or polybenzoxazole is selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor It is used in the form of the photosensitive resin composition of at least one of these resins. For example, such a photosensitive resin composition is applied to a substrate by coating or the like to form a photosensitive film, and thereafter, if necessary, exposure, development, heating, etc. are performed, whereby a cured product can be formed on the substrate. The above-mentioned polyimide precursor and the above-mentioned polybenzoxazole precursor are cyclized by heating, for example, and become polyimide and polybenzoxazole, respectively, in the cured product. The photosensitive resin composition can be applied by a known coating method, etc. Therefore, it can be said that, for example, the applied photosensitive resin composition has high flexibility in the design of the shape, size, and application position at the time of application. Excellent. In addition to the high performances possessed by polyimide, polybenzoxazole, and the like, the industrial application of the above-mentioned photosensitive resin composition is expected to expand from the viewpoint of excellent suitability for such production.

For example, Patent Document 1 describes a photosensitive resin composition comprising a polyimide precursor having a specific structure, a photopolymerization initiator, a sensitizer, an inhibitor for storage stability, and It consists of a solvent containing a sensitizer. Patent Document 2 describes a positive-type photosensitive resin composition characterized in that an acid is generated by decomposition of a polyimide precursor having a specific structure, a compound containing a vinyloxy group having a specific structure, and active light rays such as ultraviolet rays. It consists of a sensitizer, a sensitizer that promotes the decomposition of the sensitizer, and a solvent. Patent Document 3 describes a polyamic acid ester composition characterized in that (A) the polyamic acid ester of a specific structure and (B) are 0.3 to 0.3 to 10% by weight of organic titanium compound and (C) solvent are mixed.

[Patent Document 1] Japanese Patent Laid-Open No. 2003-186187 [Patent Document 2] Japanese Patent Laid-Open No. 2001-290270 [Patent Document 3] Japanese Patent Laid-Open No. 2004-091572

When forming a pattern composed of a photosensitive resin composition, it is required to improve the resolution and chemical resistance of the obtained pattern.

An object of the present invention is to provide a photosensitive resin composition having excellent resolution and chemical resistance of the obtained pattern, a method for producing a pattern composed of the photosensitive resin composition, and a photosensitive resin composition composed of the photosensitive resin composition. A film, a cured product of the above-mentioned photosensitive film, a layered product including a layer composed of the aforementioned cured product, and an element including the aforementioned cured product or the aforementioned layered product.

Hereinafter, examples of typical embodiments of the present invention are shown. <1> A photosensitive resin composition comprising: at least one resin selected from the group consisting of polyimide precursor, polybenzoxazole precursor, polyimide and polybenzoxazole; organometallic complexes; and A sensitizer with a condensed ring structure. <2> The photosensitive resin composition according to <1>, wherein The above-mentioned sensitizer contains at least one atom selected from the group consisting of a nitrogen atom and a sulfur atom as a ring member in the condensed ring structure. <3> The photosensitive resin composition according to <1> or <2>, wherein The above-mentioned sensitizer contains, as a condensed ring structure, at least one structure selected from the group consisting of an acridine structure, a thioxanthone structure, and an acridine structure. <4> The photosensitive resin composition according to any one of <1> to <3>, wherein Content of the said sensitizer is 0.5-5.0 mass parts with respect to 1 mass part of said organometallic complexes. <5> The photosensitive resin composition according to any one of <1> to <4>, wherein The above-mentioned organometallic complex is a metallocene compound. <6> The photosensitive resin composition according to any one of <1> to <5>, wherein The metal contained in the above-mentioned organometallic complex is at least one metal selected from the group consisting of titanium, zirconium and hafnium. <7> The photosensitive resin composition according to any one of <1> to <6>, wherein The organometallic complex described above has the ability to initiate photoradical polymerization. <8> A method for manufacturing a pattern, comprising: Film forming process, applying the photosensitive resin composition described in any one of <1> to <7> to a substrate to form a photosensitive film; an exposure process for exposing the above-mentioned photosensitive film; and In the developing process, the above-mentioned exposed photosensitive film is developed to obtain a pattern. <9> The method for producing a pattern according to <8>, wherein The exposure light used in the above exposure process includes light with a wavelength of 150-450 nm. <10> The manufacturing method of the pattern described in <8> or <9>, further comprising: In the heating process, the pattern obtained by the above-mentioned developing process is heated to harden the pattern. <11> A photosensitive film formed from the photosensitive resin composition according to any one of <1> to <7>. <12> A cured product of the photosensitive film described in <11>. <13> The cured product according to <12>, which is used as an interlayer insulating film for a rewiring layer. <14> A layered product comprising two or more layers composed of the cured product described in <12> or <13>, and including a metal layer between any layers composed of the cured product. <15> An element comprising the cured product according to <12> or <13>, or the laminate according to <14>. [Inventive effect]

According to the present invention, there are provided a photosensitive resin composition having excellent resolution and chemical resistance of the obtained pattern, a method for producing a pattern composed of the photosensitive resin composition, and a photosensitive film composed of the photosensitive resin composition. , a cured product of the above-mentioned photosensitive film, a layered product comprising a layer composed of the aforementioned cured product, and an element including the aforementioned cured product or the aforementioned layered product.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the illustrated embodiments. In this specification, the numerical range shown by "-" symbol shows the range which includes the numerical value described before and after "-" as a lower limit value and an upper limit value, respectively. In this specification, the term "process" 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 desired function of the process can be achieved. With regard to the labeling of groups (atomic groups) in this specification, unsubstituted and unsubstituted labels include both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes exposure by particle beams such as electron beams and ion beams in addition to exposure by light. Moreover, as light used for exposure, the bright-line spectrum of a mercury lamp, the extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, and radiation can be mentioned. In this specification, "(meth)acrylate" means both or either one of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" "Both or either one of them, and "(meth)acryloyl group" means both or either one of "acryloyl group" and "methacryloyl group". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content means the total mass of the components excluding the solvent from the total components of the composition. In addition, in this specification, the solid content concentration refers to the mass percentage of other components other than the solvent with respect to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values based on gel permeation chromatography (GPC measurement). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION), and guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) were obtained as columns. Unless otherwise specified, these molecular weights will be measured using THF (tetrahydrofuran) as an eluent. In addition, unless otherwise specified, the detection in GPC measurement used the wavelength 254nm detector of UV rays (ultraviolet rays). In this specification, when the positional relationship of each layer constituting the layered body is described as "upper" or "lower", other layers may exist above or below the layer of interest serving as a reference among the plurality of layers. That is, a third layer or a third requirement may be further interposed between the layer serving as the reference and the other layers described above, and the layer serving as the reference and the other layers do not need to be in contact with each other. In addition, unless otherwise specified, the direction in which the layers are stacked on the substrate is referred to as "up", or in the presence of a photosensitive film, the direction from the substrate toward the photosensitive film is referred to as "up", and the opposite direction is referred to as "up". "Down". In addition, the setting of such an up-down direction is for the convenience in this specification, and in an actual aspect, the "up" direction in this specification may also be different from the vertical upward direction. In this specification, unless otherwise specified, as each component contained in the composition, the composition may contain two or more types of compounds corresponding to the component. In addition, unless otherwise specified, the content of each component in the composition represents the total content of all compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23° C., the air pressure is 101,325 Pa (1 air pressure), and the relative humidity is 50% RH. In this specification, combinations of preferred aspects are preferred aspects.

(Photosensitive resin composition) The photosensitive resin composition of the present invention contains at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole (hereinafter, also referred to as Known as "specific resin".), organometallic complexes, and sensitizers with a condensed ring structure.

The photosensitive resin composition of the present invention is preferably used to form a photosensitive film for exposure and development, and is preferably used to form a film for exposure and development using a developer containing an organic solvent. As the above-mentioned exposure method, the above-mentioned developer solution, and the above-mentioned development method, for example, the exposure method described in the exposure process in the description of the pattern manufacturing method described later, the developer solution and the development method described in the development process can be used.

The photosensitive resin composition of this invention is excellent in the resolution and chemical resistance of the pattern obtained. The mechanism by which the above-mentioned effects are obtained is not clear, but is presumed as follows.

For example, as described in Patent Document 1, Patent Document 2, etc., in a photosensitive resin composition containing a specific resin, a sensitizer is used for the purpose of improving exposure sensitivity and the like. In addition, Patent Document 3 describes that chemical resistance is improved by using an organic titanium compound in the composition. Here, as a result of intensive research by the present inventors, it was found that the resolution of the obtained pattern is improved by using both an organometallic complex and a sensitizer having a condensed ring structure in the photosensitive resin composition. . The mechanism for obtaining the above effects is not clear, but it is presumed as follows: When the photosensitive resin composition contains an organometallic complex and a sensitizer of a specific structure, the electronic state of the sensitizer changes, for example, by LUMO (Lowest Unoccupied Unoccupied) Molecular Orbital: the lowest unoccupied molecular orbital) is reduced and the sensitivity of the sensitizer is increased, thereby increasing the resolution of the pattern obtained. This is considered to be because the planarity in the structure of the sensitizer having a condensed ring structure is improved and the electronic state is changed due to the interaction between the metal moiety contained in the organometallic complex and the sensitizer. Furthermore, it was found that the chemical resistance of the obtained pattern is improved by using both an organometallic complex and a sensitizer having a condensed ring structure in the photosensitive resin composition. The mechanism by which the above-mentioned effects are obtained is uncertain, but it is presumed that the specific resin interacts with the sensitizer having an organometallic complex and a condensed ring structure within the obtained pattern, whereby the chemical resistance is improved. Since the pattern is excellent in chemical resistance, it is considered that, for example, when another photosensitive resin composition containing a solvent is further applied to the pattern formed by the photosensitive resin composition of the present invention to form a layered body, etc., even if the pattern is mixed with a developing solution or When other photosensitive resin compositions come into contact with each other, the dissolution of the pattern can be suppressed. Furthermore, according to the present invention, it is considered that polar solvents such as dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP), alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solutions, dilute aqueous solutions, etc. can be obtained, for example. A pattern with excellent chemical resistance in which solubility is suppressed in an acidic aqueous solution such as a sulfuric acid aqueous solution, a dilute aqueous hydrochloric acid solution, a mixed solution of the above polar solvent and the above alkaline aqueous solution, or a mixed solution of the above polar solvent and the above acidic aqueous solution. Furthermore, since LUMO and the like are reduced by improving the planarity, the photosensitive film formed from the photosensitive resin composition of the present invention has the advantage of being excellent in exposure sensitivity when subjected to exposure such as exposure using a mask or exposure by direct laser imaging. tendency.

Hereinafter, the components contained in the photosensitive resin composition of this invention are demonstrated in detail.

＜Specific resin＞ The photosensitive resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor . As a specific resin, it is preferable that the photosensitive resin composition of this invention contains a polyimide or a polyimide precursor, and it is more preferable that it contains a polyimide precursor. Moreover, it is preferable that a specific resin has a radically polymerizable group. When a specific resin has a radically polymerizable group, it is preferable that the photosensitive resin composition contains a later-described photoradical polymerization initiator as a photosensitizer, a later-described photoradical polymerization initiator as a photosensitizer, and a later-described radical crosslinker. The linking agent is more preferable, and it is further more preferable to contain the later-described photoradical polymerization initiator as a photosensitizer, the later-described radical crosslinking agent, and the later-described sensitizer. For example, a negative photosensitive film is formed from such a photosensitive resin composition. In addition, the specific resin may have a polarity conversion group such as an acid-decomposable group. When a specific resin has an acid-decomposable group, it is preferable that the photosensitive resin composition contains a photoacid generator as a photosensitizer. For example, a chemically amplified type, that is, a positive-type photosensitive layer or a negative-type photosensitive layer is formed from the photosensitive resin composition.

在式（2）中，A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹¹ 表示2價有機基團，R¹¹⁵ 表示4價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團。[Polyimide Precursor] The polyimide precursor used in the present invention is not particularly limited in its kind or the like, but preferably contains a repeating unit represented by the following formula (2). Formula (2) [Chemical Formula 1]

In formula (2), 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 a monovalent organic group.

^{A 1} and A ² in the formula (2) each independently represent an oxygen atom or NH, preferably an oxygen atom. ^{R 111} in formula (2) represents a divalent organic group. As the divalent organic group, there can be exemplified groups including linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by a combination thereof is preferable, and a group including an aromatic group having 6 to 20 carbon atoms is more preferable. As a particularly preferred embodiment of the present invention, the case of a group represented by -Ar-L-Ar- can be exemplified. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, which may be substituted by fluorine atoms. Or a group consisting of a combination of two or more of the above. The preferred ranges of these are as described above.

R ¹¹¹ is preferably derived from a diamine. As a diamine used for manufacture of a polyimide precursor, a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine etc. are mentioned. Only one type of diamine may be used, or two or more types may be used. Specifically, it includes a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination of these. The diamine of the group is preferable, and the diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable. As an example of an aromatic group, the following aromatic group is mentioned.

式中，A係單鍵或選自可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-SO₂ -、-NHCO-或該等的組合之基團為較佳，單鍵或選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-SO₂ -之基團為更佳，-CH₂ -、-O-、-S-、-SO₂ -、-C（CF₃ ）₂ -或-C（CH₃ ）₂ -為進一步較佳。 式中，*表示與其他結構的鍵結部位。[Chemical formula 2]

In the formula, A is a single bond or is selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO ₂ -, -NHCO- The group or the combination of these is preferably, single bond or selected from alkylene with 1 to 3 carbon atoms which can be substituted by fluorine atom, -O-, -C(=O)-, -S- or - The group of SO ₂ - is more preferred, -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - or -C(CH ₃ ) ₂ - is further preferred. In the formula, * represents a bonding site with other structures.

Specific examples of the diamine include 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'-diamino-3,3'-dimethyl cyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4 ,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4, 4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2' -Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl) Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4- aminophenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis (3-amino-4-hydroxyphenyl) bis(4-amino-3-hydroxyphenyl) bis(4-amino-3-hydroxyphenyl) bis(4-amino-3-hydroxyphenyl), 4,4'-diamino-terphenyl, 4,4'-bis(4- Aminophenoxy) biphenyl, bis[4-(4-aminophenoxy)phenyl]sine, bis[4-(3-aminophenoxy)phenyl]sine, bis[4-( 2-Aminophenoxy)phenyl] benzene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-bis Methyl-4,4'-diaminodiphenyl benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene 3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diphenylmethane Aminodiphenylmethane, 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-amino) Phenyl) phenyl, 4,4'-dimethyl-3,3'-diaminodiphenyl, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenyl Phenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6- Tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, Diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4- Aminophenyl) decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexa Fluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-di Methylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4- Amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amine yl-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl, 4,4'-bis(3 -Amino-5-trifluoromethylphenoxy)diphenyl, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2 ,2',5,5',6,6'-hexafluorobitoluidine and at least one diamine in 4,4'-diaminotetraphenyl.

Moreover, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. WO 2017/038598 are also preferred.

Moreover, the diamine which has two or more alkylene glycol units in the main chain described in the paragraphs 0032 to 0034 of International Publication No. 2017/038598 can also be preferably used.

From the viewpoint of the flexibility of the obtained organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, which may be substituted by fluorine atoms. Or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms, -O-, -CO-, -S- or -SO ₂ - which may be substituted by a fluorine atom. The aliphatic hydrocarbon group here is preferably an alkylene group.

在式（51）中，R⁵⁰ ～R⁵⁷ 分別獨立地為氫原子、氟原子或1價有機基團，R⁵⁰ ～R⁵⁷ 中的至少1個為氟原子、甲基或三氟甲基。 作為R⁵⁰ ～R⁵⁷ 的1價有機基團，可舉出碳數1～10（較佳為碳數1～6）的未經取代之烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式4]

在式（61）中，R⁵⁸ 及R⁵⁹ 分別獨立地為氟原子或三氟甲基。 作為賦予式（51）或（61）的結構之二胺化合物，可舉出2,2’-二甲對聯苯胺、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該等可以使用1種或組合使用2種以上。From the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability. Formula (51) [Chemical Formula 3]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, ^{and at least one of R 50} to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group. ^Examples of the monovalent organic group of R ⁵⁰ to R 57 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably carbon number 1 to 6), and an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably carbon number 1 to 10). 1-6) fluorinated alkyl groups, etc. [Chemical formula 4]

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom or a trifluoromethyl group. 2,2'-dimethyl-p-benzidine and 2,2'-bis(trifluoromethyl)-4,4'-diamine are mentioned as the diamine compound which gives the structure of formula (51) or (61). Biphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used alone or in combination of two or more.

In addition, the following diamines can also be preferably used. [Chemical formula 5]

在式（5）中，R¹¹² 表示單鍵或可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO₂ -及-NHCO-、以及選自該等的組合之基團為較佳，單鍵或選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-CO-、-S-及-SO₂ -中之基團為更佳，選自包括-CH₂ -、-C（CF₃ ）₂ -、-C（CH₃ ）₂ -、-O-、-CO-、-S-及-SO₂ -之群組中之2價基團為進一步較佳。 ^{R 115} in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In Formula (5) or Formula (6), * each independently represents a bonding site with another structure. [Chemical formula 6]

In formula (5), R ¹¹² represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - and -NHCO-, And the group selected from these combinations is preferably, single bond or selected from alkylene with 1 to 3 carbon atoms, -O-, -CO-, -S- and -SO _{2 which can be substituted by fluorine atoms} The group in - is more preferably selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO ₂ A divalent group in the group of - is further preferred.

在式（O）中，R¹¹⁵ 表示4價有機基團。R¹¹⁵ 的較佳範圍的含義與式（2）中的R¹¹⁵ 相同，較佳範圍亦相同。Specifically, R ¹¹⁵ include the remaining tetracarboxylic acid residue and the like after removal of the anhydride groups from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical formula 7]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The same (2) R ¹¹⁵ R ¹¹⁵ is preferably in the range of meaning as in formula, preferred ranges are also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4, 4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid Dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic 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 -Perylene tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic acid Dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,2,3,4 -Mellitic dianhydride and these C1-6 alkyl groups and C1-6 alkoxy derivatives.

Moreover, as a preferable example, the tetracarboxylic dianhydride (DAA-1) - (DAA-5) described in the 0038 paragraph of International Publication No. WO 2017/038598 can also be mentioned.

It is also preferable that at least one of R ¹¹¹ and R ^{115 has an OH group.} More specifically, as R ¹¹¹ , the residue of a bisaminophenol derivative can be mentioned.

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 polymerizable group, and it is more preferable that both of them contain a polymerizable group. As a polymerizable group, it is a group which can carry out a crosslinking reaction by the action of heat, a radical, etc., and a radically polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an oxymethyl group, an epoxy group, an oxetanyl group, and a benzoyl group. oxazolyl group, blocked isocyanate group, methylol group, amine group. As a radically polymerizable group which a polyimide precursor etc. have, the group which has an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, a group represented by the following formula (III), and the like, and the group represented by the following formula (III) is better.

[Chemical formula 8]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred. In formula (III), * represents a bonding site with other structures. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ - or a polyalkeneoxy group. Preferred examples of R ²⁰¹ include ethylidene, propylidene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene Methylene, octamethylene, dodecylene, -CH ₂ CH(OH)CH ₂ -, polyalkyleneoxy, ethylidene, propylidene, trimethylene, -CH ₂ CH(OH) ) CH ₂ - and polyalkyleneoxy groups are more preferred, and polyalkyleneoxy groups are further preferred. In the present invention, the polyalkeneoxy group refers to a group in which two or more alkeneoxy groups are directly bonded to each other. The alkylene groups of a plurality of alkyleneoxy groups contained in the polyalkeneoxy group may be the same or different, respectively. When the polyalkeneoxy group contains a plurality of alkaneoxy groups with different alkylene groups, the arrangement of the alkaneoxy groups in the polyalkeneoxy group may be random, may be an arrangement with blocks, or may be alternately arranged. Alignment of patterns. The carbon number of the above-mentioned alkylene group (when the alkylene group has a substituent, the carbon number of the substituent group is included) is preferably 2 or more, more preferably 2-10, more preferably 2-6, more preferably 2-5 Preferably, 2 to 4 are still more preferable, 2 or 3 are particularly preferable, and 2 is the best. Moreover, the said alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. are mentioned. In addition, the number of alkeneoxy groups (the number of repetitions of polyalkeneoxy groups) contained in the polyalkeneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoints of solvent solubility and solvent resistance, the polyalkeneoxy group includes polyvinyloxy group, polypropeneoxy group, polytrimethyleneoxy group, polytetramethyleneoxy group, a plurality of vinyloxy groups and a plurality of A group bound by a propeneoxy group is preferred, polyvinyloxy or polypropeneoxy is more preferred, and polyvinyloxy is further preferred. In the above-mentioned groups formed by bonding a plurality of vinyloxy groups and a plurality of propeneoxy groups, the vinyloxy groups and the propeneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in alternating patterns. . The preferable aspect of the repeating number of the vinyloxy group etc. in these groups is as mentioned above.

R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an aromatic group and an aralkyl group in which an acid group is bonded to one, two, or three (preferably one) carbons constituting the aryl group. Specifically, an aromatic group having 6 to 20 carbon atoms having an acid group, and an aralkyl group having 7 to 25 carbon atoms having an acid group can be mentioned. More specifically, the phenyl group which has an acid group and the benzyl group which has an acid group are mentioned. The acid group is preferably an OH group. R ¹¹³ or R ¹¹⁴ is also preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a straight-chain or branched-chain alkyl group, a cyclic alkyl group, and an aromatic group, and more preferably an alkyl group substituted with an aromatic group. The number of carbon atoms in the alkyl group is preferably 1 to 30. The alkyl group may be any of straight chain, branched chain and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl Alkyl, octadecyl, isopropyl, isobutyl, tertiary butyl, tertiary butyl, 1-ethylpentyl, 2-ethylhexyl, 2-(2-(2-methoxy Ethoxy)ethoxy)ethoxy, 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy, 2-(2-(2-(2-methoxyethyl) oxy)ethoxy)ethoxy)ethoxy and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. As a monocyclic cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned, for example. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, camphenyl, camphenyl, decalinyl, tricyclodecyl, tetracyclodecyl, camphenyl Diacyl, dicyclohexyl and pinenyl. Among them, cyclohexyl is the most suitable from the viewpoint of achieving high sensitivity. Moreover, as the alkyl group substituted with an aromatic group, the linear alkyl group substituted with the aromatic group mentioned later is preferable. The aromatic group is specifically a substituted or unsubstituted benzene ring, naphthalene ring, pentavine ring, indene ring, azulene ring, heptavine ring, indene ring, perylene ring, fused pentabenzene ring, acenaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, tetraphenyl ring, triphenylene ring, forylene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine Ring, pyridine ring, pyrimidine ring, pyridine ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, quinoline ring , naphthyridine ring, quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, acridine ring, phenanthrene ring, thianthrene ring, chromene ring,㗁thiocycline, phenothiazine ring or phenothiazine ring. The benzene ring is the best.

In formula (2), when R ¹¹³ is a hydrogen atom or R ¹¹⁴ is a hydrogen atom, the polyimide precursor may form a conjugated salt with a tertiary amine compound having an ethylenically unsaturated bond. As an example of the tertiary amine compound which has such an ethylenically unsaturated bond, N,N- dimethylaminopropyl methacrylate is mentioned.

At least one of R ¹¹³ and R ¹¹⁴ may be a polarity converting group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group and a carboxyl group. A base ester group or the like is preferable, and an acetal group is more preferable from the viewpoint of exposure sensitivity. Specific examples of acid-decomposable groups include tertiary butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, and ethoxymethyl. base, trimethylsilyl, tertiary butoxycarbonylmethyl, trimethylsilyl ether, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

Moreover, it is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

In addition, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving the adhesion to the substrate. Specifically, as a diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are mentioned.

在式（2-A）中，A¹ 及A² 表示氧原子，R¹¹¹ 及R¹¹² 分別獨立地表示2價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團，R¹¹³ 及R¹¹⁴ 中的至少1個為包含聚合性基團之基團，兩者均為聚合性基團為較佳。The repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, at least one of the polyimide precursors and the like used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By setting it as such a structure, the width|variety of exposure latitude can be expanded further. Formula (2-A) [Chemical Formula 9]

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. , ^{at least one of R 113} and R ¹¹⁴ is a group containing a polymerizable group, and both of them are preferably a polymerizable group.

^{A 1, A 2, R 111} , R 113 and R ¹¹⁴ are each independently the meanings in the formula ^{A 1, A 2, R 111} , R 113 , and R is the same ¹¹⁴ (2), and preferred ranges are also the same. The same as R (5) in the meaning as in formula R ^{112 112,} preferred ranges are also the same.

The polyimide precursor may contain one type of repeating structural unit represented by the formula (2), or may contain two or more types. Also, structural isomers of the repeating unit represented by the formula (2) may be included. In addition to the repeating unit of the above formula (2), it is obvious that the polyimide precursor may contain other kinds of repeating structural units.

As an embodiment of the polyimide precursor of the present invention, 50 mol % or more of the total repeating units, further 70 mol % or more, and especially 90 mol % or more of the total repeating units are repeats represented by the formula (2). The polyimide precursor of the unit.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and further preferably 22,000 to 25,000. Moreover, as for the number average molecular weight (Mn), 7,200-14,000 are preferable, 8,000-12,000 are more preferable, 9,200-11,200 are still more preferable. The dispersity of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly limited. For example, it is preferably 4.5 or less, more preferably 4.0 or less, more preferably 3.8 or less, further preferably 3.2 or less, and 3.1 or less. In order to be more preferable, 3.0 or less is still further preferable, and 2.95 or less is particularly preferable. In this specification, the dispersion degree of molecular weight is a value calculated by weight average molecular weight/number average molecular weight.

[Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer whose main component is an organic solvent. In this specification, the alkali-soluble polyimide means that 0.1 g or more of polyimide is dissolved in 100 g of a 2.38 mass % tetramethylammonium aqueous solution at 23° C., and 0.5 g is dissolved from the viewpoint of pattern formation. The above polyimide is preferable, and it is more preferable to dissolve 1.0 g or more of the polyimide. The upper limit of the dissolved amount is not particularly limited, but is preferably 100 g or less. In addition, from the viewpoint of the film strength and insulating properties of the obtained organic film, polyimide is preferably a polyimide having a plurality of imide structures in the main chain. In this specification, "main chain" means the relatively longest bond chain in the molecule of the polymer compound constituting the resin, and "side chain" means other bond chains.

-Fluorine Atom- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has a fluorine atom. A fluorine atom is preferably contained in, for example, R ^{132 in the repeating unit represented by the following formula (4) or R 131} in the repeating unit represented by the following formula (4), and is contained as a fluorinated alkyl group in the following formula ( 4) R ^{132 in the repeating unit represented by or R 131} in the repeating unit represented by the following formula (4) is more preferable. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 1 to 50 mol/g, more preferably 5 to 30 mol/g.

-Silicon atom- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has a silicon atom. ^{Silicon atom, for example, R 131} contained in the repeating unit represented by the below-mentioned formula (4) is preferable, and R contained in the repeating unit represented by the below-mentioned formula (4) as the below-mentioned organic modified (poly)siloxane structure ¹³¹ is better. In addition, the above-mentioned silicon atom or the above-mentioned organic modified (poly)siloxane structure may be contained in the side chain of the polyimide, but it is preferably contained in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 0.01 to 5 mol/g, more preferably 0.05 to 1 mol/g.

-Ethylene unsaturated bond- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain, or may have an ethylenically unsaturated bond at the side chain, and preferably has an ethylenically unsaturated bond at the side chain. It is preferable that the above-mentioned ethylenically unsaturated bond has radical polymerizability. ^{R 132} in the repeating unit represented by the following formula (4) ^{or R 131} in the repeating unit represented by the following formula (4) is preferably contained in the ethylenically unsaturated bond as a group having an ethylenically unsaturated bond ^{R 132} contained in the repeating unit represented by the following formula (4) ^{or R 131} contained in the repeating unit represented by the following formula (4) is more preferable. ^{Among these, R 131} in which an ethylenically unsaturated bond is included in the repeating unit represented by the following formula (4) is preferably included in the group represented by the following formula (4) as a group having an ethylenically unsaturated bond. ^{R 131} in the repeating unit is more preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, and a group having an optionally substituted vinyl group directly bonded to an aromatic ring, (meth)acryloyl group. An amino group, a (meth)acryloyloxy group, a group represented by the following formula (IV), and the like.

[Chemical formula 10]

In formula (IV), R ²⁰ represents a hydrogen atom or a methyl group, preferably a methyl group.

In formula (IV), R ²¹ represents an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH -, (poly)alkaneoxy with carbon number 2-30 (the carbon number of alkylene is preferably 2-12, 2-6 is better, 2 or 3 is particularly preferred; the number of repetitions is 1-12 More preferably, 1 to 6 are more preferably, 1 to 3 are particularly preferred) or a group formed by combining two or more of these.

在式（R1）～（R3）中，L表示單鍵或碳數2～12的伸烷基、碳數2～30的（聚）伸烷氧基或將該等鍵結2個以上而成之基團，X表示氧原子或硫原子，*表示與其他結構的鍵結部位，●表示與式（III）中的R²⁰¹ 所鍵結之氧原子的鍵結部位。 在式（R1）～（R3）中，L中的碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳態樣與上述R²¹ 中的碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳態樣相同。 在式（R1）中，X係氧原子為較佳。 式（R1）～（R3）中，*的含義與式（IV）中的*相同，較佳態樣亦相同。 由式（R1）表示之結構例如可藉由使酚性羥基等具有羥基之聚醯亞胺與具有異氰酸基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-異氰酸基乙酯等）進行反應來獲得。 由式（R2）表示之結構例如可藉由使具有羧基之聚醯亞胺與具有羥基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-羥乙酯等）進行反應來獲得。 由式（R3）表示之結構例如可藉由使酚性羥基等具有羥基之聚醯亞胺與具有環氧丙基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸環氧丙酯等）進行反應來獲得。 作為聚伸烷氧基，從溶劑溶解性及耐溶劑性的觀點考慮，聚乙烯氧基、聚伸丙氧基、聚三亞甲氧基、聚四亞甲氧基或複數個乙烯氧基與複數個伸丙氧基鍵結之基團為較佳，聚乙烯氧基或聚伸丙氧基為更佳，聚乙烯氧基為進一步較佳。在上述複數個乙烯氧基與複數個伸丙氧基鍵結而成之基團中，乙烯氧基和伸丙氧基可無規排列，可以形成嵌段來排列，亦可以排列成交替等圖案狀。該等基團中的乙烯氧基等的重複數的較佳態樣如上所述。Among these, R ²¹ is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by the formula (R1). [Chemical formula 11]

In formulae (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkaneoxy group having 2 to 30 carbon atoms, or two or more of these bonds. In the group, X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bonding site with the oxygen atom ^{to which R 201 in formula (III) is bonded.} In the formulae (R1) to (R3), the preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkaneoxy group having 2 to 30 carbon atoms in L is the same as the carbon number in the above R ²¹ The preferable aspects of the alkylene group having 2 to 12 or the (poly)alkaneoxy group having 2 to 30 carbon atoms are the same. In formula (R1), an X-based oxygen atom is preferable. In the formulae (R1) to (R3), the meaning of * is the same as that of * in the formula (IV), and the preferred aspects are also the same. The structure represented by the formula (R1) can be obtained, for example, by combining a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanato methacrylate). ethyl ester, etc.) to obtain by reacting. The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.). The structure represented by the formula (R3) can be obtained, for example, by combining a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (eg, glycidyl methacrylate, etc.) reaction to obtain. From the viewpoints of solvent solubility and solvent resistance, the polyalkeneoxy group includes polyvinyloxy group, polypropeneoxy group, polytrimethyleneoxy group, polytetramethyleneoxy group, a plurality of vinyloxy groups and a plurality of A group bound by a propeneoxy group is preferred, polyvinyloxy or polypropeneoxy is more preferred, and polyvinyloxy is further preferred. In the above-mentioned groups formed by bonding a plurality of vinyloxy groups and a plurality of propeneoxy groups, the vinyloxy groups and the propeneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in alternating patterns. . The preferable aspect of the repeating number of the vinyloxy group etc. in these groups is as mentioned above.

In formula (IV), * represents a bonding site with another structure, and it is preferably a bonding site with the main chain of polyimide.

The amount of the ethylenically unsaturated bonds with respect to the total mass of the polyimide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g. Furthermore, from the viewpoint of production suitability, the amount of the ethylenically unsaturated bonds with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, more preferably 0.0005 to 0.05 mol/g.

-Crosslinkable group other than ethylenically unsaturated bond- The polyimide may have a crosslinkable group other than the ethylenically unsaturated bond. Examples of crosslinkable groups other than ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. A crosslinkable group other than an ethylenically unsaturated bond, for example, R ¹³¹ contained in the repeating unit represented by the formula (4) described later is preferable. The amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g. In addition, from the viewpoint of suitability for production, the amount of the crosslinkable group other than the ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, preferably 0.001 to 0.05 mol/g g is better.

-Polarity Conversion Group- The polyimide may have a polar conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R ¹¹³ and R ¹¹⁴ of the above formula (2), and the preferred embodiments are also the same.

-Acid value- When polyimide is used for alkali development, from the viewpoint of improving developability, the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and further more preferably 70 mgKOH/g or more. good. Further, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. In addition, when polyimide is used in development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 2 to 35 mgKOH/g, 3 ∼30 mgKOH/g is more preferable, and 5∼20 mgKOH/g is further preferable. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. In addition, as the acid group contained in the polyimide, from the viewpoint of both storage stability and developability, an acid group having a pKa of 0 to 10 is preferable, and an acid group of 3 to 8 is more preferable. pKa is the one which takes into account the dissociation reaction liberating hydrogen ions from an acid and expresses its equilibrium constant Ka by its negative common logarithmic pKa. In this specification, unless otherwise specified, pKa is a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, you can refer to the values described in "Revised 5th Edition Chemical Handbook Basics" edited by the Chemical Society of Japan. In addition, when the acid group is, for example, a polybasic acid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant. As the acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

-Phenolic hydroxyl group- From the viewpoint of making the developing speed by an alkali developer appropriate, it is preferable that the polyimide has a phenolic hydroxyl group. The polyimide may have a phenolic hydroxyl group at the end of the main chain, or may have a phenolic hydroxyl group at the side chain. The phenolic hydroxyl group is preferably contained in, for example, R ^{132 in the repeating unit represented by the following formula (4) or R 131} in the repeating unit represented by the following formula (4). The amount of the phenolic hydroxyl groups with respect to the total mass of the polyimide is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g.

在式（4）中，R¹³¹ 表示2價有機基團，R¹³² 表示4價有機基團。 具有聚合性基團時，聚合性基團可以位於R¹³¹ 及R¹³² 中的至少1個上，亦可以如下述式（4-1）或式（4-2）所示，位於聚醯亞胺的末端。 式（4-1） [化學式13]

式（4-1）中，R¹³³ 係聚合性基團，其他基團的含義與式（4）相同。 式（4-2） [化學式14]

R¹³⁴ 及R¹³⁵ 中的至少1個為聚合性基團，不是聚合性基團的情況下為有機基團，其他基團的含義與式（4）相同。The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imine ring, but it is preferable to include a repeating unit represented by the following formula (4), and it includes a repeating unit represented by the formula ( 4) The compound represented by the repeating unit and having a polymerizable group is more preferable. Formula (4) [Chemical Formula 12]

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. When it has a polymerizable group, the polymerizable group may be located ^{on at least one of R 131} and R ¹³² , or it may be located on a polyimide as shown in the following formula (4-1) or formula (4-2) the end of . Formula (4-1) [Chemical Formula 13]

In formula (4-1), R ¹³³ is a polymerizable group, and other groups have the same meanings as in formula (4). Formula (4-2) [Chemical Formula 14]

At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the meanings of the other groups are the same as those of formula (4).

The meaning of the polymerizable group is the same as that described in the above-mentioned polymerizable group of the polyimide precursor and the like. R ¹³¹ represents a divalent organic group. ^{As a divalent organic group, the same thing as R 111} in formula (2) can be illustrated, and the preferable range is also the same. Moreover, as ^R131 , the diamine residue which remains after removing the amine group of a diamine is mentioned. As a diamine, an aliphatic, cycloaliphatic, or aromatic diamine etc. are mentioned. Specific examples thereof include examples of formula (2) in R ¹¹¹ include polyimide precursor.

^{R 131} is preferably a diamine residue having at least two alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the occurrence of warpage during firing. More preferably, it contains a total of two or more ethylene glycol chains and propylene glycol chains, or a diamine residue of both, and more preferably contains no aromatic ring.

Examples of diamines containing either one or both of ethylene glycol chains and propylene glycol chains at least two in total include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (the above are trade names, manufactured by Huntsman Corporation), 1-(2-(2-(2-aminopropoxy) )ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc., but not Not limited to these.

R ¹³² represents a tetravalent organic group. ^{As a tetravalent organic group, the same thing as R 115} in formula (2) can be illustrated, and the preferable range is also the same. For example, ^{four linkages of the tetravalent organic group exemplified as R 115} are bonded to four -C(=O)- moieties in the above formula (4) to form a condensed ring.

And, R ¹³² include the residue of tetracarboxylic acid residue and the like after removal of the anhydride groups from the tetracarboxylic dianhydride. Specific examples, examples of the formula R ¹¹⁵ (2) of the polyimide precursor may be exemplified. From the viewpoint of the strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable to have an OH group on at least one of R ¹³¹ and R ^132. More specifically, R ¹³¹ includes 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoro Propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, the above (DA-1)～( DA-18) As a preferable example, as ^R132 , the said (DAA-1) - (DAA-5) are mentioned as a more preferable example.

Moreover, it is also preferable that polyimide has a fluorine atom in a structural unit. The content of the fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

Moreover, in order to improve the adhesiveness with a board|substrate, polyimide may be copolymerized with the aliphatic group which has a siloxane structure. Specifically, as a diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are mentioned.

In addition, in order to improve the storage stability of the composition, it is preferable to seal the main chain end of the polyimide with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloride compound, or a monoactive ester compound. Among these, it is more preferable to use a monoamine, and preferable compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, and 5-amino-8- Oxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7- aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5- aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4- Aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzene Sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-Aminothiophenol, etc. Two or more kinds of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

- Imidization rate (ring closure rate) - From the viewpoints of film strength, insulating properties, etc. of the obtained organic film, the imidization rate (also referred to as "ring closure rate") of polyimide is 70% or more It is more preferable, more than 80% is more preferable, and more than 90% is more preferable. The upper limit of the above-mentioned imidization rate is not particularly limited, and may be 100% or less. For example, the above-mentioned imidization rate can be measured by the following method. The infrared absorption spectrum of the polyimide was measured, and the peak intensity P1 in the vicinity of ^{1377 cm −1 which} is an absorption peak derived from the structure of the imide was obtained. Next, after heat-treating this polyimide at 350 degreeC for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P2 of the vicinity of ^{1377 cm-1 was calculated|required.} Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be determined according to the following formula. Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

Polyimide may include all contain one kind or R ^{131 is} R in the above formula (4) of the repeating structural unit ^132, it may also including a repeating two or more different kinds or R ^{131 is} the formula (4) ¹³² of the R unit. In addition to the repeating unit of the above formula (4), the polyimide may contain other kinds of repeating structural units.

For example, polyimide can use a method of reacting tetracarboxylic dianhydride with a diamine compound (a part of which is substituted with a monoamine, that is, a blocking agent) at a low temperature, and a method of making a tetracarboxylic dianhydride (a part of which is substituted with an acid anhydride) at low temperature. A method of reacting with a diamine compound, or a monochloride compound or a monoactive ester compound, i.e. a capping agent, obtain a diester by tetracarboxylic dianhydride and an alcohol, and then diamine (a part of which is substituted with a monoamine i.e. capping agent) A method of reacting in the presence of a terminal agent) and a condensing agent, after obtaining a diester from a tetracarboxylic dianhydride and an alcohol, the remaining dicarboxylate is chlorinated and then reacted with a diamine (a part of which is substituted with a monoamine) The polyimide precursor is obtained by the method of reacting with the end-capping agent, etc., and the polyimide precursor is obtained by the conventional imidization reaction method and the method of complete imidization is used, or the imidization reaction is stopped in the middle and a part is introduced. The method of imide structure is further synthesized by the method of introducing a part of imide structure by mixing the fully imidized polymer and its polyimide precursor. As a commercial item of polyimide, Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by Huntsman Corporation) can be exemplified.

The weight average molecular weight (Mw) of the polyimide is 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. The bending resistance of the film after hardening can be improved by making a weight average molecular weight into 5,000 or more. In order to obtain an organic film excellent in mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. Moreover, when two or more types of polyimide are contained, it is preferable that the weight average molecular weight of at least one type of polyimide is within the above-mentioned range.

在式（3）中，R¹²¹ 表示2價有機基團，R¹²² 表示4價有機基團，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價有機基團。[Polybenzoxazole Precursor] The polybenzoxazole precursor used in the present invention is not particularly limited in its structure or the like, but preferably contains a repeating unit represented by the following formula (3). Formula (3) [Chemical Formula 15]

In formula (3), 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.

In formula (3), R ¹²³ and R ^{124 have the same meanings as R 113} in formula (2), respectively, and the preferred ranges are also the same. That is, it is preferable that at least one is a polymerizable group. In formula (3), R ¹²¹ represents a divalent organic group. As a divalent organic group, it is preferable to contain at least one group among an aliphatic group and an aromatic group. As the aliphatic group, a straight-chain aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable. As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferred, and a linear or branched (preferably linear) aliphatic group is The dicarboxylic acid formed with 2 -COOH is more preferable. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, and even more preferably 4 to 15, 5 to 10 is particularly good. The straight-chain aliphatic group is preferably an alkylene group. Examples of the dicarboxylic acid containing a straight-chain aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, and succinic acid. , tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2 - methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, Adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctanedioic acid, azelaic acid acid, sebacic acid, hexadecanedioic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid , Heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid, behenandioic acid, tricosanedioic acid, tetracosane Diacid, Pentadecanedioic acid, Hexadecanedioic acid, Heptacosanedioic acid, Hecosanedioic acid, Nonacosanedioic acid, Triacosanedioic acid, Tridecanedioic acid , tridocosanedioic acid, diglycolic acid, further dicarboxylic acid represented by the following formula, and the like.

（式中，Z係碳數1～6的烴基，n係1～6的整數。）[Chemical formula 16]

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

As a dicarboxylic acid containing an aromatic group, the dicarboxylic acid which has the following aromatic groups is preferable, and the dicarboxylic acid which consists only of the following aromatic groups and two -COOH is more preferable.

式中，A表示選自包括-CH₂ -、-O-、-S-、-SO₂ -、-CO-、-NHCO-、-C（CF₃ ）₂ -及-C（CH₃ ）₂ -之群組中之2價基團，*分別獨立地表示與其他結構的鍵結部位。[Chemical formula 17]

In the formula, A represents selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ - and -C(CH ₃ ) ₂ A divalent group in the group of -, * each independently represents a bonding site with other structures.

Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, the meaning is the ^{same as that of R 115} in the above formula (2), and the preferable range is also the same. Moreover, R ¹²² is preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4 '-Dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl, 4 ,4'-Diamino-3,3'-dihydroxydiphenyl, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyl) Phenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis -(4-Amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-diamino Hydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3 '-Diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1 , 3-Diamino-4,6-dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

Among the bisaminophenol derivatives, the bisaminophenol derivatives having the following aromatic groups are preferred.

式中，X₁ 表示-O-、-S-、-C（CF₃ ）₂ -、-CH₂ -、-SO₂ -、-NHCO-，*及#分別表示與其他結構的鍵結部位。R表示氫原子或1價取代基，氫原子或烴基為較佳，氫原子或烷基為更佳。又，R¹²² 係由上述式表示之結構亦較佳。R¹²² 係由上述式表示之結構時，共計4個*及#中，任意2個為與式（3）中的R¹²² 所鍵結之氮原子的鍵結部位且另2個為與式（3）中的R¹²² 所鍵結之氧原子的鍵結部位為較佳，2個*為與式（3）中的R¹²² 所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R¹²² 所鍵結之氮原子的鍵結部位或2個*為與式（3）中的R¹²² 所鍵結之氮原子的鍵結部位且2個#為與式（3）中的R¹²² 所鍵結之氧原子的鍵結部位為更佳，2個*為與式（3）中的R¹²² 所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R¹²² 所鍵結之氮原子的鍵結部位為進一步較佳。[Chemical formula 18]

In the formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, -NHCO-, and * and # represent the bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. In addition, ^{the structure in which R 122} is represented by the above formula is also preferable. When R ¹²² is a structure represented by the above formula, among the total of 4 * and #, any two ^{are the bonding site with the nitrogen atom to which R 122} in the formula (3) is bonded, and the other two are with the formula ( bonded portion 3) of the R ¹²² are bonded is preferably an oxygen atom, with the formula 2 * (R ¹²² bonded portion of the oxygen atoms are bonded in the 3) and # 2 with the formula ^{The bonding site of the nitrogen atom to which R 122} in (3) is bonded or 2 * are the bonding sites to the nitrogen atom bonded to R ¹²² in the formula (3), and 2 # are the bonding site with the formula (3) ) in the ^{bonding site of the oxygen atom bonded by R 122} is better, 2 * are bonding sites with the oxygen atom bonded with R ¹²² in the formula (3) and 2 # are with the formula ( In 3), the bonding site of the nitrogen atom ^{to which R 122 is bonded is further preferred.}

[Chemical formula 19]

In formula (As), R ₁ is a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, a single bond, or a single bond or selected from the following An organic group in the group of formula (A-sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, and a cyclic alkyl group, and may be the same or different. R ₃ is any one of a hydrogen atom, a straight-chain or branched-chain alkyl group, an alkoxy group, an aryloxy group, and a cyclic alkyl group, and may be the same or different.

（在式（A-sc）中，*表示鍵結於由上述式（A-s）表示之雙胺基苯酚衍生物的胺基苯酚基的芳香環。）[Chemical formula 20]

(In the formula (A-sc), * represents an aromatic ring bonded to the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

It is considered that in the above formula (As), the ortho-position of the phenolic hydroxyl group, that is, R ₃ also has a substituent, the distance between the carbonyl carbon of the amide bond and the hydroxyl group is closer, and when hardened from a low temperature, it has It is especially preferable from the viewpoint of further enhancing the effect of the high cyclization rate.

In addition, in the above formula (As), when R ₂ is an alkyl group and R ₃ is an alkyl group, the high transparency to i-rays and the effect of increasing the cyclization rate during curing at low temperature are maintained, which is preferable. .

In addition, in the above formula (As), it _{is more preferable that R 1} is an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and substituted alkylene group related to R ₁ include straight-chain or branched-chain alkyl groups having 1 to 8 carbon atoms. Considering the effect of high cyclization rate at the time of lower hardening, while having sufficient solubility in the solvent and obtaining a polybenzoxazole precursor with excellent balance, -CH ₂ -, -CH(CH ₃ )-, - C(CH ₃ ) ₂ - is better.

As a method for producing the bisaminophenol derivative represented by the above formula (As), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A No. 2013-256506. incorporated into this manual.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include the contents described in paragraphs 0070 to 0080 of JP-A No. 2013-256506, which are incorporated in the present specification. Of course, it is not limited to these.

In addition to the repeating unit of the above formula (3), the polybenzoxazole precursor may also contain other kinds of repeating structural units. From the viewpoint of being able to suppress warpage accompanying ring closure, it is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit.

在式（SL）中，Z具有a結構和b結構，R^1s 係氫原子或碳數1～10的烴基，R^2s 係碳數1～10的烴基，R^3s 、R^4s 、R^5s 、R^6s 中的至少1個為芳香族基，剩餘部分為氫原子或碳數1～30的有機基團且分別可以相同，亦可以不同。a結構及b結構的聚合可以為嵌段聚合或隨機聚合。關於Z部分的莫耳%，a結構為5～95莫耳%，b結構為95～5莫耳%，a+b為100莫耳%。[Chemical formula 21]

In formula (SL), Z has a structure and b structure, R ^1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms, R ^2s is a hydrocarbon group with 1 to 10 carbon atoms, R ^3s , R ^4s , R ^5s , R ^{At least one of 6s} is an aromatic group, and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. Regarding the mol % of the Z part, the a structure is 5 to 95 mol %, the b structure is 95 to 5 mol %, and the a+b is 100 mol %.

In formula (SL), as a preferable Z, those in which R ^5s and R ^6s in the structure b are phenyl groups are exemplified. Furthermore, the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the above molecular weight in the above range, the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor can be more effectively reduced, and both the effect of suppressing warpage and the effect of improving solvent solubility can be achieved.

When the diamine residue represented by the formula (SL) is contained as another kind of repeating structural unit, it is also preferable to further include, as the repeating structural unit, the tetracarboxylic acid residue remaining after removing the acid anhydride group from the tetracarboxylic dianhydride. Examples of such tetracarboxylic acid residues include R ¹¹⁵ in the formula (2).

For example, when used in the composition described later, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. Moreover, as for the number average molecular weight (Mn), 7,200-14,000 are preferable, 8,000-12,000 are more preferable, 9,200-11,200 are still more preferable. The dispersity of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly limited, for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is further preferable, 2.3 or less is further preferable, and 2.2 The following are further preferred.

在式（X）中，R¹³³ 表示2價有機基團，R¹³⁴ 表示4價有機基團。 具有聚合性基團或酸分解性基等極性轉換基時，聚合性基團或酸分解性基等極性轉換基可以位於R¹³³ 及R¹³⁴ 中的至少1個上，亦可以如下述式（X-1）或式（X-2）所示位於聚苯并㗁唑的末端。 式（X-1） [化學式23]

在式（X-1）中，R¹³⁵ 及R¹³⁶ 中的至少1個為聚合性基團或酸分解性基等極性轉換基，不是聚合性基團或酸分解性基等極性轉換基的情況下為有機基團，其他基團的含義與式（X）相同。 式（X-2） [化學式24]

在式（X-2）中，R¹³⁷ 係聚合性基團或酸分解性基等極性轉換基，其餘為取代基，其他基團的含義與式（X）相同。[Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, and a compound represented by the following formula (X) is preferable, and is represented by the following The compound represented by formula (X) and having a polymerizable group is more preferable. As the above-mentioned polymerizable group, a radically polymerizable group is preferable. Moreover, it may be a compound represented by the following formula (X) and having a polarity converting group such as an acid-decomposable group. [Chemical formula 22]

In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. When there is a polar conversion group such as a polymerizable group or an acid-decomposable group, the polar conversion group such as a polymerizable group or an acid-decomposable group may be located ^{on at least one of R 133} and R ¹³⁴ , or it may be shown in the following formula (X -1) or formula (X-2) at the end of the polybenzoxazole. Formula (X-1) [Chemical Formula 23]

In the formula (X-1), ^{at least one of R 135} and R ¹³⁶ is a polar conversion group such as a polymerizable group or an acid-decomposable group, and is not a polar conversion group such as a polymerizable group or an acid-decomposable group The following is an organic group, and the meanings of other groups are the same as those of formula (X). Formula (X-2) [Chemical Formula 24]

In formula (X-2), R ¹³⁷ is a polar conversion group such as a polymerizable group or an acid-decomposable group, the rest are substituents, and the meanings of other groups are the same as those of formula (X).

The polar conversion group such as a polymerizable group or an acid-decomposable group has the same meaning as the polar conversion group such as a polymerizable group or an acid-decomposable group described above for the polymerizable group contained in the polyimide precursor or the like.

R ¹³³ represents a divalent organic group. As a divalent organic group, an aliphatic group or an aromatic group is mentioned. Specific examples include polystyrene and㗁example oxazole of formula (3) R ¹²¹ of the precursor. In addition, the meaning of the preferable example is the same as that of R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. ^{Examples of the tetravalent organic group include R 122} in the formula (3) of the polybenzoxazole precursor. In addition, the meaning of its preferable example is the same as that of R ¹²² . For example, ^{four bonds of the tetravalent organic group exemplified as R 122} are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. [Chemical formula 25]

The oxazole ratio of the polybenzoxazole is preferably 85% or more, more preferably 90% or more. When the oxazolation ratio is 85% or more, the film shrinkage based on ring closure (which occurs when the oxazole is formed by heating) is reduced, and the occurrence of warpage can be effectively suppressed.

Polybenzoxazole㗁azole may include all contain one kind of R in the above formula (X), the repeating structural units of ¹³¹ or R ^132, can also comprise comprise two or more different kinds of the above-mentioned formula R (X) ¹³¹ or ¹³² of the R repeating unit. Moreover, in addition to the repeating unit of the said formula (X), a polybenzoxazole may contain other kinds of repeating structural units.

For example, ^{a polybenzoxazole precursor is obtained by reacting a bisaminophenol derivative with a dicarboxylic acid containing R 133} or a compound selected from the group consisting of dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above-mentioned dicarboxylic acids. The polybenzoxazole can be obtained by using the conventional oxazole method to make it oxazole. Moreover, in the case of a dicarboxylic acid, in order to improve reaction yield etc., the active ester type dicarboxylic acid derivative which made 1-hydroxy-1,2,3-benzotriazole etc. react in advance can also be used.

The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. The bending resistance of the film after hardening can be improved by making a weight average molecular weight into 5,000 or more. In order to obtain an organic film excellent in mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. Moreover, when two or more types of polybenzoxazoles are contained, it is preferable that the weight average molecular weight of at least one type of polybenzoxazoles is in the said range.

[Production method of polyimide precursor, etc.] A polyimide precursor or the like can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. After halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent, it is preferably obtained by reacting it with a diamine. In the production method of the polyimide precursor, it is preferable to use an organic solvent during the reaction. The organic solvent 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, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone. Polyimide can be cyclized by thermal imidization, chemical imidization (for example, by making a catalyst act to promote the cyclization reaction) after synthesizing the polyimide precursor To manufacture, it can also directly synthesize polyimide.

Moreover, it is also preferable to synthesize using a non-halogen-based catalyst without using the above-mentioned halogenating agent. As the above-mentioned non-halogen-based catalyst, a known amidation catalyst that does not contain a halogen atom can be used without particular limitation, and examples thereof include boroxy hydrocarbon trimer compounds, N-hydroxy compounds, tertiary amines, and phosphoric acid. Esters, amine salts, urea compounds, etc., carbodiimide compounds. As said carbodiimide compound, N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, etc. are mentioned.

-Capping agent- When producing polyimide precursors, etc., in order to further improve storage stability, it is preferable to seal the ends of polyimide precursors, etc. . As the blocking agent, it is more preferable to use a monoamine, and preferable compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, and 5-amino-8- Oxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7- aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5- aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4- Aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzene Sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-Aminothiophenol, etc. Two or more kinds of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

-Solid Precipitation- In the manufacture of polyimide precursors, etc., a process of precipitation of solids may be included. Specifically, a solid can be deposited by precipitating the polyimide precursor and the like in the reaction liquid in water and dissolving it in a soluble solvent such as the polyimide precursor such as tetrahydrofuran. After that, by drying the polyimide precursor or the like, a powdery polyimide precursor or the like can be obtained.

〔content〕 The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more, relative to the total solid content of the composition. It is even better. The content of the resin in the composition of the present invention is preferably 99.5 mass % or less, more preferably 99 mass % or less, more preferably 98 mass % or less, and 97 mass % or less, relative to the total solid content of the composition. More preferably, 95 mass % or less is further more preferable. The composition of this invention may contain only 1 type of specific resin, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.

Moreover, it is also preferable that the photosensitive resin composition of this invention contains at least 2 types of resin. Specifically, the photosensitive resin composition of the present invention may contain a total of two or more specific resins and other resins described later, or may contain two or more specific resins, and preferably two or more specific resins. When the photosensitive resin composition of the present invention contains two or more kinds of specific resins, for example, it is preferable to contain a polyimide precursor which is a structure derived from a dianhydride (in the above formula (2) Two or more kinds of polyimide precursors with different ^{R 115} ) mentioned in the above.

<Organometallic complex> The photosensitive resin composition of this invention contains an organometallic complex. As long as the organometallic complex is an organic complex compound containing a metal atom, a complex compound containing a metal atom and an organic group is preferable, and a compound in which an organic group is coordinated with a metal atom is more preferable, Metallocene compounds are further preferred. In the present invention, the metallocene compound refers to an organometallic complex comprising two cyclopentadienyl anion derivatives which may have substituents as η5-ligands. Although it does not specifically limit as said organic group, A hydrocarbon group or the group which consists of a combination of a hydrocarbon group and a hetero atom is preferable. As a hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferable. In the present invention, at least one of the organic groups is preferably a cyclic group, and more preferably at least two of the organic groups are a cyclic group. The above-mentioned cyclic group is preferably selected from a 5-membered ring cyclic group and a 6-membered ring cyclic group, and is more preferably selected from a 5-membered ring cyclic group. The above-mentioned cyclic group may be a hydrocarbon ring or a heterocyclic ring, but a hydrocarbon ring is preferable. As the 5-membered cyclic group, a cyclopentadienyl group is preferable. In addition, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

The metal contained in the organometallic complex is not particularly limited, and it is preferably a metal conforming to Group 4 elements, more preferably at least one metal selected from the group consisting of titanium, zirconium and hafnium, At least one metal selected from the group consisting of titanium and zirconium is further preferred, and titanium is particularly preferred.

The organometallic complex may contain two or more metal atoms, or may contain only one metal atom, but it is preferable to contain only one metal atom. When the organometallic complex contains two or more metal atoms, only one type of metal atom may be contained, or two or more types of metal atoms may be contained.

The organometallic complex is preferably a titanocene compound, a zirconocene compound or a hafnium compound, more preferably a titanocene compound or a zirconocene compound, and even more preferably a titanocene compound.

The aspect in which the organometallic complex has the ability to initiate photo-radical polymerization is also one of the preferred aspects of the present invention. In the present invention, having the ability to initiate photo-radical polymerization refers to being able to generate radicals capable of initiating radical polymerization by irradiation of light. For example, when a composition comprising a radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region in which the organometallic complex absorbs light and the radical crosslinking agent does not absorb light in a wavelength region of light, it is confirmed that the radical crosslinking agent Whether or not the linking agent disappears can be confirmed by the presence or absence of the photo-radical polymerization initiating ability. When confirming the disappearance, an appropriate method can be selected according to the type of the radical crosslinking agent. For example, it may be confirmed by IR measurement (infrared spectrometry) or HPLC measurement (high performance liquid chromatography). When the organometallic complex has the ability to initiate photo-radical polymerization, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnium compound, and a titanocene compound Or zirconocene compounds are further preferred, and titanocene compounds are particularly preferred. When the organometallic complex does not have the ability to initiate photo-radical polymerization, the organometallic complex is selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium halide compounds, chelated titanium compounds, zirconocene compounds At least one compound selected from the group consisting of a titanocene compound, a zirconocene compound, and a hafnocene compound is preferably at least one compound selected from the group of the compound and the hafnocene compound. At least one compound selected from the group consisting of a titanocene compound and a zirconocene compound is further preferred, and a titanocene compound is particularly preferred.

The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.

式（P）中，M係金屬元素，R分別獨立地為取代基。 上述R分別獨立地選自芳香族基、烷基、鹵素原子及烷基磺醯氧基為較佳。As an organometallic complex, the compound represented by following formula (P) is mentioned preferably. [Chemical formula 26]

In formula (P), M is a metal element, and R is each independently a substituent. Preferably, the above Rs are each independently selected from an aromatic group, an alkyl group, a halogen atom and an alkylsulfonyloxy group.

In the formula (P), as the metal element represented by M, a titanium atom, a zirconium atom or a hafnium atom is preferable, a titanium atom or a zirconium atom is more preferable, and a titanium atom is further preferable. As the aromatic group in R in the formula (P), an aromatic group having 6 to 20 carbon atoms is mentioned, and an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, and a phenyl group and a 1-naphthyl group are mentioned. Or 2-naphthyl, etc. As the alkyl group in R in the formula (P), an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and methyl group, ethyl group, propyl group, octyl group are mentioned. base, isopropyl, tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like. As a halogen atom in said R, F, Cl, Br, and I are mentioned. As the alkyl group constituting the alkylsulfonyloxy group in the above R, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable, and methyl, ethyl, propyl base, octyl, isopropyl, tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like. The above-mentioned R may further have a substituent. Examples of the substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, Aryloxycarbonyl, aryloxy, monoalkylamine, dialkylamine, monoarylamine and diarylamine, etc.

Specific examples of the organometallic complex are not particularly limited, and tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, and diisopropoxybis(ethylacetate)titanium can be exemplified. , Diisopropoxy bis (acetone acetone) titanium and the following compounds. [Chemical formula 27]

In addition, compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 can also be used, but are not limited thereto.

The content of the organometallic complex is preferably 0.1 to 30 mass % with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 1.0 mass % or more, more preferably 1.5 mass % or more, and particularly preferably 3.0 mass % or more. The upper limit is more preferably 25% by mass or less. One type or two or more types of organometallic complexes can be used. When using 2 or more types, it is preferable that the total amount is in the said range.

<Sensitizer with a condensed ring structure> The photosensitive resin composition of this invention contains the sensitizer (henceforth a "specific sensitizer") which has a condensed ring structure. In the present invention, the condensed ring structure refers to a structure in which two ring structures share two atoms and one bond. One or both of the above-mentioned two ring structures may further form a condensed ring structure with other ring structures. The specific sensitizer should just have at least one condensed ring structure, and may contain a plurality of them. In addition, the condensed ring structure in the specific sensitizer may be a structure in which a plurality of ring structures such as acene-based hydrocarbons are condensed in a linear form, for example, a plurality of ring structures such as a phenanthrene structure may be condensed in a non-linear form. The resulting structure may be, for example, a structure in which a plurality of ring structures such as a pyrene structure are condensed with other plurality of ring structures, respectively. Among them, the condensed ring structure is preferably a structure formed by condensing 2 to 6 ring structures, more preferably a ring structure formed by condensation of 2 to 4 ring structures, and a structure formed by the condensation of 2 to 4 ring structures is more preferable. A ring structure formed by condensation of three ring structures is further preferable, and a ring structure formed by condensation of three ring structures is particularly preferable. The above-mentioned ring structure is not particularly limited, and all are preferably a 5-membered ring structure or a 6-membered ring structure. Moreover, among the above-mentioned ring structures, it is preferable that at least one is a ring structure containing a nitrogen atom described later or a ring structure containing a sulfur atom.

The specific sensitizer may be a sensitizer to the sensitizer described later, and it is a compound having the above-mentioned organometallic complex and having the ability to initiate photoradical polymerization, or a sensitizer having a sensitizing effect to the radical polymerization initiator described later. agent is better.

The specific sensitizer preferably has an absorption maximum wavelength within a wavelength range of 250 nm to 550 nm, and more preferably has a maximum absorption wavelength within a wavelength range of 300 nm to 450 nm. For example, the above-mentioned absorption maximum wavelength is measured by a known method using a spectrophotometer.

Preferably, the condensed ring structure in the specific sensitizer contains at least one atom selected from the group consisting of a nitrogen atom and a sulfur atom as a ring member in the condensed ring structure. As a ring member in the condensed ring structure containing at least one atom selected from the group consisting of a nitrogen atom and a sulfur atom, it means that at least one ring structure of at least two ring structures forming the condensed ring structure contains at least one selected from the group consisting of a nitrogen atom and a sulfur atom. At least one atom in the group of nitrogen atom and sulfur atom is used as a ring member. Examples of the ring structure including a nitrogen atom as a ring member include a pyrrolidine ring, a pyrrole ring, an imidazolium ring, an oxazolidine ring, a tetrahydrothiazole ring, an isotetrahydrothiazole ring, a triazole ring, a tetrazole ring, Piperidine ring, piperidine ring, pyridine ring, dihm ring, trihm ring, 4-piperidone ring, etc. As a ring structure containing a sulfur atom as a ring member, a thiophene ring, a tetrahydrothiophene ring, a tetrahydrothiazole ring, an isotetrahydrothiazole ring, a dithiazole ring, a 4-tetrahydrothiopyranone ring, etc. are mentioned. The ring that forms a condensed ring structure with a ring structure including at least one atom selected from the group consisting of a nitrogen atom and a sulfur atom as a ring member is not particularly limited. At least one atom in the group is a ring structure of ring members, but a hydrocarbon ring structure is preferable, an aromatic hydrocarbon ring structure is more preferable, and a benzene ring structure is further preferable.

在式（1-1）、式（2-1）或式（3-1）中，R¹¹ ～R¹⁹ 分別獨立地表示氫原子或取代基，R¹¹ ～R¹⁹ 中的至少2個可以鍵結而形成環結構，R²¹ ～R²⁸ 分別獨立地表示氫原子或取代基，R²¹ ～R²⁸ 中的至少2個可以鍵結而形成環結構，R³¹ ～R³⁹ 分別獨立地表示氫原子或取代基，R³¹ ～R³⁹ 中的至少2個可以鍵結而形成環結構。From the viewpoints of resolution, exposure sensitivity, and chemical resistance, it is preferred that the specific sensitizer contains at least one structure selected from the group consisting of an acridine structure, a thioxanthone structure, and an acridine structure as the condensed ring structure. good. The specific sensitizer may contain only one at least one structure selected from the group consisting of an acridine structure, a thioxanthone structure, and an acridine structure, or may contain two or more types. When two or more types are included, these structures may be the same or different. Moreover, it is preferable that a specific sensitizer is a compound represented by any one of following formula (1-1), following formula (2-1), and following formula (3-1). [Chemical formula 28]

In formula (1-1), formula (2-1) or formula (3-1), R ¹¹ to R ¹⁹ each independently represent a hydrogen atom or a substituent, and at least two of ^{R 11} to R ^{19 may be bonded} to form a ring structure, R ²¹ to R ²⁸ each independently represent a hydrogen atom or a substituent, ^{at least two of R 21} to R ²⁸ may be bonded to form a ring structure, and R ³¹ to R ³⁹ each independently represent a hydrogen atom Or as a substituent, ^{at least two of R 31} to R ³⁹ may be bonded to form a ring structure.

In formula (1-1), R ¹¹ to R ¹⁸ each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, a hydrocarbon group or a halogen atom. The hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an alkyl group or an aromatic hydrocarbon group is preferable, and an alkyl group is more preferable. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is even more preferable. As the above-mentioned halogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is preferable, and a chlorine atom or a bromine atom is more preferable. In formula (1-1), R ¹⁹ represents a hydrogen atom or a substituent, preferably a hydrogen atom, a hydrocarbon group or a halogen atom, more preferably a hydrogen atom or a hydrocarbon group. In formula (1-1), the preferable aspects of the hydrocarbon group and the halogen atom in ^{R 19} are the same as the preferable aspects of the hydrocarbon group and the halogen atom in ^{R 11} to R ^{18 .} In the present invention, ^{at least two of R 11} to R ¹⁹ may be bonded to form a ring structure, but an ^{aspect in which none of R 11} to R ¹⁹ forms a ring structure is also one of the preferred aspects.

In formula (2-1), R ²¹ to R ²⁸ each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, a hydrocarbon group or a halogen atom, more preferably a hydrogen atom or a halogen atom, and particularly preferably a hydrogen atom. The hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an alkyl group or an aromatic hydrocarbon group is preferable, and an alkyl group is more preferable. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is even more preferable. As the above-mentioned halogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is preferable, and a chlorine atom or a bromine atom is more preferable. In the present invention, ^{at least two of R 21} to R ²⁸ may be bonded to form a ring structure, but an ^{aspect in which none of R 21} to R ²⁸ forms a ring structure is also one of the preferred aspects.

In formula (3-1), R ³¹ to R ³⁸ each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, a hydrocarbon group or a halogen atom. As the above-mentioned hydrocarbon group, either an aliphatic hydrocarbon group or an aromatic hydrocarbon group is used, but an alkyl group or an aromatic hydrocarbon group is preferable. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is even more preferable. As the above-mentioned halogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is preferable, and a chlorine atom or a bromine atom is more preferable. In formula (3-1), R ³⁹ represents a hydrogen atom or a substituent, preferably a hydrogen atom, a hydrocarbon group or a halogen atom, more preferably a hydrogen atom or a hydrocarbon group. In formula (3-1), ^{preferable aspects of the hydrocarbon group and halogen atom in R 39} are the same as those of the hydrocarbon group and halogen atom in R ³¹ to R ³⁸ . In the present invention, ^{at least two of R 31} to R ³⁹ may be bonded to form a ring structure, but an ^{aspect in which none of R 31} to R ³⁹ forms a ring structure is also one of the preferred aspects.

式（3-2）中，R³¹ ～R³⁸ 的含義分別獨立地與上述式（3-1）中的R³¹ ～R³⁸ 相同，較佳態樣亦相同。 式（3-2）中，L表示m價的連結基，係可以具有取代基之m價的烴基為較佳。作為L，例如，可舉出烴基或烴基、-O-、C（=O）-、-S-、-S（=O）₂ -、或者將該等組合2個以上而成之基團，至少包含烴基之基團為較佳，烴基為更佳。 上述烴基可以為脂肪族烴基、芳香族烴基或由該等的組合表示之基團，但飽和脂肪族烴基為較佳。 式（3-2）中，m表示2以上的整數，係2～10的整數為較佳。In addition, the specific sensitizer may also be a compound containing as a partial structure: R in the structure represented by any one of the formula (1-1), the formula (2-1), and the formula (3-1) ^A structure in which at least one of 11 to R ¹⁹ , R ²¹ to R ²⁸ , and R ³¹ to R ³⁹ is a bonding site with another structure. For example, as shown in the following formula (3-2), in the structure represented by the formula (3-1), R ^{39 is} connected as a bonding site to another structure, and the like is exemplified. [Chemical formula 29]

In the formula (3-2), R ³¹ ~ R ³⁸ meaning are independently the same as those in (3-1) R Formula ³¹ ~ R ^38, preferred aspects are also the same. In formula (3-2), L represents an m-valent linking group, which is preferably an m-valent hydrocarbon group which may have a substituent. Examples of L include a hydrocarbon group or a hydrocarbon group, -O-, C(=O)-, -S-, -S(=O) ₂ -, or a group in which two or more of these are combined, A group containing at least a hydrocarbon group is preferable, and a hydrocarbon group is more preferable. The above-mentioned hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these, but a saturated aliphatic hydrocarbon group is preferable. In formula (3-2), m represents an integer of 2 or more, preferably an integer of 2 to 10.

The molecular weight of the specific sensitizer is preferably 100 to 2,000, more preferably 150 to 1,000.

It does not specifically limit as a specific example of a specific sensitizer, 2, 4- dimethyl thioxanthone, N-phenyldiethanolamine, 7-(diethylamino)coumarin-3- Ethyl carboxylate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, acridone, N-methylacridone, N-butanone Acridone, N-butyl-chloroacridone, 9-phenylacridine, 1,7-bis(9,9'-acridine)heptane, p-dimethylaminobenzylidene dihydrogen Indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylidene)benzothiazole, 2-(p-dimethylamine ylphenylvinylidene) isonaphthothiazole, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetoxy-7-dimethylaminocoumarin, 3 -Ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin Bean, 2-mercaptobenzimidazole, 2-mercaptobenzobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl) benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, dibenzothiophene, benzo[b]naphtho[1,2-d]thiophene, benzene And[b]naphtho[1,2-d]thiophene, 4-phenyldibenzothiophene, etc.

It is preferable that content of a specific sensitizer is 0.1-30 mass % with respect to the total solid content system of the photosensitive resin composition of this invention. The lower limit is more preferably 0.2 mass % or more, more preferably 0.5 mass % or more, and particularly preferably 1.0 mass % or more. The upper limit is more preferably 25% by mass or less. One type or two or more types of organometallic complexes can be used. When using 2 or more types, it is preferable that the total amount is in the said range.

Moreover, it is preferable that content of a specific sensitizer is 0.5-5.0 mass parts with respect to 1 mass part of said organometallic complexes, 0.6-3.0 mass parts is more preferable, 0.75-2.0 mass parts is still more preferable.

＜Other resin＞ The composition of the present invention may contain the above-mentioned specific resin and other resins (hereinafter, also simply referred to as "other resins") different from the specific resin. Examples of other resins include polyamide imide, polyamide imide precursor, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, acrylic resin, etc. . For example, by further adding an acrylic resin, a composition excellent in coatability can be obtained, and an organic film excellent in solvent resistance can be obtained. For example, by adding an acrylic resin having a weight-average molecular weight of 20,000 or less and a high polymerizable group value to the composition in place of or in addition to the cross-linking agent described later, it is possible to improve the coatability and organic properties of the composition. The solvent resistance of the film, etc.

When the composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 1% by mass or more, more preferably 1% by mass or more, with respect to the total solid content of the composition. It is more preferable that it is more than 5 mass %, it is more preferable that it is more than 5 mass %, and it is still more preferable that it is more than 10 mass %. In addition, the content of other resins in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, and more preferably 60% by mass or less with respect to the total solid content of the composition. % or less is more preferable, and 50 mass % or less is still more preferable. Moreover, as one of the preferable aspects of the composition of the present invention, it can also be an aspect in which the content of other resins is low. In the above aspect, the content of other resins is preferably 20 mass % or less, more preferably 15 mass % or less, more preferably 10 mass % or less, and 5 mass % or less, based on the total solid content of the composition. It is more preferable, and 1 mass % or less is even more preferable. The lower limit of the above-mentioned content is not particularly limited, and may be 0 mass % or more. The composition of this invention may contain only 1 type of other resin, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.

＜Solvent＞ It is preferable that the photosensitive resin composition of this invention contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfites, amides, ureas, and alcohols.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. , butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, Ethoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), alkyl 3-alkoxypropanoates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionate alkyl esters (for example, 2-alkane Methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methyl propionate and 2-alkane Ethyl oxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate , ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate , dimethyl malonate, diethyl malonate, etc. are preferred.

As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl seleux acetate, ethyl seleux 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 Ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate and the like are preferred.

Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucan ketone, dihydro-levothane Dextranone etc. are preferable.

Examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

As the sulfites, for example, dimethyl sulfite is mentioned as a preferable one.

Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide Amine, N,N-Dimethylisobutyramine, 3-Methoxy-N,N-Dimethylpropionamide, 3-Butoxy-N,N-Dimethylpropionamide, N- Preferable ones are carboxyloxymorpholine, N-acetyloxymorpholine, and the like.

Preferable examples of the urea include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methyl alcohol Oxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether base ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl benzyl alcohol, n-amyl alcohol , methyl amyl alcohol and diacetone alcohol, etc.

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

In the present invention, it is selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl xelousel acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, gamma-butyrolactone, dimethylsulfoxide, ethyl carbitol acetate, butyl carbitol One kind of solvent or a mixed solvent composed of two or more kinds of alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate is preferable. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone together. Moreover, the combination of N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and γ-butyrolactone is also preferable.

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 an amount of 5 to 80% by mass, and the total solid content concentration is set to 5 to 75% by mass. The amount of mass % is more preferable, the total solid content concentration is more preferably 10 to 70 mass %, and the total solid content concentration is more preferably 40 to 70 mass %. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

A solvent may contain only 1 type, and may contain 2 or more types. When two or more kinds of solvents are contained, it is preferable that the total is within the above-mentioned range.

＜Sensitizer＞ The composition of the present invention preferably contains a photosensitizer. The sensitizer does not contain the compound which is the above-mentioned organometallic complex and has the ability to initiate photoradical polymerization. As a photosensitizer, a photopolymerization initiator is preferable.

[Photopolymerization initiator] The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer. The photopolymerization initiator 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 having photosensitivity to light in the ultraviolet region to the visible region is preferred. In addition, it can also be an activator that has some effect on a sensitizer excited by light to generate active radicals.

In the present invention, the compound conforming to the organometallic complex does not conform to the photosensitive agent and the photoradical polymerization initiator.

When the composition of the present invention has the ability to initiate photo-radical polymerization, it is also preferable that the composition of the present invention does not substantially contain a radical polymerization initiator other than the above-mentioned organometallic complex. The fact that radical polymerization initiators other than the above-mentioned organometallic complexes are not substantially contained means that the content of other radical polymerization initiators other than the above-mentioned organometallic complexes in the composition of the present invention is relative to the above-mentioned organometallic complexes. The total mass of the complex is 5 mass % or less, preferably 3 mass % or less, more preferably 1 mass % or less, and still more preferably 0.1 mass %. Furthermore, when the composition of the present invention contains an organometallic complex having the ability to initiate radical polymerization, it is also preferable that the composition of the present invention contains the above-mentioned organometallic complex and other photoradical polymerization initiators. When an organometallic complex and other photoradical polymerization initiators are contained in the composition of the present invention, the amount of the organometallic complex relative to the total content of the organometallic complex and other photoradical polymerization initiators The content is preferably 20 to 80 mass %, more preferably 30 to 70 mass %. In addition, as the above-mentioned other photoradical polymerization initiators, an oxime compound described later is preferable.

Preferably, the photoradical polymerization initiator contains at least one compound having a molar absorption coefficient of ^{at least about 50 L/mol -1} /cm ^-1 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferable to measure at a concentration of 0.01 g/L by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent.

As the photoradical polymerization initiator, any known compounds can be used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazole skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, and hexaarylbis Oxime compounds such as imidazoles and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, Metallocene compounds, organoboron compounds, iron aromatic complexes, etc. For such details, reference can be made to the descriptions of paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of International Publication No. 2015/199219, which are incorporated in the present specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP-A No. 2015-087611 can be exemplified, the content of which is incorporated in the present specification. Among the commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one embodiment of the present invention, as the photo-radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.

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

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

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

As an acylphosphine-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide etc. are mentioned. In addition, commercially available IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF Corporation) can be used.

As a photoradical polymerization initiator, an oxime compound is mentioned more preferably. By using the oxime compound, the exposure latitude can be further effectively improved. Since the oxime compound has a wide exposure latitude (exposure margin) and also functions as a photohardening accelerator, it is particularly preferable.

As specific examples of the oxime compound, the compound described in JP 2001-233842 A, the compound described in JP 2000-080068 A, and the compound described in JP 2006-342166 A can be used.

Preferable oxime compounds include, for example, compounds of the following structures, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3 -Propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one , 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy imino-1-phenylpropan-1-one, etc. In the composition of the present invention, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator (oxime-based photopolymerization initiator). The oxime-based photopolymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[Chemical formula 30]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, Japanese Patent Laid-Open No. 2012-014052) can also be preferably used. Photo-radical polymerization initiator 2) described in Gazette No. In addition, TR-PBG-304 (manufactured by Changzhou Trolly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used. Moreover, the oxime compound of the following structure can also be used. [Chemical formula 31]

As a photopolymerization initiator, an oxime compound having a perylene ring can also be used. Specific examples of the oxime compound having a perylene ring include the compounds described in JP 2014-137466 A and the compounds described in JP 06636081 .

As the photopolymerization initiator, an oxime compound having at least one benzene ring of a carbazole ring serving as a skeleton of a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

Oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013 - Compound (C-3) and the like described in paragraph 0101 of Gazette 164471.

As the optimum oxime compound, the oxime compound having a specific substituent disclosed in JP-A No. 2007-269779 or the oxime compound having a thioaryl group disclosed in JP-A No. 2009-191061 can be mentioned. .

From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyltrisium compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl groups Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl - Compounds in the group of benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

More preferred photo-radical polymerization initiators are trihalomethyltrisium compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salts Compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyltriazole compounds, α-amino ketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds It is more preferable to use at least one compound, it is even more preferable to use a metallocene compound or an oxime compound, and it is even more preferable to use an oxime compound.

In addition, as the photoradical polymerization initiator, N, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. can also be used. ,N'-Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-merolinylphenyl)-butanone- Aromatic ketones such as 1,2-methyl-1-[4-(methylthio)phenyl]-2-endolinyl-acetone-1 and other aromatic ketones, alkylanthraquinones, etc. are condensed with aromatic rings. Quinones benzoin, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. Moreover, the compound represented by following formula (I) can also be used.

[Chemical formula 32]

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

[Chemical formula 33]

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. WO 2015/125469 can also be used as the photo-radical 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 15% by mass relative to the total solid content of the composition of the present invention, More preferably, it is 1.0 to 10 mass %. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably within the above range.

[Photoacid generator] Moreover, it is also preferable that the composition of this invention contains a photoacid generator as a photosensitizer. By containing the photoacid generator, for example, acid is generated in the exposed part of the photosensitive film, the solubility of the exposed part in the developing solution (for example, aqueous alkali solution) is increased, and a positive effect in which the exposed part is removed by the developing solution can be obtained. type pattern. Moreover, it is also possible to adopt an aspect in which the composition contains a photoacid generator and a crosslinking agent other than the radical crosslinking agent described later, for example, the crosslinking of the above crosslinking agent is accelerated by the acid generated in the exposed part In response, the exposed portion is less likely to be removed by the developing solution than the non-exposed portion. According to this aspect, a negative pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, and examples thereof include quinonediazide compounds, diazonium salts, phosphonium salts, onium salt compounds such as pernium salts and iodonium salts, and imide sulfonic acids. sulfonate, oxime sulfonate, diazobis, diazo, o-nitrobenzyl sulfonate and other sulfonate compounds.

Examples of the quinonediazide compound include a sulfonic acid of quinonediazide bonded to a polyhydroxy compound via an ester, a sulfonic acid of quinonediazide bonded to a polyamine compound via a sulfonamide, and a quinonediazide compound. The sulfonic acid of diazide is bonded to the polyhydroxypolyamine compound through at least one of an ester bond and a sulfonamide bond, and the like. In the present invention, for example, it is preferable that 50 mol% or more of the entire functional groups of the polyhydroxy compound and polyamine compound are substituted with quinonediazide.

In the present invention, as the quinonediazide, both 5-naphthoquinonediazidesulfonyl and 4-naphthoquinonediazidesulfonyl can be preferably used. The 4-naphthoquinonediazide sulfonate compound has absorption in the i-ray region of a mercury lamp, so it is suitable for i-ray exposure. The absorption of the 5-naphthoquinonediazide sulfonate compound extends to the g-ray region of the mercury lamp, so it is suitable for g-ray exposure. In the present invention, it is preferable to select a 4-naphthoquinonediazidesulfonate compound and a 5-naphthoquinonediazidesulfonate compound according to the wavelength of exposure. In addition, a naphthoquinonediazidesulfonyl ester compound having a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group in the same molecule may be contained, and a 4-naphthoquinonediazidesulfonyl group may also be contained. A nitrogen sulfonate compound and a 5-naphthoquinonediazide sulfonate compound.

The above-mentioned naphthoquinonediazide compound can be synthesized by esterification of a compound having a phenolic hydroxyl group with a quinonediazidesulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinonediazide compounds, the resolution, sensitivity, and residual film rate are further improved. As the above-mentioned naphthoquinone diazide compound, for example, 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, Salts or ester compounds of these compounds and the like.

As the onium salt compound or the sulfonate compound, the compounds described in paragraphs 0064 to 0122 of JP-A No. 2008-013646 can be mentioned.

It is also preferable that the photoacid generator is a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, and is represented by the following formula (OS-1), the following formula (OS-103), the formula (OS-104), or the formula (OS-105) The indicated oxime sulfonate compounds are preferred.

[Chemical formula 34]

In formula (OS-1), X ³ represents an alkyl group, an alkoxy group or a halogen atom. When ^{there are a plurality of X 3} , they may be the same or different. The alkyl group and the alkoxy group in the above-mentioned X ^{3 may have a substituent.} As the alkyl group in the above-mentioned X ³ , a linear or branched alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group in the above-mentioned X ³ , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom in the above-mentioned X ³ , a chlorine atom or a fluorine atom is preferable. In formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. m3 is 2 or 3, a plurality of X ³ may be the same, also be different. In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 1 carbon atoms. The halogenated alkoxy group of ~5, the phenyl group that can be substituted by W, the naphthyl group that can be substituted by W, or the anthranilic acid group that can be substituted by W are preferred. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms. , an aryl group with a carbon number of 6-20, a halogenated aryl group with a carbon number of 6-20.

In the formula (OS-1) in, m3 line 3, X ³ based methyl, X ³ is substituted ortho to the position of lines, R ³⁴ carbon atoms based linear alkyl group of 1 to 10, 7,7-dimethyl Compounds of -2-oxonorbornylmethyl or p-tolyl are particularly preferred.

Specific examples of the oxime sulfonate compound represented by the formula (OS-1) can be exemplified in paragraphs 0064 to 0068 of JP 2011-209692 A and 0158 to 0167 in JP 2015-194674 A The following compounds are described, and these contents are incorporated into this specification.

[Chemical formula 35]

In formulas (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, and when there are plural R ^s2 groups, some R s2 independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group. Halogen atoms, some R ^s6 when there are plural, respectively independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, and ns represents 1 or 2, ms represents an integer from 0 to 6. In formulas (OS-103) to (OS-105), an alkyl group (preferably carbon number 1-30), aryl group (preferably carbon number 6-30) or heteroaryl represented ^{by R s1} (preferably having 4 to 30 carbon atoms) may have a substituent T.

In formulas (OS-103) to (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms) , a hydrogen atom or an alkyl group is more preferable. ^{In some R s2} when there are two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, one is an alkyl group, an aryl group or a halogen atom, more preferably, one is an alkyl group, an aryl group or a halogen atom Alkyl groups and the remainder are hydrogen atoms are particularly preferred. The alkyl or aryl group represented by R ^{s2 may have a substituent T.} In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, and O is preferable. In the above formulae (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

In the formulae (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2. In formulas (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and alkoxy group (preferably having 1 to 30 carbon atoms) represented ^{by R s6 may have substitutions} base. In formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Further, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), and is represented by the above formula (OS- 104) The compound represented by the following formula (OS-107) is particularly preferred, and the compound represented by the above formula (OS-105) is represented by the following formula (OS-108) or formula (OS-109) The compounds indicated are particularly preferred. [Chemical formula 36]

In formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, R ^t8 represents a hydrogen atom, a carbon number of 1 to 8 Alkyl, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl or chlorophenyl, R ^t9 represents hydrogen atom, halogen atom, methyl or methoxy group, R ^t2 represents hydrogen atom or methyl group. In formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

In formulas (OS-106) to (OS-111), R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, or a methoxymethyl group. alkyl group, phenyl group or chlorophenyl group, preferably an alkyl group with 1 to 8 carbon atoms, a halogen atom or a phenyl group, an alkyl group with 1 to 8 carbon atoms is more preferable, and an alkyl group with 1 to 6 carbon atoms is even more preferable Good, methyl is particularly good.

In formulas (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and a hydrogen atom is preferable. R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. Moreover, about the steric structure (E, Z) of an oxime, any one of the said oxime sulfonate compounds may be sufficient as it, and a mixture may be sufficient as it. Specific examples of the oxime sulfonate compounds represented by the above formulae (OS-103) to (OS-105) include paragraphs 0088 to 0095 of JP 2011-209692 A and JP 2015-194674 A. The compounds described in paragraphs 0168 to 0194 of the gazette are incorporated into the present specification.

As another preferable aspect of the oxime sulfonate compound which contains at least one oxime sulfonate group, the compound represented by following formula (OS-101) and formula (OS-102) is mentioned.

[Chemical formula 37]

In formula (OS-101) or formula (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, Sulfo, cyano, aryl or heteroaryl. The aspect in which R ^u9 is a cyano group or an aryl group is more preferable, and the aspect in which R ^u9 is a cyano group, a phenyl group or a naphthyl group is further preferable. In formula (OS-101) or formula (OS-102), R ^u2a represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, ^{-CR u6} H- or CR ^u6 R ^u7 -, R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkane group carbonyl, arylcarbonyl, amido, sulfo, cyano or aryl. Two of R ^u1 to R ^u4 may each be bonded to each other to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom or an alkyl group is preferable, and an ^{aspect in which at least two of R u1} to R ^u4 are bonded to each other to form an aryl group is also preferable. Among them, the aspect in which all of R ^u1 to R ^u4 are hydrogen atoms is preferable. All of the above-mentioned substituents may further have a substituent.

More preferably, the compound represented by the above formula (OS-101) is a compound represented by the formula (OS-102). Moreover, as for the three-dimensional structure (E, Z, etc.) of an oxime or a benzothiazole ring, any one of the said oxime sulfonate compounds may be sufficient, respectively, and a mixture may be sufficient as them. Specific examples of the compound represented by the formula (OS-101) include compounds described in paragraphs 0102 to 0106 of JP 2011-209692 A and 0195 to 0207 in JP 2015-194674 A. etc. are incorporated into this manual. Among the above compounds, b-9, b-16, b-31 and b-33 are preferred.

Moreover, as a photoacid generator, a commercial item can be used. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, WPAG- 699 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), Omnicat 250, Omnicat 270 (all manufactured by IGM Resins BV), Irgacure 250, Irgacure 270, Irgacure 290 (all manufactured by BASF Corporation), MBZ-101 (Midori Kagaku Co. , Ltd.) and so on.

Moreover, the compound represented by the following structural formula can also be mentioned as a preferable example. [Chemical formula 38]

As the photoacid generator, an organic halogenated compound can also be used. Specific examples of the organic halogenated compound include Wakabayashi et al. "Bull Chem. Soc Japan" 42, 2924 (1969), the specification of US Pat. No. 3,905,815, Japanese Patent Publication No. 46-004605, and Japanese Patent Publication No. 48-036281 No., Japanese Patent Laid-open No. 55-032070, Japanese Patent Laid-open No. 60-239736, Japanese Patent Laid-open No. 61-169835, Japanese Patent Laid-open No. 61-169837, Japanese Patent Laid-open No. 62-058241, Japanese Patent Laid-open No. 61-169837 Compounds described in Sho 62-212401, JP Sho 63-070243, JP Sho 63-298339, MP Hutt "Jurnal of Heterocyclic Chemistry" 1 (No3), (1970), etc., are particularly exemplified The oxazole compound substituted by trihalomethyl: S-triazole compound. More preferably, at least one mono-, di- or trihalogen-substituted methyl group is bonded to an s-tris-tris-s-tris-derivatives. Specifically, for example, 2,4,6-tris(monochloro) methyl)-s-tris-tris, 2,4,6-tris (dichloromethyl)-s-tris, 2,4,6-tris (trichloromethyl)-s-tris, 2-methyl Base-4,6-bis(trichloromethyl)-s-tris, 2-n-butyl-4,6-bis(trichloromethyl)-s-tris, 2-(α,α,β -Trichloroethyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-phenyl-4,6-bis(trichloromethyl)-s-tris-s, 2-(p- Methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris, 2-(3,4-epoxyphenyl)-4, 6-bis(trichloromethyl)-s -Tris, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-tris, 2-[1-(p-methoxyphenyl)-2,4-butanedi Alkenyl]-4,6-bis(trichloromethyl)-s-tris-tris, 2-styryl-4,6-bis(trichloromethyl)-s-tris, 2-(p-methoxy styryl)-4,6-bis(trichloromethyl)-s-tris-styryl, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-s- Tris, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tris, 2-(4-naphthoxynaphthalene)-4,6-bis(trichloromethyl) -s-tris-tris, 2-phenylsulfanyl-4,6-bis(trichloromethyl)-s-tris-tris, 2-benzylsulfanyl-4,6-bis(trichloromethyl)-s-tris 𠯤, 2,4,6-tris(dibromomethyl)-s-tris𠯤, 2,4,6-tris(tribromomethyl)-s-tris𠯤, 2-methyl-4,6-bis (Tribromomethyl)-s-tris, 2-methoxy-4,6-bis(tribromomethyl)-s-tris, etc.

As a photoacid generator, an organic borate compound can also be used. As the organic borate compound, for example, Japanese Patent Application Laid-Open No. 62-143044, Japanese Patent Application Laid-Open No. 62-150242, Japanese Patent Application Laid-Open No. 9-188685, Japanese Patent Application Laid-Open No. 9-188686, Japanese Patent Application Laid-Open No. 9-188686, 188710, Japanese Patent Laid-Open No. 2000-131837, Japanese Patent Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc. and Kunz, Martin "Rad Tech'98. Proceeding April 19-22, 1998 , the organoborate salts described in "Chicago" etc., the organoboronium complexes or organoboronium oxides described in Japanese Patent Laid-Open No. 6-157623, Japanese Laid-Open No. 6-175564, and Japanese Laid-Open No. 6-175561 Substituted tetramethylene complexes, Japanese Patent Laid-Open No. 6-175554, Organoboronium iodine complexes described in Japanese Patent Laid-Open No. 6-175553, Organoboronium phosphonium complexes described in Japanese Patent Laid-Open No. 9-188710 , Japanese Patent Laid-Open No. 6-348011, Japanese Laid-Open No. 7-128785, Japanese Laid-Open No. 7-140589, Japanese Laid-Open No. 7-306527, Japanese Laid-Open No. 7-292014, etc. A transition metal complex complex and the like are specific examples.

As a photoacid generator, a dioxane compound can also be used. As the dioxane compound, the compounds described in Japanese Patent Application Laid-Open No. Sho 61-166544, Japanese Patent Application No. 2001-132318, and the like, and the diazodithio compound can be mentioned.

As said onium salt compound, the diazonium salt described in SISchlesinger, Photogr. Sci. Eng., 18, 387 (1974), TSBal et al, Polymer, 21, 423 (1980), US Pat. , Ammonium salts described in Japanese Patent Laid-Open No. 4-365049, etc., phosphonium salts described in each specification of US Patent No. 4,069,055, US Patent No. 4,069,056, European Patent No. 104,143, US Patent No. 339,049, US Patent No. Specifications of No. 410,201, iodonium salts described in Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 390,214, European Patent No. 233,567, European Patent No. 297,443 , European Patent No. 297,442, US Patent No. 4,933,377, US Patent No. 161,811, US Patent No. 410,201, US Patent No. 339,049, US Patent No. 4,760,013, US Patent No. 4,734,444, US Patent No. 2,833,827, Germany Permamate salts described in each specification of Patent No. 2,904,626, German Patent No. 3,604,580, and German Patent No. 3,604,581, JV Crivello et al, Macromolecules, 10(6), 1307 (1977), JV Crivello et al, J.Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), selenium salts, CSWen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988) described in Onium salts such as pyridinium salts, etc.

在式（RI-I）中，Ar₁₁ 表示可以具有1～6個取代基之碳數20以下的芳基，作為較佳取代基，可舉出碳數1～12的烷基、碳數1～12的烯基、碳數1～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的烷基胺基、碳數1～12的二烷基胺基、碳數1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫基烷基、碳數1～12的硫基芳基。Z₁₁ ^- 表示1價陰離子，鹵素離子、過氯酸根離子、六氟磷酸根離子、四氟硼酸根離子、磺酸根離子、亞磺酸根離子、硫磺酸根離子、硫酸根離子，從穩定性方面考慮，過氯酸根離子、六氟磷酸根離子、四氟硼酸根離子、磺酸根離子、亞磺酸根離子為較佳。在式（RI-II）中，Ar₂₁ 、Ar₂₂ 表示可以各自獨立地具有1～6個取代基之碳數20以下的芳基，作為較佳取代基，可舉出碳數1～12的烷基、碳數1～12的烯基、碳數1～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的烷基胺基、碳數1～12的二烷基胺基、碳數1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫基烷基、碳數1～12的硫基芳基。Z₂₁ ^- 表示1價陰離子，鹵素離子、過氯酸根離子、六氟磷酸根離子、四氟硼酸根離子、磺酸根離子、亞磺酸根離子、硫磺酸根離子、硫酸根離子，從穩定性、反應性方面考慮，過氯酸根離子、六氟磷酸根離子、四氟硼酸根離子、磺酸根離子、亞磺酸根離子、羧酸根離子為較佳。在式（RI-III）中，R₃₁ 、R₃₂ 、R₃₃ 表示可以各自獨立地具有1～6個取代基之碳數20以下的芳基或烷基、烯基、炔基，從反應性、穩定性方面考慮，較佳為芳基。作為較佳取代基，可舉出碳數1～12的烷基、碳數1～12的烯基、碳數1～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的烷基胺基、碳數1～12的二烷基胺基、碳數1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫基烷基、碳數1～12的硫基芳基。Z₃₁ ^- 表示1價陰離子，鹵素離子、過氯酸根離子、六氟磷酸根離子、四氟硼酸根離子、磺酸根離子、亞磺酸根離子、硫磺酸根離子、硫酸根離子，從穩定性、反應性方面考慮，過氯酸根離子、六氟磷酸根離子、四氟硼酸根離子、磺酸根離子、亞磺酸根離子、羧酸根離子為較佳。As an onium salt, the onium salt represented by the following general formula (RI-I) - (RI-III) is mentioned. [Chemical formula 39]

In formula (RI-I), Ar ₁₁ represents an aryl group with 20 or less carbon atoms which may have 1 to 6 substituents, and preferable substituents include an alkyl group with 1 to 12 carbons, an alkyl group with 1 to 12 carbon atoms, Alkenyl group of to 12, alkynyl of carbon number of 1 to 12, aryl group of carbon number of 1 to 12, alkoxy of carbon number of 1 to 12, aryloxy group of carbon number of 1 to 12, halogen atom, carbon number of 1 ~12 alkylamine group, carbon number 1-12 dialkylamine group, carbon number 1-12 alkylamide group or arylamide group, carbonyl, carboxyl, cyano, sulfonyl, carbon A thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, sulfuric acid ion, sulfate ion, considering the stability , Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ represent aryl groups having 1 to 6 substituents each independently having 20 carbon atoms or less, and preferable substituents include those having 1 to 12 carbon atoms. Alkyl, alkenyl with 1-12 carbons, alkynyl with 1-12 carbons, aryl with 1-12 carbons, alkoxy with 1-12 carbons, aryloxy with 1-12 carbons, Halogen atom, alkylamine group having 1 to 12 carbon atoms, dialkylamine group having 1 to 12 carbon atoms, alkylamide group or arylamide group having 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group , sulfonyl group, thioalkyl group with 1 to 12 carbon atoms, thioaryl group with 1 to 12 carbon atoms. Z ₂₁ ^- represents a monovalent anion, halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, from stability, reaction From the viewpoint of properties, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferred. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ represent an aryl group, an alkyl group, an alkenyl group, and an alkynyl group with a carbon number of 20 or less, which may each independently have 1 to 6 substituents, and are represented by reactive groups. , In view of stability, it is preferably an aryl group. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an aryl group having 1 to 12 carbon atoms. alkoxy group, aryloxy group with 1-12 carbon atoms, halogen atom, alkylamine group with 1-12 carbon atoms, dialkylamine group with 1-12 carbon atoms, alkyl amide group with 1-12 carbon atoms An amino group or an arylamide group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₃₁ ^- represents a monovalent anion, halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, from stability, reaction From the viewpoint of properties, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferred.

[化學式41]

[化學式42]

[化學式43]

Specific examples include the following. [Chemical formula 40]

[Chemical formula 41]

[Chemical formula 42]

[Chemical formula 43]

When a photoacid generator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and even more preferably 2 to 15 mass % with respect to the total solid content of the composition of the present invention. A photoacid generator may contain only 1 type, and may contain 2 or more types. When two or more types of photoacid generators are contained, it is preferable that the total is within the above-mentioned range.

[Photobase generator] The photosensitive resin composition of the present invention may contain a photobase generator as a photosensitizer. The photosensitive resin composition can also contain a photobase generator and a crosslinking agent described later, for example, the cyclization of a specific resin is accelerated by the alkali generated in the exposed portion, and the crosslinking reaction of the crosslinking agent is accelerated. etc., whereby the exposed portion is less likely to be removed by the developing solution than the non-exposed portion. According to this aspect, a negative relief pattern can be obtained.

As a photobase generator, if a base is generated by exposure, it will not specifically limit, A well-known thing can be used. For example, M.Shirai and M.Tsunooka, Prog.Polym.Sci., 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev. , 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol. , 13, 153 (2000); M.Winkle, and K.Graziano, J.Photopolym.Sci.Technol., 3,419 (1990); M.Tsunooka, H.Tachi, and S.Yoshitaka, J.Photopolym.Sci.Technol. , 9, 13 (1996); K.Suyama, H.Araki, M.Shirai, J.Photopolym.Sci.Technol., 19,81 (2006), there can be mentioned transition metal compound complexes, compounds with ammonium Substances with structures such as salts, ionic compounds such as those whose amidine moieties are latentized by forming salts with carboxylic acids, ionic compounds whose salts are neutralized by forming salts, urethane derivatives, oxime ester derivatives, A base component such as an acyl compound is a nonionic compound latentized by a urethane bond, an oxime bond, or the like. In the present invention, examples of the photobase generator include carbamate derivatives, amide derivatives, amide derivatives, α-cobalt complexes, imidazole derivatives, cinnamamide derivatives, and oxime derivatives. as a better example.

Although it does not specifically limit as an alkaline substance generate|occur|produced from a photobase generator, The compound which has an amine group, especially polyamines, such as a monoamine and a diamine, and an amidine, etc. are mentioned. From the viewpoint of the imidization rate, it is preferable that the pKa in DMSO (dimethylsulfite) of the above-mentioned basic substance-based conjugate acid is larger. The above-mentioned pKa is preferably 1 or more, and more preferably 3 or more. The upper limit of the above pKa is not particularly limited, but 20 or less is preferable. Here, the above pKa represents the logarithm of the reciprocal of the first dissociation constant of an acid, and can refer to Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC Edited by: Braude, EA , Nachod, FC; Academic Press, New York, 1955), Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using the software of ACD/pKa (manufactured by ACD/Labs) was used as pKa.

From the viewpoint of the storage stability of the photosensitive resin composition, the photobase generator is preferably a photobase generator that does not contain a salt in its structure, and the nitrogen atom of the alkali moiety generated in the photobase generator has no charge. is better. As a photobase generator, the base generated is preferably potentialized by covalent bonds, and the mechanism of base generation is that the covalent bond between the nitrogen atom of the generated base part and the adjacent atom is cut to generate the base The mechanism is better. If it is a photobase generator which does not contain a salt in a structure, since a photobase generator can be made neutral, a solvent solubility becomes more favorable, and a service life is extended. From such a reason, the amine produced from the photobase generator used in the present invention is preferably a primary amine or a secondary amine. In addition, from the viewpoint of the chemical resistance of the pattern, it is preferable that the photobase generator contains a salt in the structure as the photobase generator.

In addition, considering the above-mentioned reasons, as the photobase generator, the base generated as described above is preferably latentized by a covalent bond, and the generated base is preferably latentized by an amide bond, a urethane bond, and an oxime bond. good. As the photobase generator of the present invention, for example, the photobase generator having a cinnamamide structure disclosed in Japanese Patent Laid-Open No. 2009-080452 and International Publication No. 2009/123122, such as Japanese Patent Laid-Open No. 2006 - Photobase generators with urethane structure disclosed in Japanese Patent Laid-Open No. 189591 and Japanese Patent Laid-Open No. 2008-247747, such as those disclosed in Japanese Patent Laid-Open No. 2007-249013 and Japanese Patent Laid-Open No. 2008-003581 The photobase generator of an oxime structure and a carbamoyl oxime structure, etc., are not limited to these, and the structure of a well-known photobase generator can be used.

In addition, examples of the photobase generator include compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of JP-A No. 2012-093746, and those described in paragraphs 0022 to 0069 of JP-A No. 2013-194205. The compounds described in Japanese Patent Laid-Open No. 2013-204019, Paragraphs 0026 to 0074, and the compounds described in International Publication No. 2010/064631, Paragraph 0052 are exemplified.

Moreover, as a photobase generator, a commercial item can be used. Commercially available products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB- 174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, WPBG-082 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), A2502, B5085, N0528, N1052, O0396, O0447, O0448 ( Tokyo Chemical Industry Co., Ltd.) and so on.

When a photobase generator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and more preferably 2 to 15% by mass relative to the total solid content of the photosensitive resin composition of the present invention. better. Only one type of photobase generator may be contained, or two or more types may be contained. When two or more types of photobase generators are contained, it is preferable that the total is within the above-mentioned range.

<Thermal polymerization initiator> The composition of the present invention may contain a thermal polymerization initiator, especially a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the resin and the crosslinking agent can also be polymerized in the heating process described later, so that the solvent resistance can be further improved.

As a thermal radical polymerization initiator, the compound described in the paragraphs 0074-0118 of Unexamined-Japanese-Patent No. 2008-063554 is mentioned specifically,.

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 5 to 15 mass % with respect to the total solid content of the composition of the present invention. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, the total amount is preferably within the above range.

<Thermal acid generator> The composition of the present invention may contain a thermal acid generator. The thermal acid generator has the effect of generating an acid by heating, promoting a compound selected from the group consisting of a methylol group, an alkoxymethyl group or an oxymethyl group, an epoxy compound, an oxetane compound, and a benzoyl group Cross-linking reaction of at least one of the 𠯤 compounds.

The thermal decomposition initiation temperature of the thermal acid generator is preferably 50°C to 270°C, more preferably 50°C to 250°C. In addition, if an acid is not generated during drying (pre-baking: about 70 to 140° C.) after the composition is applied to the substrate, and the final heating (curing: about 70° C.) after patterning is selected for subsequent exposure and development 100 to 400° C.), which generates an acid as a thermal acid generator, is preferable because it can suppress the decrease in sensitivity during development. When the thermal acid generator was heated to 500°C at 5°C/min in a pressure-resistant capsule, the peak temperature of the exothermic peak with the lowest temperature was determined as the thermal decomposition initiation temperature. Q2000 (manufactured by TA Instruments Inc.) etc. are mentioned as an apparatus used when measuring the thermal decomposition start temperature.

Acid-based strong acids generated from thermal acid generators are preferably, for example, arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or Halogenated alkyl sulfonic acids such as trifluoromethanesulfonic acid are preferred. Examples of such thermal acid generators include those described in paragraph 0055 of JP-A-2013-072935.

Among them, from the viewpoint of less residue in the organic film and less likely to degrade the physical properties of the organic film, as thermal acid generators, those that generate alkyl sulfonic acids having 1 to 4 carbon atoms and halogenated alkyl sulfonic acids having 1 to 4 carbon atoms are used as thermal acid generators. More preferably, methanesulfonic acid (4-hydroxyphenyl) dimethyl strontium, methanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl) dimethyl sulfoxide, methanesulfonic acid benzyl (4 -Hydroxyphenyl)methyl perionium, benzyl methanesulfonate (4-((methoxycarbonyl)oxy)phenyl)methyl perionate, methanesulfonic acid (4-hydroxyphenyl)methyl ((2- Methylphenyl)methyl)perylium, (4-hydroxyphenyl)dimethylperylene trifluoromethanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethyltrifluoromethanesulfonate Benzyl trifluoromethanesulfonate (4-hydroxyphenyl) methyl strontium, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl)oxy)phenyl)methyl sulfa, trifluoromethanesulfonate Methanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)coronium, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2 (5H)-ylidene)-2-(o-tolyl)propionitrile and 2,2-bis(3-(methanesulfonamido)-4-hydroxyphenyl)hexafluoropropane are preferred.

Moreover, it is also preferable to use the compound described in Unexamined-Japanese-Patent No. 2013-167742 No. 0059 as a thermal acid generator.

The content of the thermal acid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, with respect to 100 parts by mass of the specific resin. Since a crosslinking reaction is accelerated|stimulated by containing 0.01 mass part or more, the mechanical property and solvent resistance of an organic film can be improved further. In addition, from the viewpoint of the electrical insulating properties of the organic film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is still more preferable.

＜Onium salt＞ The photosensitive resin composition of the present invention may further contain an onium salt. In particular, when the photosensitive resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain an onium salt. The type and the like of the onium salt are not particularly limited, but preferably ammonium salt, imide salt, perionium salt, iodonium salt, or phosphonium salt can be mentioned. Among these, ammonium salts or imide salts are preferable from the viewpoint of high thermal stability, and periconium salts, iodonium salts, or phosphonium salts are preferable from the viewpoint of compatibility with polymers.

The onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bound through a covalent bond. That is, the onium salt can be an intramolecular salt having a cation part and an anion part in the same molecular structure, or an intermolecular salt in which cation molecules and anion molecules of different molecules are ionically bonded, but the intermolecular salt is better. Moreover, in the photosensitive resin composition of this invention, the said cation part or a cation molecule and the said anion part or an anion molecule may be bonded by an ionic bond, and may dissociate. As the cation in the onium salt, ammonium cation, pyridinium cation, perium cation, iodonium cation or phosphonium cation are preferred, and at least one cation selected from the group consisting of tetraalkylammonium cation, pericynium cation and iodonium cation is better.

The onium salt used in the present invention may also be a thermal alkali generator described later. The thermal base generator refers to a compound that generates a base by heating, and for example, a compound that generates a base when heated to 40° C. or higher is exemplified. Examples of the onium salt include the onium salts described in paragraphs 0122 to 0138 of International Publication No. 2018/043262. In addition, onium salts that can be used in the field of polyimide precursors can also be used without particular limitations.

When the photosensitive resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass relative to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 0.5 mass % or more, still more preferably 0.85 mass % or more, and still more preferably 1 mass % or more. The upper limit is more preferably 30 mass % or less, more preferably 20 mass % or less, still more preferably 10 mass % or less, and may be 5 mass % or less, or 4 mass % or less. One or more of the onium salts can be used. When using 2 or more types, it is preferable that the total amount is in the said range.

<Heat base generator> The photosensitive resin composition of this invention may further contain a heat base generator. In particular, when the photosensitive resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain a thermal base generator. The thermal base generator may be a compound corresponding to the above-mentioned onium salt, or may be another thermal base generator other than the above-mentioned onium salt. As the thermal alkali generator other than the above-mentioned onium salt, a nonionic thermal alkali generator can be mentioned. As a nonionic thermal base generator, the compound represented by formula (B1) or formula (B2) is mentioned. [Chemical formula 44]

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. In addition, none of Rb ¹ , Rb ² and Rb ³ has a carboxyl group. In addition, in this specification, a tertiary amine structure means the structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the carbon atom to be bonded is a carbon atom forming a carbonyl group, that is, when forming an amide group together with a nitrogen atom, it is not limited to this.

In formulas (B1) and (B2), ^{at least one of Rb 1} , Rb ² and Rb ³ preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring formed by condensing two monocyclic rings is preferable. The single ring system is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. Monocyclic cyclohexane ring and benzene ring are preferable, and cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are hydrogen atoms, alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), alkenyl (having 2 to 24 carbon atoms) is better, 2-18 is better, 3-12 is further better), aryl (carbon number 6-22 is better, 6-18 is better, 6-10 is further better) or arane A base (preferably with a carbon number of 7 to 25, more preferably 7 to 19, and further preferably 7 to 12) is preferable. These groups may have a substituent within a range in which the effects of the present invention are exhibited. Rb ¹ and Rb ² may be bonded to each other to form a ring. As the ring to be formed, a nitrogen-containing heterocyclic ring having 4 to 7 members is preferable. In particular, Rb ¹ and Rb ² are linear, branched or cyclic alkyl groups that may have substituents (the number of carbon atoms is preferably 1-24, more preferably 2-18, and more preferably 3-12) Preferably, a cycloalkyl group which may have a substituent (3-24 carbon atoms are preferable, 3-18 is more preferable, and 3-12 is further preferable) is more preferable, and a cyclohexyl group which may have a substituent group is further preferable .

Examples of Rb ³ include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), and an aryl group (preferably having 6 to 22 carbon atoms, and having 6 to 18 carbon atoms). is more preferred, 6-10 is further preferred), alkenyl (carbon number 2-24 is preferred, 2-12 is more preferred, 2-6 is further preferred), aralkyl (carbon number 7-23) is better, 7-19 is better, 7-12 is further better), arylalkenyl (carbon number 8-24 is better, 8-20 is better, 8-16 is further better), Alkoxy (preferably carbon number 1-24, more preferably 2-18, further preferably 3-12), aryloxy (preferably carbon number 6-22, more preferably 6-18, 6 -12 is more preferred) or aralkoxy (the number of carbon atoms is preferably 7-23, more preferably 7-19, and more preferably 7-12). Among them, cycloalkyl (preferably carbon number 3-24, more preferably 3-18, and more preferably 3-12), arylalkenyl and aralkoxy are preferred. Rb ³ may further have a substituent within a range in which the effects of the present invention are exhibited.

The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical formula 45]

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ^{32 have the same meanings as Rb 1} and Rb ² in formula (B1), respectively. Rb ¹³ is an alkyl group (preferably carbon number 1-24, more preferably 2-18, and further preferably 3-12), alkenyl (preferably carbon number 2-24, more preferably 2-18, 3-12 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 are more preferable, 7-12 are more preferable), and may have a substituent within the range which exhibits the effect of this invention. Among them, Rb ^13- series aralkyl groups are preferred.

Rb ³³ and Rb ³⁴ are independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), an alkenyl group (preferably having a carbon number of 2 to 12). preferably, 2-8 are more preferred, 2-3 are further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), aralkyl ( The number of carbon atoms is preferably 7 to 23, more preferably 7 to 19, and further preferably 7 to 11), and hydrogen atom is more preferred.

Rb ³⁵ is an alkyl group (preferably carbon number 1-24, more preferably 1-12, further preferably 3-8), alkenyl (preferably carbon number 2-12, more preferably 2-10, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 are more preferable, 7-12 are more preferable), aryl group is preferable.

It is also preferable that the compound represented by the formula (B1-1) is a compound represented by the formula (B1-1a). [Chemical formula 46]

Same as Rb Rb ¹¹ and Rb ¹² meaning as in formula (B1-1) ¹¹ and Rb ^12. Rb ¹⁵ and Rb ¹⁶ are hydrogen atoms, alkyl (preferably carbon number 1-12, more preferably 1-6, more preferably 1-3), alkenyl (preferably carbon number 2-12, 2 ～6 is better, 2-3 is further better), aryl (carbon number is 6-22 is better, 6-18 is better, 6-10 is further better), aralkyl (carbon number is 7 -23 is preferred, 7-19 is more preferred, 7-11 is further preferred), hydrogen atom or methyl group is preferred. Rb ¹⁷ is an alkyl group (preferably carbon number 1-24, more preferably 1-12, further preferably 3-8), alkenyl (preferably carbon number 2-12, more preferably 2-10, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 are more preferable, 7-12 are further preferable), among which aryl group is preferable.

The molecular weight of the nonionic thermal alkali generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

The following compounds can be mentioned as a specific example of the compound which is a thermal base generator among the above-mentioned onium salts or a specific example of a thermal base generator other than the above-mentioned onium salt.

[Chemical formula 47]

[Chemical formula 48]

[Chemical formula 49]

It is preferable that content of another thermal alkali generator is 0.1-50 mass % with respect to the total solid content of the photosensitive resin composition of this invention. The lower limit is more preferably 0.5 mass % or more, and even more preferably 1 mass % or more. The upper limit is more preferably 30 mass % or less, and even more preferably 20 mass % or less. One type or two or more types of thermal alkali generators can be used. When using 2 or more types, it is preferable that the total amount is in the said range.

＜Crosslinking agent＞ It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent. As a crosslinking agent, a radical crosslinking agent or another crosslinking agent is mentioned.

<Radical crosslinking agent> It is preferable that the photosensitive resin composition of this invention may further contain a radical crosslinking agent. The radical crosslinking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. As a group containing the said ethylenically unsaturated bond, the group which has an ethylenically unsaturated bond, such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, is mentioned. Among these, as the group containing the above-mentioned ethylenically unsaturated bond, a (meth)acryloyl group is preferable, and a (meth)acryloyloxy group is more preferable from the viewpoint of reactivity.

The radical crosslinking agent may be a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more ethylenically unsaturated bonds. The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the aforementioned ethylenically unsaturated bonds. Moreover, from the viewpoint of the film strength of the obtained pattern, it is preferable that the photosensitive resin composition of this invention contains the compound which has 3 or more of ethylenically unsaturated bonds as a radical crosslinking agent. As the compound having 3 or more of the above-mentioned ethylenically unsaturated bonds, a compound having 3 to 15 ethylenically unsaturated bonds is preferable, a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 3 to 15 ethylenically unsaturated bonds is more preferable. Compounds having 6 ethylenically unsaturated bonds are further preferred. In addition, the compound having three or more of the above-mentioned ethylenically unsaturated bonds is preferably a compound having three or more groups including the above-mentioned ethylenically unsaturated bond, more preferably a compound having 3 to 15 groups, and a compound having 3 to 10 compounds are more preferable, and 3 to 6 compounds are particularly preferable. Furthermore, it is also preferable that the photosensitive resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds from the viewpoint of the film strength of the obtained pattern. .

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters, The amines are preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, the addition reaction products of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl groups, amine groups, and hydrogen thiol groups, and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used. , Dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. In addition, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and further have halogen groups Or the substitution reaction products of unsaturated carboxylic acid esters or amides and monofunctional or polyfunctional alcohols, amines, and thiols of releasable substituents such as tosyloxy group are also preferred. In addition, as another example, a compound group substituted with vinylbenzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether, allyl ether, and the like can also be used instead of the above-mentioned unsaturated carboxylic acid. As a specific example, reference can be made to the descriptions of paragraphs 0113 to 0122 of JP 2016-027357 A, which are incorporated in the present specification.

Moreover, it is also preferable that the radical crosslinking agent is 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 neopentaerythritol tri(meth)acrylate. (Meth)acrylate, Neotaerythritol Tetra (meth)acrylate, Dipivalerythritol Penta (meth)acrylate, Dipivalerythritol Hexa (meth)acrylate, Hexylene Glycol (Methyl) base) acrylate, trimethylolpropane tris (acryloyloxypropyl) ether, tris (acryloyloxyethyl) isocyanate, glycerol or trimethylolethane, etc. in the addition of polyfunctional alcohols Compounds that are (meth)acrylated after ethylene oxide or propylene oxide, as in Japanese Patent Publication No. Sho 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. Sho 51-037193 The (meth)acrylate urethanes described, the polyester acrylates described in Japanese Patent Laid-Open No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490 are used as cyclic Polyfunctional acrylates or methacrylates such as epoxy acrylates, which are reaction products of oxygen resins and (meth)acrylic acid; and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferred. Moreover, the polyfunctional (meth)acrylate etc. obtained by making a polyfunctional carboxylic acid react with a compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, can also be mentioned.

Further, as a preferable radical crosslinking agent other than the above, those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216 and the like can also be used. Compounds having two or more groups having ethylenically unsaturated bonds, cardo resins.

Furthermore, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, Japanese Patent Publication No. Hei 02- Vinylphosphonic acid-based compounds and the like described in Gazette 025493. Moreover, the compound containing a perfluoroalkyl group described in Unexamined-Japanese-Patent No. 61-022048 can also be used. Furthermore, those described as photopolymerizable 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 Laid-Open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, the contents of which are incorporated herein. in the manual.

In addition, the following compounds described in Japanese Patent Laid-Open No. 10-062986 as formula (1) and formula (2) together with specific examples can also be used as a radical crosslinking agent: adding epoxy to a polyfunctional alcohol A compound obtained by (meth)acrylic esterification after ethane or propylene oxide.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A No. 2015-187211 can also be used as a radical crosslinking agent, and these contents are incorporated in the present specification.

As a radical crosslinking agent, dipeotaerythritol triacrylate (as a commercial item, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipeotaerythritol tetraacrylate (as a commercial item , is KAYARAD D-320; Nippon Kayaku Co., Ltd., A-TMMT: Shin-Nakamura Chemical Co., Ltd. KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipeptaerythritol hexa(meth)acrylate (commercially available, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH ; Shin-Nakamura Chemical Co., Ltd.) and the structure in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues is preferred. These oligomer types can also be used.

As a commercial item of a radical crosslinking agent, for example, SR-494 which is a tetrafunctional acrylate having 4 vinyloxy chains, manufactured by Sartomer Company, Inc., and a bifunctional acrylate having 4 vinyloxy chains are mentioned. Methacrylate SR-209, 231, 239 manufactured by Sartomer Company, Inc., DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, DPCA-60 having 3 Isobutoxy chain trifunctional acrylate TPA-330, urethane oligomer UAS-10, 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.

As a radical crosslinking agent, for example, the aminomethyl group described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Acrylic acid esters, ethylene oxides 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 The urethane compounds of the backbone are also preferred. Furthermore, as the radical crosslinking agent, those described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. Hei 01-105238 having an amine group structure in the molecule can also be used. or compounds of sulfide structure.

The free-radical cross-linking agent may be a free-radical cross-linking agent having an acid group such as a carboxyl group and a phosphoric acid group. Among the free-radical crosslinking agents having acid groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, and the unreacted hydroxyl groups of aliphatic polyhydroxy compounds are reacted with non-aromatic carboxylic acid anhydrides to give acid groups. Free-radical cross-linking agents based on the base are more preferred. Particularly preferred is a radical crosslinking agent that has an acid group by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride, and the aliphatic polyhydroxy compound is used as neotaerythritol or dipivale. Compounds of tetraols. As a commercial item, M-510, M-520 etc. are mentioned as a polybasic acid-modified acrylic oligomer by TOAGOSEI CO., Ltd., for example.

The preferred acid value of the free radical crosslinking agent having an acid group is 0.1-40 mgKOH/g, particularly preferably 5-30 mgKOH/g. As long as the acid value of the radical crosslinking agent is within the above-mentioned range, it is excellent in workability in production and further in developability. In addition, the polymerizability was good. On the other hand, the acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, particularly preferably 1 to 100 mgKOH/g, from the viewpoint of the development speed during alkali development. The said acid value is measured according to the description of JISK0070:1992.

It is preferable to use bifunctional methacrylate or acrylate for the photosensitive resin composition of this invention from a viewpoint of the resolution of a pattern and the stretchability of a film. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethylacrylate can be used Base Acrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate, Neopentyl Glycol Dimethacrylate base acrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-triacrylate Cyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, bisphenol PO adduct diacrylate of A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-propenyloxypropyl methacrylate, EO modified diacrylic acid isocyanurate ester, isocyanuric acid modified dimethacrylate, other bifunctional acrylates with urethane bonds, and bifunctional methacrylates with urethane bonds. These can be used in mixture of 2 or more types as needed. Moreover, from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the pattern, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylate can be preferably used Butoxyethyl acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (Meth)acrylic acid derivatives such as (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N- N-vinyl compounds such as vinylpyrrolidone and N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. base compounds, etc. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable.

When a radical crosslinking agent is contained, it is preferable that the content exceeds 0 mass % and 60 mass % or less with respect to the total solid content of the photosensitive resin composition of this invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

A radical crosslinking agent may be used individually by 1 type, and may be used in mixture of 2 or more types. When two or more types are used at the same time, the total amount thereof is preferably within the above range.

<Other crosslinking agents> It is preferable that the photosensitive resin composition of this invention contains another crosslinking agent different from the said radical crosslinking agent. In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, which has a plurality of cross-linking agents in the molecule which are promoted by the sensitivity of the above-mentioned photosensitizer (in combination with other compounds in the composition or The compound of the group that forms a covalent bond between its reaction products is preferably, and it has a plurality of groups in the molecule that are promoted by the action of acid or base (produced by other compounds in the composition or their reaction). Compounds with groups that form covalent bonds between substances are more preferred. The above acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator which is a photosensitive agent in the exposure process. As other cross-linking agents, compounds having at least one group selected from the group consisting of methylol and alkoxymethyl are preferred, and compounds having at least one group selected from the group including methylol and alkoxymethyl are preferred. A compound having a structure in which at least one group in the group is directly bonded to a nitrogen atom is more preferable. Examples of other crosslinking agents include compounds having a structure in which an amine group-containing compound such as melamine, acetylene urea, urea, alkylene urea, and benzoguanamine is reacted with formaldehyde, or formaldehyde is reacted with alcohol and used in combination A hydroxymethyl group or an alkoxymethyl group is substituted for the hydrogen atom of the above-mentioned amine group. The production method of these compounds is not particularly limited, as long as it is a compound having the same structure as the compound produced by the above-mentioned method. Moreover, the oligomer which the methylol groups of these compounds self-condenses may be sufficient. As the above-mentioned amine group-containing compound, the crosslinking agent using melamine is called melamine type crosslinking agent, the crosslinking agent using acetylene carbamide, urea or alkylene urea is called urea type crosslinking agent, and the alkylene urea is called urea type crosslinking agent. The crosslinking agent of base urea is called alkylene urea crosslinking agent, and the crosslinking agent using benzoguanamine is called benzoguanamine crosslinking agent. Among these, the photosensitive resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and preferably contains at least one compound selected from the group consisting of an acetylene urea-based crosslinking agent described below. At least one compound in the group of a linking agent and a melamine-based crosslinking agent is more preferable.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like.

Specific examples of the urea-based crosslinking agent include, for example, monomethylolated acetylene carbamide, dimethylolated acetylene carbamide, trimethylolated acetylene carbamide, tetramethylolated acetylene carbamide, and monomethoxy methoxymethylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetramethoxymethylated acetylene carbamide, monoethoxymethylated acetylene carbamide, diethoxy Methylated acetylene carbamide, triethoxymethylated acetylene carbamide, tetraethoxymethylated acetylene carbamide, monopropoxymethylated acetylene carbamide, dipropoxymethylated acetylene carbamide, tripropoxymethylated acetylene carbamide Methylated acetylene carbamide, tetrapropoxymethylated acetylene carbamide, monobutoxymethylated acetylene carbamide, dibutoxymethylated acetylene carbamide, tributoxymethylated acetylene carbamide, or tetrabutoxymethylated acetylene carbamide Acetylene carbamide cross-linking agents such as methylated acetylene carbamide; Urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea, etc., Monomethylolated ethylene urea or dimethylolated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxy Ethylene urea cross-links such as methylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea joint agent, Monomethylolated propylene urea, dimethylolated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxy Propylene urea such as methylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea, etc. joint agent, 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole pyridone etc.

Specific examples of the benzoguanamine-based crosslinking agent include, for example, monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, and tetrahydroxymethylated benzoguanamine. Methylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated Benzoguanamine, Monoethoxymethylated Benzoguanamine, Diethoxymethylated Benzoguanamine, Triethoxymethylated Benzoguanamine, Tetraethoxymethylated Benzoguanamine Guanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine , Monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc.

In addition, as a compound having at least one group selected from the group consisting of methylol and alkoxymethyl, those selected from the group consisting of methylol and alkoxymethyl can also be preferably used. A compound in which at least one group in the group is directly bonded to an aromatic ring (preferably a benzene ring). Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl) base) benzophenone, hydroxymethyl benzoate, hydroxymethyl benzene, bis(hydroxymethyl) biphenyl, dimethyl bis(hydroxymethyl) biphenyl, bis(methoxymethyl) benzene, bis( Methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxy methoxymethylbenzene, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylenetriphenyl [2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1 ,3-benzenedimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

As other crosslinking agents, commercially available products can be used, and preferable ones include 46DMOC, 46DMOEP (the above are manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP- Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML- BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, the same below) MX-290, NIKALACMX-280, NIKALACMX-270, NIKALACMX-279, NIKALACMW-100LM, NIKALACMX-750LM (the above are manufactured by SANWA CHEMICAL CO., LTD. )Wait.

Moreover, it is also preferable that the photosensitive resin composition of this invention contains at least 1 sort(s) of compound chosen from the group which consists of an epoxy compound, an oxetane compound, and a benzodiazepine compound as another crosslinking agent.

[Epoxy compound (a compound having an epoxy group)] The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200° C. or lower and does not undergo a dehydration reaction due to the cross-linking, so it is difficult to cause film shrinkage. Therefore, low-temperature curing and warpage of the photosensitive resin composition can be effectively suppressed by containing the epoxy compound.

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 repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol bicyclic Oxypropyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbons type epoxy resins; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy-containing silicones such as polymethyl (glycidoxypropyl) siloxane, etc., but It is 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, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) ) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740, RIKARESIN (registered trademark) BEO-20E (the above trade names, manufactured by DIC Corporation), RIKARESIN (registered trade mark) BEO-60E, RIKARESIN (registered trade mark) HBE-100, RIKARESIN (registered trade mark) DME-100, RIKARESIN (registered trade mark) L-200 (trade mark) name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, 2081, 2000, 3000 , EHPE3150, EPOLEAD (registered trademark) GT400, CELVENUS (registered trademark) B0134, B0177 (the above trade names, manufactured by DAICEL CORPORATION), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH- 75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10 S (the above trade names, manufactured by Nippon Kayaku Co., Ltd.), etc.

[Oxetane compounds (compounds having oxetanyl groups)] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyl oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4 -Benzenedicarboxylic 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 may be used alone, or two kinds may be mixed above.

[Benzoxazole compounds (compounds with a benzoxazolyl group)] Since the crosslinking reaction is caused by the ring-opening addition reaction, the benzodiazepine compound does not degas during hardening, thereby reducing thermal shrinkage and suppressing the occurrence of warpage, which is preferable.

Preferable examples of benzodiazepine compounds include Ba-type benzodiazepines, Bm-type benzodiazepines, Pd-type benzodiazepines, and Fa-type benzodiazepines (the above are trade names, manufactured by Shikoku Chemicals Corporation Manufactured), benzos adducts of polyhydroxystyrene resins, and novolac-type dihydrobenzos. These may be used alone, or two or more of them may be mixed.

The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and more preferably 0.5 to 15% by mass, with respect to the total solid content of the photosensitive resin composition of the present invention, and 1.0 -10 mass % is particularly preferred. The other crosslinking agent may be contained only by one type, or may contain two or more types. When two or more kinds of other thermal crosslinking agents are contained, it is preferable that the total is within the above-mentioned range.

<Compounds with Sulfonamide Structure and Compounds with Thiourea Structure> From the viewpoint of improving the adhesiveness of the obtained pattern to the substrate, the photosensitive resin composition of the present invention further contains at least one selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure compound is preferred.

在式（S-1）中，R表示氫原子或有機基團，R可以與其他結構鍵結而形成環結構，*分別獨立地表示與其他結構的鍵結部位。 上述R係與下述式（S-2）中的R² 相同的基團為較佳。 具有磺醯胺結構之化合物可以為具有2個以上磺醯胺結構之化合物，具有1個磺醯胺結構之化合物為較佳。[Compound having a sulfonamide structure] The sulfonamide structure is a structure represented by the following formula (S-1). [Chemical formula 50]

In formula (S-1), R represents a hydrogen atom or an organic group, R may be bonded to other structures to form a ring structure, and * each independently represents a bonding site to other structures. The above R is preferably the same group as ^{R 2} in the following formula (S-2). The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, and a compound having one sulfonamide structure is preferred.

在式（S-2）中，R¹ 、R² 及R³ 分別獨立地表示氫原子或1價有機基團，R¹ 、R² 及R³ 中的2個以上可以相互鍵結而形成環結構。 R¹ 、R² 及R³ 分別獨立地表示1價有機基團為較佳。 作為R¹ 、R² 及R³ 的例子，可舉出氫原子或烷基、環烷基、烷氧基、烷基醚基、烷基矽基、烷氧基矽基、芳基、芳基醚基、羧基、羰基、烯丙基、乙烯基、雜環基、或者將該等組合2個以上而成之基團等。 作為上述烷基，碳數1～10的烷基為較佳，碳數1～6的烷基為更佳。作為上述烷基，例如，可舉出甲基、乙基、丙基、丁基、戊基、己基、異丙基、2-乙基己基等。 作為上述環烷基，碳數5～10的環烷基為較佳，碳數6～10的環烷基為更佳。作為上述環烷基，例如，可舉出環丙基、環丁基、環戊基及環己基等。 作為上述烷氧基，碳數1～10的烷氧基為較佳，碳數1～5的烷氧基為更佳。作為上述烷氧基，可舉出甲氧基、乙氧基、丙氧基、丁氧基及戊氧基等。 作為上述烷氧基矽基，碳數1～10的烷氧基矽基為較佳，碳數1～4的烷氧基矽基為更佳。作為上述烷氧基矽基，可舉出甲氧基矽基、乙氧基矽基、丙氧基矽基及丁氧基矽基等。 作為上述芳基，碳數6～20的芳基為較佳，碳數6～12的芳基為更佳。上述芳基可具有烷基等取代基。作為上述芳基，可舉出苯基、甲苯基、二甲苯基及萘基等。 作為上述雜環基，可舉出從三唑環、吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡唑環、異㗁唑環、異噻唑環、四唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、哌啶環、哌𠯤環、口末啉環、二氫哌喃環、四氫哌喃環、三𠯤環等雜環結構去除1個氫原子之基團等。The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2). [Chemical formula 51]

In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, ^{and two or more of R 1} , R ² and R ³ may be bonded to each other to form a ring structure. It ^{is preferable that R 1} , R ² and R ³ each independently represent a monovalent organic group. Examples of R ¹ , R ² and R ³ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, and an aryl group. An ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined, and the like. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group, etc. are mentioned, for example. As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. As said cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned, for example. As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, etc. are mentioned. As the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. As said alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc. are mentioned. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. The above-mentioned aryl group may have a substituent such as an alkyl group. As said aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned. Examples of the heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, 1 hydrogen is removed from heterocyclic structures such as pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, quinoline ring, dihydropyran ring, tetrahydropyran ring, triscal ring, etc. groups of atoms, etc.

Among these, ^{compounds in which R 1} is an aryl group and R ² and R ³ are each independently a hydrogen atom or an alkyl group are preferred.

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, Hydroxynaphthylsulfonamide, naphthyl-1-sulfonamide, naphthyl-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-di Methylmethanesulphonamide, N,N-Dimethylethanesulphonamide, N,N-Diethylmethanesulphonamide, N-Methoxymethanesulphonamide, N-Dodecylmethanesulphonamide , N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide, etc.

式（T-1）中，R⁴ 及R⁵ 分別獨立地表示氫原子或1價有機基團，R⁴ 及R⁵ 可以鍵結而形成環，R⁴ 可以與*所鍵結之其他結構鍵結而形成環結構，R⁵ 可以與*所鍵結之其他結構鍵結而形成環結構，*分別獨立地表示與其他結構的鍵結部位。[Compound having a thiourea structure] The thiourea structure is a structure represented by the following formula (T-1). [Chemical formula 52]

In formula (T-1), R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, R ⁴ and R ⁵ can be bonded to form a ring, and R ⁴ can be bonded to * other structural bonds form a ring structure, R ⁵ may form a ring structure by bonding with other structures to which * is bonded, and * each independently represents a bonding site with other structures.

Preferably, R ⁴ and R ⁵ are each independently a hydrogen atom. Examples of R ⁴ and R ⁵ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, A carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, a group formed by combining two or more of these, and the like. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group, etc. are mentioned, for example. As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. As said cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned, for example. As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, etc. are mentioned. As the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. As said alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc. are mentioned. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. The above-mentioned aryl group may have a substituent such as an alkyl group. As said aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned. Examples of the heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, 1 hydrogen is removed from heterocyclic structures such as pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, quinoline ring, dihydropyran ring, tetrahydropyran ring, triscal ring, etc. groups of atoms, etc. The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferred.

式（T-2）中，R⁴ ～R⁷ 分別獨立地表示氫原子或1價有機基團，R⁴ ～R⁷ 中的至少2個可以相互鍵結而形成環結構。The compound having a thiourea structure is preferably a compound represented by the following formula (T-2). [Chemical formula 53]

In formula (T-2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a monovalent organic group, ^{and at least two of R 4} to R ⁷ may be bonded to each other to form a ring structure.

Formula (T-2), the same as R (T-1) and the meanings of R ⁴ and R ⁵ of the formula ⁴ and R ^5, preferred aspects are also the same. In formula (T-2), it ^{is preferable that R 6} and R ⁷ are each independently a monovalent organic group. In the formula (T-2), ^{the preferred embodiment of the monovalent organic group in R 6} and R ⁷ and the preferred embodiment of the monovalent organic group in R ⁴ and R ⁵ in the formula (T-1) same.

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1- Adamantyl thiourea, N-benzylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diphenylthiourea Isopropylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea , N,N-diphenylthiourea, ethylenethiourea (2-imidazoline thione), Carbimazole, 1,3-dimethyl-2-thiohydantoin, etc.

〔content〕 The total content of the compound having a sulfonamide structure and the compound having a thiourea structure relative to the total mass of the photosensitive resin composition of the present invention is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, 0.2-3 mass % is more preferable. The photosensitive resin composition of the present invention may contain only one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or may contain two or more types. When only one type is contained, the content of the compound is within the above-mentioned range, and when two or more types are contained, the total amount thereof is preferably within the above-mentioned range.

<Migration inhibitor> It is preferable that the photosensitive resin composition of this invention may further contain a migration inhibitor. By including the migration inhibitor, the transfer of metal ions originating from the metal layer (metal wiring) into the photosensitive film can be effectively suppressed.

The migration inhibitor is not particularly limited, and examples include those having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, iso thiazole ring, tetrazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, quinoline ring, 2H-pyran ring and 6H-pyran ring, tri-pyran ring) compounds, compounds with thiourea and hydrogen thio groups, hindered phenolic compounds, salicylic acid derivatives, and hydrazine derivatives. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

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

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, and JP 2011-059656 The compounds described in paragraph 0052 of Gazette No. 2012-194520, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A No. 2012-194520, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like.

Specific examples of the migration inhibitor include the following compounds.

[Chemical formula 54]

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 % with respect to the total solid content of the photosensitive resin composition. % is further preferred.

Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more kinds of migration inhibitors, it is preferable that the total is within the above-mentioned range.

<Polymerization inhibitor> It is preferable that the photosensitive resin composition of this invention contains a polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, gallic phenol, p-tertiary phenol can be preferably used Butylcatechol (tert-Butylcatechol), 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tertiary butyl-4-methyl phenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl -N-sulfopropylamino)phenol, N-nitrosophenylhydroxylamine first cerium salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy- 3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris 𠯤-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 1,1-diphenyl- 2-picrohydrazino, copper(II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine ammonium salt, N,N'-diphenyl-para Phenyldiamine, 2,4-di-tertiary butylphenol, di-tertiary butylhydroxytoluene, 1,4-naphthoquinone, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of International Publication No. WO 2015/125469 can also be used.

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

[Chemical formula 55]

When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the photosensitive resin composition of the present invention is 0.01 to 20.0 mass %, and 0.01 to 5 mass % is relatively Preferably, 0.02-3 mass % is more preferable, 0.05-2.5 mass % is more preferable.

Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more kinds of polymerization inhibitors, it is preferable that the total is within the above-mentioned range.

<Metal Adhesion Improver> It is preferable that the photosensitive resin composition of this invention contains the metal adhesiveness improver for improving the adhesiveness with the metal material used for electrodes, wiring, etc.. Examples of the metal adhesion improver include silane coupling agents, aluminum-based adhesive agents, titanium-based adhesive agents, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, and β-keto acids. Ester compounds, amine compounds, etc.

Examples of the silane coupling agent include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, and International Publication No. 2011/080992 The compounds described in paragraphs 0063 to 0071 of JP 2014-191252 A, the compounds described in paragraphs 0060 to 0061 of JP 2014-191252 A, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, International Publication No. 2014 The compound described in paragraph 0055 of No. /097594. Furthermore, as described in paragraphs 0050 to 0058 of JP 2011-128358 A, it is also preferable to use two or more different silane coupling agents. Moreover, it is also preferable to use the following compounds as a silane coupling agent. In the following formula, Et represents an ethyl group.

作為其他矽烷偶合劑，例如，可舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-（3,4-環氧環己基）乙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、N-2-（胺乙基）-3-胺丙基甲基二甲氧基矽烷、N-2-（胺乙基）-3-胺丙基三甲氧基矽烷、3-胺丙基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、3-三乙氧基矽基-N-（1,3-二甲基-亞丁基）丙胺、N-苯基-3-胺丙基三甲氧基矽烷、三-（三甲氧基矽基丙基）異氰脲酸酯、3-脲丙基三烷氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、3-三甲氧基矽基丙基琥珀酸酐。該等能夠單獨使用1種或組合使用2種以上。[Chemical formula 56]

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-epoxypropylene. Oxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxy Propyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-Methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N-2 -(Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane , Tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane Silane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

[Aluminum-based Adhesives] Examples of the aluminum-based adhesive adjuvant include tris(ethylacetate)aluminum, tris(acetoacetone)aluminum, ethylacetatediisopropylaluminum, and the like.

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

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By setting it as the said lower limit or more, the adhesiveness of a pattern and a metal layer becomes favorable, and by setting it as the said upper limit or less, the heat resistance and mechanical properties of a pattern become favorable. Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is in the said range.

<Metal Adhesion Improver> It is preferable that the photosensitive resin composition of this invention contains the metal adhesiveness improver for improving the adhesiveness with the metal material used for electrodes, wiring, etc.. As the metal adhesion improving agent, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032-0043 of JP-A 2013-072935 can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the heterocyclic polymer precursor. Scope. By setting it as the said lower limit or more, the adhesiveness of the pattern and a metal layer after a heating process becomes favorable, and by setting it as below the said upper limit value, the heat resistance and mechanical properties of the cured product after a heating process become favorable. Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is in the said range.

＜Other additives＞ The photosensitive resin composition of the present invention can contain various additives, for example, sensitizers, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, as needed, within the range where the effects of the present invention can be obtained agents, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. When these additives are blended, the total blending amount thereof is preferably 3 mass % or less of the solid content of the photosensitive resin composition.

[Sensitizer] The photosensitive resin composition of this invention may contain the sensitizer (it is also called "other sensitizer") different from the said specific sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in an electronically excited state contacts with a thermal hardening accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., to produce electron transfer, energy transfer, and heat generation. Thereby, the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator are decomposed by chemical change, and generate radicals, acids, or bases. Examples of other sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethyl) Aminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene) -4-Methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminobenzene Allylidene indanone, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, N -Phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluenediethanolamine, N-phenylethanolamine, 4-merinobenzophenone, isodimethylaminobenzoate Amyl ester, isoamyl diethylaminobenzoate, 1-phenyl-5-mercaptotetrazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzene Tolyl, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. As a sensitizer, a sensitizing dye can also be used. For details of the sensitizing dye, the descriptions in paragraphs 0161 to 0163 of JP 2016-027357 A can be referred to, and the contents are incorporated in the present specification.

When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass relative to the total solid content of the photosensitive resin composition of the present invention Preferably, 0.5-10 mass % is more preferable. A sensitizer may be used individually by 1 type, and may use 2 or more types together.

[Chain transfer agent] The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, on pages 683-684 of the Dictionary of Polymers, 3rd edition (edited by The Society of Polymer Science, Japan, 2005). As a chain transfer agent, the compound group which has SH, PH, SiH and GeH in a molecule|numerator, for example is used. These generate free radicals by supplying hydrogen to less reactive radicals, or can generate free radicals by deprotonation after oxidation. In particular, a thiol compound can be preferably used.

In addition, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used as the chain transfer agent.

When the photosensitive resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, preferably 1 to 10 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. The mass part is more preferable, and 1 to 5 mass parts is further preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more types of chain transfer agents, the total is preferably within the above range.

又，界面活性劑亦能夠使用國際公開第2015/199219號的0159～0165段中記載之化合物。 關於氟系界面活性劑，亦能夠將在側鏈具有乙烯性不飽和基之含氟聚合物用作氟系界面活性劑。作為具體例，可舉出日本特開2010-164965號公報的0050～0090段及0289～0295段中記載之化合物，例如DIC Corporation製的MEGAFACE RS-101、RS-102、RS-718K等。[Surfactant] From the viewpoint of further improving coatability, a surfactant may be added to the photosensitive resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Moreover, the following surfactant is also preferable. In the following formula, the parentheses representing the repeating units of the main chain represent the content (mol %) of each repeating unit, and the parentheses representing the repeating units of the side chains represent the repeating number of each repeating unit. [Chemical formula 57]

In addition, the compound described in the paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used as the surfactant. Regarding the fluorine-based surfactant, a fluoropolymer having an ethylenically unsaturated group in a side chain can also be used as the fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, for example, MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40 mass %, more preferably 5 to 30 mass %, and particularly preferably 7 to 25 mass %. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the composition.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are Dow Corning Toray Co. ., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (the above are Shin-Etsu Chemical Co. ., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie GmbH), etc.

Examples of hydrocarbon-based surfactants include Pionin A-76, Newkalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T, etc. (the above are manufactured by TAKEMOTO OIL & FAT CO., LTD.), etc.

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylates, Glycerol ethoxylates, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene Ethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), TETRONIC 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), SOLSPERSE 20000 (manufactured by Boyd & Moore Executive Search.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), Pionin D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT CO., LTD.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

Specific examples of the cationic surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer POLYFLOW No.75, No.77, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

As anionic surfactant, W004, W005, W017 (made by Yusho Co., Ltd.), SANDET BL (made by SANYO KASEI Co., Ltd.) etc. are mentioned specifically,.

When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0, with respect to the total solid content of the photosensitive resin composition of the present invention. quality%. Only one type of surfactant may be used, or two or more types may be used. When two or more types of surfactants are used, the total is preferably within the above-mentioned range.

[Higher fatty acid derivatives] In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the photosensitive resin composition of the present invention so that it is biased in the drying process after coating. on the surface of the photosensitive resin composition.

In addition, the compound described in the paragraph 0155 of International Publication No. 2015/199219 can also be used as the higher fatty acid derivative.

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. Only one type of higher fatty acid derivatives may be used, or two or more types may be used. When there are two or more kinds of higher fatty acid derivatives, it is preferable that the total is within the above-mentioned range.

[Thermal polymerization initiator] The resin composition of the present invention may contain a thermal polymerization initiator, especially a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also be advanced, so that the solvent resistance can be further improved.

As a thermal radical polymerization initiator, the compound described in the paragraphs 0074-0118 of Unexamined-Japanese-Patent No. 2008-063554 is mentioned specifically,.

When a thermal polymerization 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 15% by mass relative to the total solid content of the resin composition of the present invention. . Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, the total amount is preferably within the above range.

[Inorganic particles] The resin composition of the present invention may contain inorganic fine particles. Specifically, as inorganic particles, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc. can be included.

The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. When the average particle diameter of the said inorganic particle is less than 0.01 micrometer, the mechanical properties of the said cured film may deteriorate. Moreover, when the average particle diameter of the said inorganic particle exceeds 2.0 micrometers, the resolution may fall by the scattering of exposure light.

[Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and trisulfuric acid-based absorbers can be used. Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, p-butylphenyl salicylate, and the like. Examples of the benzophenone-based ultraviolet absorber include Examples include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-Tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone Wait. In addition, as examples of benzotriazole-based ultraviolet absorbers, 2-(2'-hydroxy-3',5'-di-tertiarybutylphenyl)-5-chlorobenzotriazole, 2-(2 '-Hydroxy-3'-tertiary butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tertiary pentyl-5'-isobutyl) phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2' -Hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl) Benzotriazole, 2-(2'-Hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-Hydroxy-5'-(1,1,3,3-tetramethyl) Phenyl]benzotriazole, etc.

Examples of substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like . Furthermore, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4, 6-Bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2- Hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-(2,4-dihydroxyphenyl)-4,6-bis( 2,4-Dimethylphenyl)-1,3,5-tris(hydroxyphenyl)tris-compounds such as 2,4-bis(2-hydroxy-4-propoxyphenyl)-6 -(2,4-Dimethylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4 -Methylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethyl Phenyl)-1,3,5-tris(bis(hydroxyphenyl)tris) compounds such as bis(hydroxyphenyl)tris; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis) Butoxyphenyl)-1,3,5-tris𠯤, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris𠯤, 2,4, 6-Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris-tris(hydroxyphenyl)tris-compounds, etc.

In this invention, the said various ultraviolet absorbers may be used individually by 1 type, and may be used in combination of 2 or more types. The composition of the present invention may or may not contain the ultraviolet absorber, but when included, the content of the ultraviolet absorber is relatively 0.001 mass % or more and 1 mass % or less with respect to the total solid mass of the composition of the present invention. Preferably, it is 0.01 mass % or more and 0.1 mass % or less is more preferable.

[Organo-titanium compound] The resin composition of the present embodiment may contain an organic titanium compound. When the resin composition contains an organic titanium compound, even if it is cured at a low temperature, a resin layer excellent in chemical resistance can be formed.

As an organotitanium compound which can be used, the thing which an organic group couple|bonded with a titanium atom via a covalent bond or an ionic bond is mentioned. Specific examples of organotitanium compounds are shown in the following I) to VII): I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable in view of excellent storage stability of the negative photosensitive resin composition and obtaining a favorable cured pattern. Specific examples are titanium bis(triethanolamine) diisopropoxytitanium, bis(n-butoxy) bis(2,4-glutarate) titanium, diisopropoxybis(2,4-glutaric acid) ester) titanium, diisopropoxy bis (tetramethyl pimelic acid ester) titanium, diisopropoxy bis (ethyl acetate) titanium, etc. II) Tetraalkoxytitanium compounds: for example, tetrakis(n-butoxy)titanium, tetraethoxytitanium, tetrakis(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium Titanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetrakis (n-nonyloxy)titanium, tetrakis (n-propoxytitanium), tetrastearyltitanium, Tetrakis[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyltrimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium , bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium, etc. IV) Monoalkoxytitanium compounds: for example, tris(dioctyl phosphate) isopropoxytitanium, tris(dodecylbenzenesulfonate) isopropoxytitanium, and the like. V) Titanium oxide compounds: for example, bis(glutarate) titanium oxide, bis(tetramethylpimelate) titanium oxide, phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanate and the like.

Among them, the organotitanium compound is selected from the group consisting of the above-mentioned I) chelate titanium compound, II) tetraalkoxytitanium compound and III) titanocene compound from the viewpoint of exhibiting better chemical resistance. At least one compound is preferred. In particular, diisopropoxybis(ethylacetate)titanium, tetrakis(n-butoxy)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-di Fluoro-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

When the organic titanium compound is blended, the blending amount thereof is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the precursor of the cyclized resin. When the compounding amount is 0.05 parts by mass or more, the obtained cured pattern exhibits favorable heat resistance and chemical resistance, and on the other hand, when it is 10 parts by mass or less, the storage stability of the composition is excellent.

〔Antioxidants〕 The composition of the present invention may contain antioxidants. By containing an antioxidant as an additive, the ductility property of the film after hardening and the adhesiveness with a metal material can be improved. As an antioxidant, a phenol compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. A hindered phenol compound is mentioned as a preferable phenol compound. A compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Moreover, the compound which has a phenol group and a phosphite group in the same molecule about an antioxidant is also preferable. In addition, phosphorus-based antioxidants can also be preferably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tertiarybutyldibenzo[d,f] [1,3,2]Dioxaphosphin-2-yl)oxy]ethyl]amine, bis(2,4-di-tert-butyl-6-methylphenyl)idene Ethyl phosphate, etc. Examples of commercially available antioxidants include ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (the above are manufactured by ADEKA CORPORATION), etc. In addition, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as antioxidants. Moreover, the composition of this invention may contain a latent antioxidant as needed. Examples of potential antioxidants include compounds in which the site functioning as an antioxidant is protected by a protective group, in which the protective group is heated at 100 to 250°C or heated to 80°C in the presence of an acid/base catalyst. It functions as an antioxidant by heating to 200°C and desorption. Examples of potential antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A No. 2017-008219. As a commercial item of a latent antioxidant, ADEKA ARKLS GPA-5001 (made by ADEKA CORPORATION) etc. are mentioned. As examples of preferable antioxidants, 2,2-thiobis(4-methyl-6-tertiary butylphenol), 2,6-di-tertiary butylphenol, and compounds represented by the general formula (3) can be mentioned. represented compound.

[Chemical formula 58]

In the general formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and R ⁶ represents an alkylene group having 2 or more carbon atoms. R ⁷ represents an alkylene group having 2 or more carbon atoms, and includes a monovalent to tetravalent organic group selected from at least one selected from an O atom and a N atom. k represents an integer of 1-4.

The compound represented by the general formula (3) suppresses the oxidative degradation of the aliphatic group and the phenolic hydroxyl group of the resin. Moreover, metal oxidation can be suppressed by the rust preventive effect on the metal material.

In order to be able to act on both the resin and the metal material, k is an integer of 2 to 4 more preferably. Examples of R ⁷ include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, A vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, a combination of these, etc. may further have a substituent. Among them, from the viewpoints of solubility in the developing solution and metal adhesion, alkyl ethers and -NH- are preferred, and from the viewpoints of interaction with resin and metal adhesion by metal complex formation , -NH- is better.

The compounds represented by the following general formula (3) can be exemplified by the following compounds, but are not limited to the following structures.

[Chemical formula 59]

[Chemical formula 60]

[Chemical formula 61]

[Chemical formula 62]

The amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. When the amount added is less than 0.1 part by mass, the effect of improving the ductility after hardening and the adhesion to the metal material cannot be easily obtained, and when it is more than 10 parts by mass, the resin composition may be formed due to the interaction with the sensitizer. Sensitivity decreased. Only one type of antioxidant may be used, or two or more types may be used. When using 2 or more types, it is preferable that these total amounts are in the said range.

＜Restrictions on other contained substances＞ From the viewpoint of coating surface properties, the water content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass. As a method of maintaining the water content, adjustment of the humidity under storage conditions, reduction of the porosity of the storage container, etc. are mentioned.

From the viewpoint of insulating properties, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million: parts per million), more preferably less than 1 mass ppm, and further less than 0.5 mass ppm better. As a metal, sodium, potassium, magnesium, calcium, iron, chromium, nickel, etc. are mentioned. When a plurality of metals are contained, it is preferable that the sum of these metals is within the above-mentioned range.

In addition, as a method for reducing the metal impurities unexpectedly contained in the photosensitive resin composition of the present invention, there can be mentioned a method of selecting a raw material with a small metal content as a raw material constituting the photosensitive resin composition of the present invention, The raw material constituting the photosensitive resin composition of the present invention is filtered through a filter, the inside of the apparatus is lined with polytetrafluoroethylene or the like, and the contamination is suppressed as much as possible by distillation and the like.

Considering the use as a semiconductor material, and from the viewpoint of wiring corrosion, in the photosensitive resin composition of the present invention, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm ppm is further preferred. Among them, it is preferable that it is less than 5 mass ppm in the state of halide ions, it is more preferable that it is less than 1 mass ppm, and it is more preferable that it is less than 0.5 mass ppm. As a halogen atom, a chlorine atom and a bromine atom are mentioned. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably within the above ranges, respectively. As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably used.

As the storage container of the photosensitive resin composition of the present invention, a conventionally known storage container can be used. In addition, for the purpose of suppressing the contamination of impurities into the raw material and the photosensitive resin composition as the storage container, it is also preferable to use a multilayer bottle having an inner wall of the container composed of six kinds of resins in six layers, or a bottle having a seven-layer structure of six kinds of resins. good. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Application of photosensitive resin composition> It is preferable that the photosensitive resin composition of this invention is used for formation of the interlayer insulating film for rewiring layers. In addition, it can also be used for forming an insulating film of a semiconductor element, forming a stress buffer film, or the like.

<Preparation of photosensitive resin 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 a conventionally known method.

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and particles in the photosensitive resin composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, 5 μm or less is preferable, 3 μm or less is more preferable, and 1 μm or less is still more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. Filters can be used pre-cleaned with organic solvents. In the filter filtration process, a plurality of filters can be used in parallel or in series. When using multiple filters, filters with different pore sizes or materials can be used in combination. Also, the various materials can be filtered multiple times. When filtering multiple times, you can filter for loops. Moreover, filtration may be performed after pressurization. When filtration is performed after pressurization, the pressure for pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, and even more preferably 0.05 MPa or more and 0.7 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent material can also be performed. It is also possible to combine filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be mentioned.

(Photosensitive film, cured product, laminate, element, and method for producing the same) Next, a photosensitive film, a cured product, a layered body, an element, and a method for producing these will be described.

The photosensitive film of the present invention is a film formed from the photosensitive resin composition of the present invention. The photosensitive film of the present invention is formed, for example, by applying the photosensitive resin composition of the present invention to a substrate. Although it does not specifically limit as a kind of application method and a base material, Preferably, the application method and base material in the film formation process mentioned later are mentioned. As a film thickness of a photosensitive film, the film thickness of the hardened|cured material mentioned later can be made into the film thickness in the range mentioned later. For example, the film thickness of the photosensitive film may be determined in consideration of shrinkage due to curing at the time of forming the cured product, and the like.

The cured product of the present invention is a cured product of the photosensitive resin composition of the present invention or a cured product of the photosensitive film of the present invention. The cured product of the present invention is preferably a pattern obtained by the pattern forming method of the present invention described later. The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention or the photosensitive film of the present invention. The thickness of the cured film of this invention can be 0.5 micrometer or more, for example, and can be 1 micrometer or more. Moreover, as an upper limit, it can be 100 micrometers or less, and can also be 30 micrometers or less. The cured product of the present invention is preferably used as an interlayer insulating film for a rewiring layer.

Two or more layers composed of the cured product of the present invention may be laminated, and further three to seven layers may be laminated to form a laminated body. The layered product of the present invention includes two or more layers composed of a cured product, and an aspect in which a metal layer is included between any layers composed of the cured product is preferred. For example, a layered body including at least a layered structure in which three layers of a layer composed of a first cured product, a metal layer, and a layer composed of a second cured product are laminated in this order is preferably used. The layer composed of the first cured product and the layer composed of the second cured product are both layers composed of the cured product of the present invention, and examples thereof include the layer composed of the first cured product and the layer composed of the second cured product. It is preferable that the layer which consists of a thing is the aspect of the film which hardens the photosensitive resin composition of this invention. The photosensitive resin composition of the present invention for forming the layer composed of the first cured product and the photosensitive resin composition of the present invention for forming the layer composed of the second cured product may be compositions of the same composition , and can also be composed of different compositions. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a rewiring layer.

As a field|area to which the cured product of this invention can be applied, the insulating film of a semiconductor element, the interlayer insulating film for rewiring layers, a stress buffer film, etc. are mentioned. Other examples include sealing films, substrate materials (base films for flexible printed wiring boards, cover films, interlayer insulating films), and those that are patterned by etching the insulating films for practical mounting as described above. situation etc. For such uses, for example, Science & Technology Co., Ltd. "High-functionalization and Application Technology of Polyimide" April 2008, Masaki Kakimoto/Supervisor, CMC Technical Library "Polyimide Materials" "Foundation and Development of Polyimide", published in November 2011, Japan Polyimide and Aromatic Polymer Research Association/Editor "Latest Polyimide Fundamentals and Applications" NTS, August 2010, etc.

In addition, the cured product of the present invention can also be used in the production of layouts such as offset printing plates and screen plates, applications in etching and molding parts, and production of protective varnishes and dielectric layers in electronics, especially microelectronics.

The production method of the pattern of the present invention (hereinafter, also simply referred to as "the production method of the present invention".) is preferably a film forming process including applying the photosensitive resin composition of the present invention to a substrate to form a film (photosensitive film). . The pattern manufacturing method of the present invention preferably includes the above-mentioned film forming process, an exposure process of exposing the above-mentioned film, and a development process of developing the above-mentioned exposed film to obtain a pattern. Furthermore, the pattern manufacturing method of the present invention includes the above-mentioned film forming process and the above-mentioned development process as required, and preferably includes a heating process for hardening the pattern by heating the pattern obtained by the above-mentioned development process. Specifically, processes including the following (a) to (c) are preferred, and processes including (a) to (d) are more preferred. (a) Film-forming process for forming a film (photosensitive film) by applying a photosensitive resin composition to a substrate (b) Exposure process for exposing the above film (c) The developing process of developing the above-mentioned film after the above-mentioned exposure to obtain a pattern (d) Heating process for hardening the pattern by heating the pattern obtained by the above-mentioned developing process The photosensitive film can be further cured by heating in the above-mentioned heating process.

The manufacturing method of the laminated body which concerns on the preferable embodiment of this invention includes the manufacturing method of the pattern of this invention. The manufacturing method of the laminated body of this embodiment forms a pattern according to the pattern manufacturing method mentioned above, and further performs the process of (a), the process of (a)-(c), or the process of (a)-(d) again. In particular, it is preferable that each of the above-mentioned processes is sequentially performed a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating patterns in this way, a laminated body can be formed. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the pattern, between the patterns, or both. In addition, in the production of the layered body, it is not necessary to repeat all the processes (a) to (d), as described above, by performing at least (a), preferably (a) to (c) or (a) a plurality of times as described above. The process of ~(d) can obtain the laminated body of a pattern.

<Film formation process (layer formation process)> The production method of the preferred embodiment of the present invention includes a film forming step (layer forming step) of applying a photosensitive resin composition to a substrate to form a film (layer).

The type of the base material can be appropriately set according to the application, but is not particularly limited, and examples include semiconductor production base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor Coating, magnetic film, reflective film, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass: spin-on glass), TFT (Thin Film Transistor) array substrate, plasma display panel (PDP) electrode plates, etc. Moreover, layers, such as an adhesive layer and an oxide layer, may be provided on the surface of these base materials. In the present invention, in particular, semiconductor fabrication substrates are preferable, and silicon substrates, Cu substrates, and mold substrates are more preferable. Moreover, layers, such as an adhesion layer and an oxide layer, which consist of hexamethyldisilazane (HMDS) etc. may be provided on the surface of these base materials. Moreover, as a base material, a plate-shaped base material (substrate) is used, for example. The shape of the base material is not particularly limited, and may be a circular shape or a rectangular shape, but a rectangular shape is preferred. As a size of a base material, if it is a circular shape, a diameter is 100-450 mm, for example, Preferably it is 200-450 mm. In the case of a rectangular shape, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.

In addition, when a photosensitive film is formed on the surface of the resin layer (layer composed of the cured product) and the surface of the metal layer, the resin layer and the metal layer serve as base materials.

As a method of applying the photosensitive resin composition to a base material, coating is preferable.

Specifically, as the application method, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, Slot coating method and inkjet method, etc. From the viewpoint of the thickness uniformity of the photosensitive film, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferred. A resin layer having a desired thickness can be obtained by appropriately adjusting the solid content concentration and coating conditions according to the method. In addition, the coating method can be appropriately selected according to the shape of the substrate. In the case of a circular substrate such as a wafer, spin coating, spray coating, inkjet method, etc. are preferred, and in the case of a rectangular substrate, slit coating is preferred. The cloth method, spray method, ink jet method, etc. are preferable. In the case of the spin coating method, for example, it can be applied at a rotational speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. Moreover, depending on the viscosity of the photosensitive resin composition or the set film thickness, it is also preferable to apply it for 10 to 180 seconds at a rotational speed of 300 to 3,500 rpm. In addition, in order to obtain a uniform film thickness, it is also possible to combine a plurality of rotational speeds and apply the coating. Moreover, the method of transcribe|transferring the coating film formed by previously applying on the dummy support by the said applying method can also be applied to a base material. Regarding the transfer method, in the present invention, the production methods described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 and paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can be preferably used. . In addition, a process of removing excess film at the end of the base material may also be performed. Examples of such a process include edge bead removal (EBR), air knife, backwash, and the like. In addition, the following pre-wetting process can also be used: before the resin composition is applied to the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

＜Drying process＞ The manufacturing method of the present invention may also include a drying process to remove the solvent after the film formation process (layer formation process). The preferred drying temperature is 50-150°C, more preferably 70-130°C, and even more preferably 90-110°C. As the drying time, 30 seconds to 20 minutes can be illustrated, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<Exposure process> The manufacturing method of this invention may include the exposure process which exposes the said film (photosensitive film). As long as the exposure amount of the photosensitive resin composition can be cured, is not particularly limited, for example, under an exposure energy in terms of wavelength of 365nm is irradiated 100 ~ 10,000mJ / cm ² is preferred, irradiation of 200 ~ 8,000mJ / cm ² is better.

The exposure light used in the above exposure process preferably includes light with a wavelength of 150-1,000 nm, more preferably includes light with a wavelength of 150-450 nm, and further preferably includes light with a wavelength of 240-550 nm.

As for the exposure wavelength, in terms of the relationship with the light source, (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, and g-rays are exemplified (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), broad spectrum (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm ), ArF excimer laser (wavelength 193nm), F ₂ excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser The second harmonic is 532nm, the third harmonic is 355nm, etc. Regarding the photosensitive resin composition in the present invention, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by i-ray is preferable. Thereby, in particular, high exposure sensitivity can be obtained. In addition, from the viewpoint of operability and productivity, a broad-spectrum (three wavelengths of g, h, and i rays) light source of a high-pressure mercury lamp or a semiconductor laser of 405 nm is also preferable.

＜Development process＞ The manufacturing method of the present invention may include a development process of developing the exposed film (photosensitive film) (developing the above-mentioned film). By performing development, the unexposed part (non-exposed part) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include discharging of the developing solution from a nozzle, spray spraying, and immersion of the substrate in the developing solution, and the nozzle can be preferably discharged. The developing process can include a process of continuously supplying the developer to the substrate, a process of keeping the developer on the substrate in a substantially static state, a process of vibrating the developer by ultrasonic waves, and a combination of these processes.

Development is performed using a developer. The developer can be used without any particular limitation as long as the unexposed portion (non-exposed portion) can be removed. As the developer, a developer containing an organic solvent or an aqueous alkali solution can be used.

In the present invention, the developer preferably contains an organic solvent with a ClogP value of -1 to 5, and more preferably contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by entering the structural formula in ChemBioDraw.

When the developing solution is a developing solution containing an organic solvent, as the organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, propyl acetate, etc. are preferably mentioned. Butyl butyrate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkoxyacetic acid Alkyl esters (eg: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, Methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkoxy propionate alkyl esters (example: 3-alkoxy propionate methyl ester, 3-alkoxy ethyl propionate) etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkane Alkyl oxypropionate (e.g. methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., 2-methoxypropionate) acid methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy Methyl-2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (e.g., methyl 2-methoxy-2-methylpropanoate, 2-ethoxy-2 -ethyl methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, 2-oxobutyrate Ethyl butyrate etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cyrus acetate, Ethyl celsuluce 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 acetic acid Esters, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl ketone, N-methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl ketone, etc. yl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., and as sulfites, preferably dimethyl Moreover, the mixture of these organic solvents can also be mentioned preferably.

When the developing solution is a developing solution containing an organic solvent, in the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. Moreover, when a developing solution contains an organic solvent, 1 type of organic solvent can be used, or 2 or more types can be mixed and used.

When the developer is a developer containing an organic solvent, preferably 50% by mass or more of the developer is an organic solvent, more preferably 70% by mass or more is an organic solvent, and more preferably 90% by mass or more is an organic solvent. Moreover, 100 mass % of the developer may be an organic solvent.

The developer may further contain other components. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

When the developer is an alkaline aqueous solution, the alkaline compound that can be contained in the alkaline aqueous solution includes TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate, and the like, and TMAH is preferred. For example, when TMAH is used, the content of the alkaline compound in the developer in the total amount of the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[How to supply developer] The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the substrate in the developer, a method of overcoating the substrate by supplying the developer on the substrate with a nozzle, or a method of continuously supplying the developer . The type of the nozzle is not particularly limited, and examples thereof include a straight-through nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removal of the non-image area, and the efficiency in manufacturing, the method of supplying the developer with a direct current nozzle or the method of continuously supplying the developer with a spray nozzle is preferable. From the viewpoint of the permeability of the image area, the method of supplying by a spray nozzle is more preferable. Alternatively, a process may be adopted: after continuously supplying the developer with a direct current nozzle, the substrate is rotated to remove the developer from the substrate, and after spin drying, after the continuous supply by the direct current nozzle again, the substrate is rotated to remove the developer from the substrate , the process can also be repeated several times. In addition, as a method of supplying the developer in the developing process, a process of continuously supplying the developer on the substrate, a process of keeping the developer on the substrate in a substantially static state, using ultrasonic waves, etc. to make the developer on the substrate can be used. The process of vibration and the process of combining them, etc.

The development time is preferably 5 seconds to 10 minutes, and more preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, but it is usually 10 to 45°C, preferably 20 to 40°C.

After the treatment with the developer, further rinsing may be performed. In addition, a method of supplying a rinsing liquid or the like may be employed before the developing liquid in contact with the pattern is completely dried. Rinse is preferably performed with a solvent different from that of the developer. For example, rinsing can be performed using the solvent contained in the photosensitive resin composition. When the developing solution is a developing solution containing an organic solvent, as a rinse solution, PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropyl alcohol), etc. are mentioned, and PGMEA is preferable. Moreover, water is preferable as a rinsing liquid in the development based on the developing liquid containing an alkaline aqueous solution. The flushing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 5 seconds to 1 minute. The temperature of the rinsing liquid at the time of rinsing is not particularly limited, but it is preferably 10 to 45°C, more preferably 18 to 30°C.

As the organic solvent when the rinse liquid contains an organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, Isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate ( Example: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid methyl ester, ethyl ethoxyacetate, etc.), 3-alkoxypropionic acid alkyl esters (for example: methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid Alkyl esters (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy-2- Methyl methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate acid ethyl ester, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl seleuronate, ethyl selenium can be preferably cited Threonyl acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N -Methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are preferably used, and as sulfites, dimethine is preferably used Methyl sulfite and alcohols include methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, Triethylene glycol etc., and N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide etc. are mentioned preferably as amides.

When the rinsing liquid contains an organic solvent, one type of organic solvent or two or more types can be used in combination. In the present invention, especially cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are preferred, cyclopentanone, γ-butyrolactone, Dimethyl sulfoxide, PGMEA, and PGME are more preferable, and cyclohexanone and PGMEA are further preferable.

When the rinsing liquid contains an organic solvent, more than 50 mass % of the washing liquid is preferably an organic solvent, more preferably 70 mass % or more is an organic solvent, and more preferably 90 mass % or more is an organic solvent. Moreover, 100 mass % of the rinse liquid may be an organic solvent.

The rinse fluid may further contain other ingredients. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

[How to supply the rinse solution] The method of supplying the rinse liquid is not particularly limited as long as a desired pattern can be formed, and there are the following methods: a method of immersing the substrate in the rinse liquid, a method of forming a liquid film of the rinse liquid on the substrate, and a shower head A method of supplying a rinsing liquid to a substrate, and a method of continuously supplying a rinsing liquid to the substrate by a method such as a straight-through nozzle. From the viewpoints of penetrability of the rinsing liquid, removability of the non-image area, and efficiency in manufacturing, a method of supplying the rinsing liquid using a shower nozzle, a straight-through nozzle, a spray nozzle, etc., and a method of continuously supplying the rinsing liquid through a spray nozzle is preferable However, from the viewpoint of the permeability of the rinse liquid to the image portion, the method of supplying it with a spray nozzle is more preferable. The type of the nozzle is not particularly limited, and examples thereof include a straight-through nozzle, a shower nozzle, and a spray nozzle. That is, the rinsing process is preferably a process of supplying or continuously supplying the rinsing liquid to the exposed film by using a DC nozzle, and even more preferably a process of supplying the rinsing liquid through a spray nozzle. Also, as a method of supplying the rinsing liquid in the rinsing process, a process of continuously supplying the rinsing liquid to the substrate, a process of maintaining the rinsing liquid on the substrate in a substantially static state, and using ultrasonic waves to make the rinsing liquid on the substrate can be used. The process of vibration and the process of combining them, etc.

＜Heating process＞ The manufacturing method of the present invention preferably includes a process (heating process) in which the developed film is heated at 50-450°C. It is preferable to include the heating process after the film forming process (layer forming process), drying process and developing process. In the heating process, for example, a base is generated by decomposing the above-mentioned thermal base generator, and a cyclization reaction as a precursor of a specific resin is carried out. In addition, the photosensitive resin composition of the present invention may contain a radical crosslinking agent other than the precursor as a specific resin, and can also cure the radical crosslinking agent other than the precursor as an unreacted specific resin, etc. in this process. As the heating temperature (maximum heating temperature) of the middle layer in the heating process, 50°C or higher is preferable, 80°C or higher is more preferable, 140°C or higher is further preferable, 150°C or higher is further preferable, and 160°C or higher is still further Preferably, 170°C or higher is still more preferable. The upper limit is preferably 500°C or lower, more preferably 450°C or lower, still more preferably 350°C or lower, still more preferably 250°C or lower, and still more preferably 220°C or lower.

The heating is preferably carried out at a temperature increase rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min from the temperature at the start of heating to the maximum heating temperature. By setting the temperature increase rate to 1°C/min or more, excessive volatilization of the amine can be prevented while ensuring productivity, and by setting the temperature increase rate to 12°C/min or less, the residual stress of the pattern can be alleviated. In addition, in the case of an oven capable of rapid heating, the heating rate is preferably 1 to 8°C/sec, more preferably 2 to 7°C/sec, and 3 to 3°C/sec from the temperature at the start of heating to the maximum heating temperature. 6°C/sec is more preferable.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the process of heating up to the maximum heating temperature is started. For example, when the photosensitive resin composition is applied to the substrate and then dried, the temperature of the dried film (layer) is, for example, 30 to 200°C lower than the boiling point of the solvent contained in the photosensitive resin composition. It is better to start the temperature gradually rising.

The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes. Moreover, by using the photosensitive resin composition of this invention, the said heating time can also be performed for 15 minutes or less.

In particular, when forming a multilayer laminate, it is preferable to heat at a heating temperature of 180°C to 320°C, and more preferably to heat at 180°C to 260°C, from the viewpoint of the interlayer adhesion of the pattern. The reason for this has not been identified, but it is considered that by setting this temperature, the acetylene groups of the specific resin between the layers undergo a cross-linking reaction with each other.

Heating can be done in stages. As an example, the following pretreatment process can be performed: heating from 25°C to 180°C at 3°C/min, holding at 180°C for 60 minutes, heating from 180°C to 200°C at 2°C/min, holding at 200°C for 120 minute. The heating temperature in the pretreatment process is preferably 100-200°C, more preferably 110-190°C, and even more preferably 120-185°C. In the pretreatment process, as described in the specification of US Pat. No. 9,159,547, it is also preferable to perform the treatment while irradiating ultraviolet rays. The characteristics of the film can be improved by this kind of pretreatment process. The pretreatment process can be carried out in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pretreatment can be a process of more than two stages. For example, the pretreatment process 1 can be performed in the range of 100-150°C, and then the pretreatment process 2 can be performed in the range of 150-200°C.

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

The heating process is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, and argon from the viewpoint of preventing the decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. It does not specifically limit as a heating method, For example, a hotplate, an infrared furnace, an electric heating oven, a hot air oven, etc. are mentioned.

<Metal layer formation process> The manufacturing method of the present invention preferably includes a metal layer forming process in which a metal layer is formed on the surface of the developed film (photosensitive film).

The metal layer is not particularly limited. Existing metal types can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper, aluminum, and alloys containing these metals are more preferred. Copper is further preferred.

The method of forming the metal layer is not particularly limited, and conventional methods can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, methods of combining these, and the like are contemplated. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating are exemplified.

The thickness of the metal layer is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and even more preferably 1 to 10 μm at the thickest part.

＜Lamination process＞ Preferably, the manufacturing method of the present invention further includes a lamination process.

The lamination process involves performing (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, (d) on the surface of a pattern (a layer composed of a hardened material) or a metal layer in sequence. A series of heating processes. However, it may be an aspect in which only the film formation process of (a) is repeated. In addition, (d) the heating process may be collectively performed at the end or in the middle of the lamination. That is, it is good also as an aspect in which the process of (a)-(c) is repeated a predetermined number of times, and the heating of (d) is performed after that, and the photosensitive film to be laminated|stacked may be hardened collectively by this. In addition, the (c) development process may include (e) the metal layer forming process, and in this case, the heating of (d) may be performed each time, or the heating of (d) may be performed collectively after lamination for a predetermined number of times. It goes without saying that the above-mentioned drying process, heating process, etc. may be further appropriately included in the lamination process.

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

The above-mentioned lamination process is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably performed 3 to 5 times. In addition, each layer in the lamination process may be the same layer in composition, shape, film thickness, etc., or may be different layers.

For example, the structure of resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably 2 or more and 20 or less resin layers, and the structure of 3 or more and 7 or less layers is More preferably, 3 or more layers and 5 or less layers are further more preferable.

In the present invention, it is particularly preferable to form a pattern (resin layer) of the photosensitive resin composition so as to cover the metal layer after the metal layer is provided. Specifically, it is possible to repeat (a) the film forming process, (b) the exposure process, (c) the developing process, (e) the metal layer forming process, and (d) the heating process in this order, or repeating the (a) The film formation process, (b) exposure process, (c) development process, (e) metal layer formation process and (d) heating process are arranged at the end or in the middle. By alternately performing the lamination process of laminating the photosensitive film and the metal layer forming process, the cured material (pattern) and the metal layer can be alternately laminated.

(Surface activation treatment process) The manufacturing method of the laminated body of the present invention may include a surface activation treatment process of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment. The surface activation treatment process is usually performed after the metal layer formation process, but the metal layer formation process can also be performed after the surface activation treatment process for the photosensitive resin composition layer after the above-mentioned exposure and development process. The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the exposed photosensitive resin composition layer, or may be performed on both the metal layer and the exposed photosensitive resin composition layer. at least in part. The surface activation treatment is preferably performed on at least a part of the metal layer, and the surface activation treatment is preferably performed on a part or all of the region of the metal layer where the photosensitive resin composition layer is formed on the surface. As described above, by subjecting the surface of the metal layer to the surface activation treatment, the adhesiveness with the resin layer provided on the surface can be improved. Moreover, it is also preferable to perform a surface activation process with respect to a part or all of the photosensitive resin composition layer (resin layer) after exposure. As described above, by subjecting the surface of the photosensitive resin composition layer to the surface activation treatment, the adhesiveness with the metal layer and the resin layer provided on the surface activated by the surface activation treatment can be improved. As the surface activation treatment, specifically, it can be selected from plasma treatment, corona discharge treatment, CF ₄ Etching treatment of /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, and then immersion in water containing Treatment in organic surface treatment agents of at least one compound of amine group and thiol group, mechanical roughening treatment using a brush, plasma treatment is preferred, especially oxygen plasma treatment using oxygen as a raw material gas is better. In the case of corona discharge treatment, the energy ^{is preferably 500 to 200,000 J/m 2} , more preferably 1000 to 100,000 J/m ² , and most preferably 10,000 to 50,000 J/m ² .

The present invention also discloses an element (eg, a semiconductor element) comprising the cured product or the laminate of the present invention. As a specific example of an element using the photosensitive resin composition of the present invention for forming an interlayer insulating film for a rewiring layer, reference can be made to the descriptions in paragraphs 0213 to 0218 of JP-A No. 2016-027357 and the descriptions in FIG. 1 . 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, ratios, processing contents, processing steps, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

<Synthesis Example 1: Synthesis of Polymer A-1> 14.06 g (64.5 mmol) of pyromellitic dianhydride (those dried at 140° C. for 12 hours) and 16.8 g (129 mmol) of methacrylic acid 2- Hydroxyethyl ester, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol), and 100 g of diglyme (diglyme) were mixed and stirred at a temperature of 60° C. for 18 hours to produce The diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of SOCl _{2 was} added over 10 minutes while maintaining the temperature at -10±4°C. During the addition of SOCl ₂ , the viscosity increased. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at -5 to 0°C over 20 minutes. . Next, after allowing the reaction mixture to react at 0° C. for 1 hour, 70 g of ethanol was added, and the mixture was stirred at room temperature overnight. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm (revolutions per minute) for 15 minutes. The polyimide precursor was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor was dried under reduced pressure at 45° C. for 3 days, whereby polymer A-1 was obtained. The weight average molecular weight of this polymer A-1 was 19,000. The obtained polymer A-1 is presumed to contain a repeating unit represented by the following formula (A-1). [Chemical formula 63]

<Synthesis Example 2: Synthesis of Polymer A-2> In Synthesis Example 1, 14.06 g (64.5 mmol) of pyromellitic dianhydride (those dried at 140° C. for 12 hours) was changed to 20.0 g (64.5 mmol) mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride (those dried at 140°C for 12 hours) were synthesized in the same manner as in Synthesis Example 1, whereby polymerization was obtained. Object A-2. The weight average molecular weight of polymer A-2 was 22,000. The obtained polymer A-2 is presumed to contain a repeating unit represented by the following formula (A-2). Among the repeating units represented by the formula (A-2), there are a single bond contained in a biphenyl structure derived from 3,3',4,4'-biphenyltetracarboxylic anhydride and a single bond derived from 3,3',4,4 The case where the ester structure formed by '-biphenyl tetracarboxylic anhydride and 2-hydroxyethyl methacrylate exists in the meta position on the benzene ring, the case where it exists in the para position (for example, from the following formula (A-2-2 ) represented by repeating units, etc.), it is believed that these structures are mixed in the polyimide precursor A-2. Similarly, the following will show the polyamides produced when 3,3',4,4'-biphenyltetracarboxylic anhydride or 4,4'-oxydiphthalic anhydride is used as the acid dianhydride in the synthesis example. In the chemical formula of the repeating unit contained in the imine precursor, the single bond or 4,4'-oxydiphthalic acid contained in the biphenyl structure derived from 3,3',4,4'-biphenyltetracarboxylic anhydride The positional relationship on the benzene ring of the ether bond contained in the formic anhydride and the ester bond and the amide bond bonded to the benzene ring contained in each repeating unit is not limited to the structure described in the chemical formula, and it is assumed that the above positional relationship is different. mixed existence. [Chemical formula 64]

<Synthesis Example 3: Synthesis of Polymer A-3> In Synthesis Example 1, 14.06 g (64.5 mmol) of pyromellitic dianhydride (those dried at 140° C. for 12 hours) was changed to 20.0 g (64.5 mmol) mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), except that it was synthesized in the same manner as in Synthesis Example 1, whereby a polymer A- 3. The weight average molecular weight of polymer A-3 was 19,300. The obtained polymer A-3 is presumed to contain a repeating unit represented by the following formula (A-3). [Chemical formula 65]

<Synthesis Example 4: Synthesis of Polymer A-4> In Synthesis Example 1, 14.06 g (64.5 mmol) of pyromellitic dianhydride (dry at 140° C. for 12 hours) was changed to 4,4′ - 9.49 g (32.25 mmol) of biphenyltetracarboxylic dianhydride and 10.0 g (32.25 mmol) of oxydiphthalic dianhydride (all were dried at 140° C. for 12 hours), except that 1 was synthesized in the same manner, whereby polymer A-4 was obtained. The weight average molecular weight of polymer A-4 was 18,000. The obtained polymer A-4 is presumed to contain two types of repeating units represented by the following formula (A-4). [Chemical formula 66]

<Synthesis Example 5: Synthesis of Polymer A-5> 28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in N-methylpyrrolidine with stirring 200 g of ketone was used to prepare solution A. Next, 12.1 g (153 mmol) of pyridine was added to the solution A, and 1.38 g (70.1 mmol) of heptanediyl chloride dissolved in N- was added dropwise to the solution A over 1 hour while maintaining the temperature at -10 to 0°C. A solution of 75 g of methylpyrrolidone. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was further stirred for 60 minutes. After cooling the said reaction liquid to 25 degreeC, 0.005g of p-methoxyphenol was added, and it melt|dissolved. To this solution, 16.75 g (160 mmol) of methacryloyl chloride was added dropwise, and the mixture was stirred at 25° C. for 2 hours, and further stirred at 60° C. for 3 hours. Next, the polybenzoxazole precursor resin was precipitated in 6 liters of water, and the water-polybenzoxazole precursor resin mixture was stirred at 500 rpm for 15 minutes. The polybenzoxazole precursor resin was collected by filtration, stirred again in 6 liters of water for 30 minutes, and filtered again. Next, the obtained polybenzoxazole precursor resin was dried under reduced pressure at 45° C. for 3 days, whereby polymer A-5 was obtained. The weight average molecular weight of the obtained polymer A-5 was 20,000. The obtained polymer A-5 is presumed to contain a repeating unit represented by the following formula (A-5). [Chemical formula 67]

<Synthesis Example 6: Synthesis of Polymer A-6> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser, and an internal thermometer, 2-hydroxy-4,4'-diamine group was removed while removing water. 43.25 g (200 mmol) of diphenyl ether was dissolved in 300 g of N-methylpyrrolidone (NMP). Next, 88.85 g (200 mmol) of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride was added, and the mixture was stirred at a temperature of 40° C. for 2 hours. Next, 50 mL of toluene and 2.18 g (10 mmol) of 3-aminophenol were added, and the mixture was stirred at 40° C. for 2 hours. After stirring, the temperature was raised to 180° C. while flowing nitrogen at a flow rate of 200 ml/min, and the mixture was stirred for 6 hours. After cooling the said reaction liquid to 25 degreeC, 0.005g of p-methoxyphenol was added, and it melt|dissolved. To this solution, 16.75 g (160 mmol) of methacryloyl chloride was added dropwise, and the mixture was stirred at 25° C. for 2 hours, and further stirred at 60° C. for 3 hours. This was cooled to 25 degreeC, 10 g of acetic acid was added, and it stirred at 25 degreeC for 1 hour. After stirring, it was precipitated in 2 liters of water/methanol=75/25 (volume ratio), and stirred at 2,000 rpm for 30 minutes. The precipitated polyimide resin was collected by filtration, rinsed with 1.5 liters of water, and then the filtrate was mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again. The obtained polyimide was dried at 40° C. for 1 day under reduced pressure, whereby a polymer A-6 was obtained. The weight average molecular weight of polymer A-6 was 18,500. The obtained polymer A-6 is presumed to contain a repeating unit represented by the following formula (A-6). [Chemical formula 68]

<Synthesis Example 7: Synthesis of Polymer A-7> 28.0 g (76.4 mmol) of 2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in N-methylpyrrolidine with stirring 200 g of ketone was used to prepare solution A. Next, 12.1 g (153 mmol) of pyridine was added to the solution A, and 1.38 g of 2,5-dihydroxy p-benzodicarboxylic acid dichloride was added dropwise to the solution A over 1 hour while maintaining the temperature at -10 to 0°C. (70.1 mmol, synthetic product) was dissolved in a solution of 75 g of N-methylpyrrolidone. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was further stirred for 60 minutes. After stirring, the temperature was raised to 180° C. while flowing nitrogen at a flow rate of 200 ml/min, and the mixture was stirred for 6 hours. After cooling the said reaction liquid to 25 degreeC, 0.005g of p-methoxyphenol was added, and it melt|dissolved. To this solution, 16.75 g (160 mmol) of methacryloyl chloride was added dropwise, and the mixture was stirred at 25° C. for 2 hours, and further stirred at 60° C. for 3 hours. Next, the polybenzoxazole resin was precipitated in 6 liters of water, and the water-polybenzoxazole resin mixture was stirred at 500 rpm for 15 minutes. The polybenzoxazole resin was collected by filtration, stirred again in 6 liters of water for 30 minutes, and filtered again. Next, the obtained polybenzoxazole resin was dried under reduced pressure at 45° C. for 3 days, whereby polymer A-7 was obtained. The weight average molecular weight of the obtained polymer A-7 was 19,200. The obtained polymer A-7 is presumed to contain a repeating unit represented by the following formula (A-7). [Chemical formula 69]

<Synthesis Example 8: Synthesis of Polymer A'-1> 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of A diester of pyromellitic dianhydride and 2-hydroxyethyl methacrylate was produced by mixing pyridine (258 mmol) and 200 g of γ-butyrolactone, and stirring at room temperature for 36 hours. Next, under ice-cooling, a solution obtained by dissolving 26.6 g of dicyclohexylcarbodiimide (DCC) in 25 g of γ-butyrolactone was added dropwise with stirring. Next, 12.0 g of 4,4'-diaminodiphenyl ether suspended in 45 ml of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethanol was added, followed by stirring for 1 hour, and then, 100 ml of γ-butyrolactone was added. A reaction liquid was obtained by removing the precipitate formed in the reaction mixture by filtration. Next, the polyimide precursor was precipitated in 3 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm (revolutions per minute) for 15 minutes. The polyimide precursor was obtained by filtration and dissolved in 300 mL of tetrahydrofuran, and then the polyimide precursor was obtained again as a precipitate in 2 liters of water. The obtained polyimide precursor was dried under reduced pressure at 45°C for 3 days, whereby polymer A'-1 was obtained. The weight average molecular weight of the polymer A'-1 was 21,000. It is presumed that the obtained polymer A'-1 contains the repeating unit represented by the above formula (A-1).

<Synthesis Example 9: Synthesis of Polymer A'-2> In Synthesis Example 8, 14.06 g (64.5 mmol) of pyromellitic dianhydride (those dried at 140° C. for 12 hours) were changed to 20.0 g (64.5 mmol) of 3,3′,4,4′- A polymer A'-2 was obtained by synthesizing in the same manner as in Synthesis Example 8 except for the biphenyltetracarboxylic anhydride (those dried at 140° C. for 12 hours). The weight average molecular weight of polymer A'-2 was 22,500. It is presumed that the obtained polymer A'-2 contains the repeating unit represented by the above formula (A-2).

<Synthesis Example 10: Synthesis of Polymer A'-3> In Synthesis Example 8, 14.06 g (64.5 mmol) of pyromellitic dianhydride (those dried at 140° C. for 12 hours) were changed to 20.0 g (64.5 mmol) of 4,4′-oxydiphthalic acid A polymer A'-3 was obtained by synthesizing in the same manner as in Synthesis Example 8 except for the formic anhydride (those dried at 140° C. for 12 hours). The weight average molecular weight of polymer A'-3 was 21,200. It is presumed that the obtained polymer A'-3 contains the repeating unit represented by the above formula (A-3).

<Synthesis Example 11: Synthesis of Polymer A'-4> In Synthesis Example 8, 14.06 g (64.5 mmol) of pyromellitic dianhydride (those dried at 140° C. for 12 hours) was changed to 9.49 g (32.25 mmol) of 4,4′-biphenyltetracarboxylic dianhydride A polymer was obtained by synthesizing in the same manner as in Synthesis Example 8, except that 10.0 g (32.25 mmol) of oxydiphthalic dianhydride (all were dried at 140° C. for 12 hours) A'-4. The weight average molecular weight of polymer A'-4 was 21,000. It is presumed that the obtained polymer A'-4 contains two kinds of repeating units represented by the above formula (A-4).

<Examples and Comparative Examples> In each Example, each photosensitive resin composition was obtained by mixing the components described in the following Tables 1 to 4, respectively. In addition, in each comparative example, each composition for comparison was obtained by mixing the components shown in following Table 4, respectively. Specifically, the content of each component described in Tables 1 to 4 was set to the amount (parts by mass) described in each column of Tables 1 to 4. The obtained photosensitive resin composition and the composition for comparison were subjected to pressure filtration under a pressure of 0.3 MPa using a filter made of polytetrafluoroethylene having a filter pore width of 0.8 μm. In addition, in Tables 1 to 4, the description of "-" means that the composition does not contain the component.

[Table 1] Example Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8 9 composition resin A-1 - - - - - - - - - A-2 - - - - - - - - - A-3 36.393 36.393 36.393 36.393 36.393 36.393 36.393 36.393 36.393 A-4 - - - - - - - - - A-5 - - - - - - - - - A-6 - - - - - - - - - A-7 - - - - - - - - - Sensitizer B-1 1.283 - 0.5415 6.415 - - - - - B-2 - - - - - - - - - B-3 - 1.283 - - - - - - - B-4 - - - - 1.283 - - - - B-5 - - - - - 1.283 - - - B-6 - - - - - - 1.283 - - B-7 - - - - - - - 1.283 - B-8 - - - - - - - - 1.283 B-9 - - - - - - - - - B-10 - - - - - - - - - B-11 - - - - - - - - - B-12 - - - - - - - - - cross-linking agent E-1 5.501 5.501 5.501 5.501 5.501 5.501 5.501 5.501 5.501 E-2 - - - - - - - - - Organometallic complexes C-1 - - - - - - - - - C-2 - - - - - - - - - C-3 - - - - - - - - - C-4 - - - - - - - - - C-5 1.283 1.283 1.283 1.283 1.283 1.283 1.283 1.283 1.283 C-6 - - - - - - - - - Photoradical Polymerization Initiator F-1 - - - - - - - - - polymerization inhibitor G-1 - - - - - - - - - G-2 0.073 0.073 0.073 0.073 0.073 0.073 0.073 0.073 0.073 G-3 - - - - - - - - - migration inhibitor H-1 - - - - - - - - - H-2 0.121 0.121 0.121 0.121 0.121 0.121 0.121 0.121 0.121 Metal Adhesion Improver I-1 - - - - - - - - - I-2 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 solvent J-1 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 J-2 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 Evaluation Resolution A A B B A A A A A Exposure sensitivity A A B B A A A A A drug resistance A B A A A A A A A Resolution (Direct Exposure) A A A A A A A A A

[Table 2] Example Example Example Example Example Example Example Example Example 10 11 12 13 14 15 16 17 18 composition resin A-1 - - - - - - 36.393 - - A-2 - - - - - - - 36.393 18.1965 A-3 36.393 36.393 36.393 36.393 36.393 36.393 - - 18.1965 A-4 - - - - - - - - - A-5 - - - - - - - - - A-6 - - - - - - - - - A-7 - - - - - - - - - Sensitizer B-1 - - - - 0.6415 0.6415 1.283 1.283 1.283 B-2 - - - - - 0.6415 - - - B-3 - - - - - - - - - B-4 - - - - - - - - - B-5 - - - - - - - - - B-6 - - - - - - - - - B-7 - - - - - - - - - B-8 - - - - 0.6415 - - - - B-9 1.283 - - - - - - - - B-10 - 1.283 - - - - - - - B-11 - - 1.283 - - - - - - B-12 - - - 1.283 - - - - - cross-linking agent E-1 5.501 5.501 5.501 5.501 5.501 5.501 5.501 5.501 5.501 E-2 - - - - - - - - - Organometallic complexes C-1 - - - - - - - - - C-2 - - - - - - - - - C-3 - - - - - - - - - C-4 - - - - - - - - - C-5 1.283 1.283 1.283 1.283 1.283 1.283 1.283 1.283 1.283 C-6 - - - - - - - - - Photoradical Polymerization Initiator F-1 - - - - - - - - - polymerization inhibitor G-1 - - - - - - - - - G-2 0.073 0.073 0.073 0.073 0.073 0.073 0.073 0.073 0.073 G-3 - - - - - - - - - migration inhibitor H-1 - - - - - - - - - H-2 0.121 0.121 0.121 0.121 0.121 0.121 0.121 0.121 0.121 Metal Adhesion Improver I-1 - - - - - - - - - I-2 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 solvent J-1 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 J-2 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 Evaluation Resolution A A A A A A A A A Exposure sensitivity A A A A A A A A A drug resistance A A A A A A A A A Resolution (Direct Exposure) A A A A A A A A A

[table 3] Example Example Example Example Example Example Example Example Example 19 20 twenty one twenty two twenty three twenty four 25 26 27 composition resin A-1 - - - - - - - - - A-2 - - - - - - - - - A-3 - - - - 36.393 35.11 35.11 35.11 35.11 A-4 36.393 - - - - - - - - A-5 - 36.393 - - - - - - - A-6 - - 36.393 - - - - - - A-7 - - - 36.393 - - - - - Sensitizer B-1 1.283 1.283 1.283 1.283 1.283 1.283 1.283 1.283 1.283 B-2 - - - - - - - - - B-3 - - - - - - - - - B-4 - - - - - - - - - B-5 - - - - - - - - - B-6 - - - - - - - - - B-7 - - - - - - - - - B-8 - - - - - - - - - B-9 - - - - - - - - - B-10 - - - - - - - - - B-11 - - - - - - - - - B-12 - - - - - - - - - cross-linking agent E-1 5.501 5.501 5.501 5.501 - 5.501 5.501 5.501 5.501 E-2 - - - - 5.501 - - - - Organometallic complexes C-1 - - - - - 1.283 - - - C-2 - - - - - - 1.283 - - C-3 - - - - - - - 1.283 - C-4 - - - - - - - - 1.283 C-5 1.283 1.283 1.283 1.283 1.283 - - - - C-6 - - - - - - - - - Photoradical Polymerization Initiator F-1 - - - - - 1.283 1.283 1.283 1.283 polymerization inhibitor G-1 - - - - - - - - - G-2 0.073 0.073 0.073 0.073 0.073 0.073 0.073 0.073 0.073 G-3 - - - - - - - - - migration inhibitor H-1 - - - - - - - - - H-2 0.121 0.121 0.121 0.121 0.121 0.121 0.121 0.121 0.121 Metal Adhesion Improver I-1 - - - - - - - - - I-2 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 solvent J-1 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 J-2 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 Evaluation Resolution A A A A A A A A A Exposure sensitivity A A A A A A A A A drug resistance A A A A A B B A A Resolution (Direct Exposure) A A A A A A A A A

[Table 4] Example Example Example Example Example Example Comparative example 28 29 30 31 32 33 1 2 3 composition resin A-1 - - - - - - - - - A-2 - - - - - - - - - A-3 35.11 35.11 36.393 36.393 36.393 36.393 36.393 36.393 36.393 A-4 - - - - - - - - - A-5 - - - - - - - - - A-6 - - - - - - - - - A-7 - - - - - - - - - Sensitizer B-1 1.283 1.283 1.283 1.283 1.283 1.283 - 1.283 - B-2 - - - - - - - - 1.283 B-3 - - - - - - - - - B-4 - - - - - - - - - B-5 - - - - - - - - - B-6 - - - - - - - - - B-7 - - - - - - - - - B-8 - - - - - - - - - B-9 - - - - - - - - - B-10 - - - - - - - - - B-11 - - - - - - - - - B-12 - - - - - - - - - cross-linking agent E-1 5.501 5.501 5.501 5.501 5.501 5.501 5.501 5.501 5.501 E-2 - - - - - - - - - Organometallic complexes C-1 0.6415 - - - - - - - - C-2 - - - - - - - - - C-3 - - - - - - - - - C-4 - - - - - - - - - C-5 0.6415 - 1.283 1.283 1.283 1.283 1.283 - 1.283 C-6 - 1.283 - - - - - - - Photoradical Polymerization Initiator F-1 1.283 1.283 - - - - - 1.283 - polymerization inhibitor G-1 - - 0.073 - - - - - - G-2 0.073 0.073 - - - 0.073 0.073 0.073 0.073 G-3 - - - 0.073 - - - - - migration inhibitor H-1 - - - - 0.073 - - - - H-2 0.121 0.121 0.121 0.121 0.121 - 0.121 0.121 0.121 Metal Adhesion Improver I-1 - - - - - 0.121 - - - I-2 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 solvent J-1 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 J-2 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 Evaluation Resolution A A A A A A C C A Exposure sensitivity A A A A A A C C A drug resistance A A A A A A A A C Resolution (Direct Exposure) A A A A A A C A A

The details of each component described in Tables 1 to 4 are as follows.

[resin] ・A-1 to A-7: The above-mentioned polymers A-1 to A-7

[Sensitizer] ・B-1: 2,4-Dimethylthioxanthone ・B-2: N-Phenyldiethanolamine ・B-3: Ethyl 7-(diethylamino)coumarin-3-carboxylate ・B-4: 2,4-Dimethylthioxanthone ・B-5: 2-Chlorothioxanthone ・B-6: 2,4-Diisopropylthioxanthone ・B-7: Acridone ・B-8: N-Methylacridone ・B-9: N-butylacridone ・B-10: N-butyl-2-chloroacridone ・B-11: 9-Phenylacridine ・B-12: 1,7-bis(9-acridine)heptane The above-mentioned B-2 is a sensitizer that does not have a condensed ring structure.

上述式中，Me表示甲基。[Organometallic complex] ・C-1: Titanium tetraisopropoxide (manufactured by Matsumoto Fine Chemical Co., Ltd.) ・C-2: Titanium diisopropoxybis(acetylacetone) (Matsumoto Fine Chemical) Co., Ltd.) ・C-3 to C-6: Compounds of the following structures, and C-5 is also a compound having the ability to initiate radical polymerization. [Chemical formula 70]

In the above formula, Me represents a methyl group.

[Crosslinking agent] ・E-1: SR-209 (tetraethylene glycol dimethacrylate, manufactured by Sartomer Company, Inc.) ・E-2: A-DPH (dinepentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Photoradical Polymerization Initiator] ・F-1: IRGACURE OXE 01 (manufactured by BASF)

[Polymerization inhibitor] ・G-1: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・G-2: p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・G-3: 2-Nitroso-1-naphthol

[Migration inhibitor] ・H-1: Compound of the following structure, manufactured by Tokyo Chemical Industry Co., Ltd. ・H-2: Compound of the following structure, manufactured by Tokyo Chemical Industry Co., Ltd. [Chemical formula 71]

上述式中，Et表示乙基。[Metal Adhesion Improver] ・I-1: Compound of the following structure, manufactured by Sigma-Aldrich Co. LLC ・I-2: Compound of the following structure, manufactured by Sigma-Aldrich Co. LLC [Chemical formula 72]

In the above formula, Et represents an ethyl group.

[Solvent] ・J-1: γ-Butyrolactone (manufactured by SANWAYUKA INDUSTRY CORPORATION) ・J-2: Dimethyl sulfite (manufactured by FUJIFILM Wako Pure Chemical Corporation)

<Evaluation> [Evaluation of Resolution] The photosensitive resin composition prepared in each Example or the composition for comparison prepared in each Comparative Example was spin-coated on a silicon wafer. The spin-coated silicon wafer was dried on a hot plate at 100° C. for 5 minutes, thereby forming a photosensitive film with a uniform thickness of 10 μm on the silicon wafer. The photosensitive film on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). Exposure was performed using i-rays, and at a wavelength of 365 nm, with ^{exposure energies of 200, 300, 400, 500, 600, 700, and 800 mJ/cm 2} , light with a line and space pattern formed in a 1 μm scale from 5 μm to 25 μm was used. The mask was exposed to light to obtain a resin layer. The resin layer was developed with cyclopentanone for 60 seconds, and the minimum line width in the exposure amount at which the line width became the widest among the exposure amounts of ^{200 to 800 mJ/cm 2 was used as an index value, and the evaluation criteria were described below.} evaluation. The evaluation result is described in the column of "resolution" in the table. The smaller the index value, the larger the difference in solubility between the light-irradiated portion and the light-non-irradiated portion in the developing solution, and a better result. In addition, when the change of the line width is small with respect to the change of the exposure energy, it shows that the resolution is excellent, and it becomes a preferable result. The measurement limit is 5 μm. -Evaluation Criteria- A: The above-mentioned index value is 5 μm or more and less than 10 μm. B: The above-mentioned index value is 10 μm or more and less than 20 μm. C: The above index value is 20 μm or more or the line and space pattern cannot be formed.

[Evaluation of exposure sensitivity] The line-and-space pattern of the resin layer was formed on the silicon wafer by the same method as in the evaluation of the above-mentioned resolution. Each silicon wafer was cut while cooling the above line and space pattern with liquid nitrogen, and the cross section of the line and space pattern was measured using a sample coating device for scanning electron microscope (ion sputtering device E-1030, manufactured by HITACHI). Vapor deposition treatment was performed. After the above-mentioned vapor deposition process, the scanning electron microscope measurement was performed from the cross-sectional side, and the angle between the side surface of the line and space pattern with the smallest line width and the surface of the silicon wafer was calculated from the line and space pattern formed, and the angle was calculated as follows: The evaluation criteria were evaluated. It can be said that the closer the angle is to 90°, the better the exposure sensitivity of the photosensitive resin composition. -Evaluation criteria- A: The pattern whose angle is 75° or more and less than 90° is formed. B: No pattern is formed, but the above angle is less than 75° or 90° or more. C: The formation of a pattern was not confirmed.

[Evaluation of Chemical Resistance] The photosensitive resin composition prepared in each Example or the composition for comparison prepared in each Comparative Example was spin-coated on a silicon wafer. The spin-coated silicon wafer was dried on a hot plate at 100° C. for 5 minutes, thereby forming a photosensitive film with a uniform thickness of 10 μm on the silicon wafer. The photosensitive film on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). Exposure was performed using i-rays, and at a wavelength of 365 nm, with ^{exposure energies of 200, 300, 400, 500, 600, 700, and 800 mJ/cm 2} , light with a line and space pattern formed in a 1 μm scale from 5 μm to 25 μm was used. The mask was exposed to light to obtain a resin layer. In the evaluation of chemical resistance, development was not performed in order to simplify the evaluation. The above-mentioned exposed resin layer and silicon wafer were heated at a temperature increase rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained for 180 minutes to obtain a cured film. The obtained cured film was immersed in the following chemicals under the following conditions, and the dissolution rate was calculated. Drug: a 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and a 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) Evaluation conditions: Put the above cured film in the above drug at 75°C The dissolution rate (nm/min) was calculated by immersing for 15 minutes and comparing the film thickness of the cured film before and after the immersion. The obtained value of the dissolution rate was evaluated according to the following evaluation criteria, and the evaluation results were described in the "chemical resistance" column of Tables 1 to 4. It can be said that the slower the dissolution rate, the better the chemical resistance. -Evaluation Criteria- A: The dissolution rate is less than 250 nm/min. B: The dissolution rate is 250 nm/min or more and less than 500 nm/min. C: The dissolution rate is 500 nm/min or more.

[Evaluation of Resolution (Direct Exposure)] The photosensitive resin composition in each Example or Comparative Example was spin-coated on a silicon wafer. The above-mentioned silicon wafer was dried on a hot plate at 100° C. for 5 minutes, whereby a photosensitive film having a uniform thickness of 10 μm was formed on the silicon wafer. Using a direct exposure device (AdTech DE-6UH III), the photosensitive film on the silicon wafer was exposed. With regard to exposure, at a wavelength of 405 nm, each exposure energy of 200, 300, 400, 500, 600, 700, and 800 mJ/cm ² was performed, and the exposed portion became a line portion on a 1 μm scale from 5 μm to 25 μm and a line portion on a space pattern. The resin layer is obtained by direct imaging exposure of a laser such as the like. The resin layer was developed with cyclopentanone for 60 seconds, and the minimum line width in the exposure amount at which the line width became the widest among the exposure amounts of ^{200 to 800 mJ/cm 2 was used as an index value, and the evaluation criteria were described below.} evaluation. The evaluation results are described in the column of "resolution (direct exposure)" in the table. The smaller the index value, the larger the difference in solubility between the light-irradiated portion and the light-non-irradiated portion in the developing solution, and a better result. The measurement limit is 5 μm. -Evaluation Criteria- A: The above-mentioned index value is 5 μm or more and less than 10 μm. B: The above-mentioned index value is 10 μm or more and less than 20 μm. C: The above index value is 20 μm or more or the line and space pattern cannot be formed.

Furthermore, in the examples in which the polymers A-1, A-2, A-3 and A-4 were used as resins, the polymer A-1 was changed to the polymer A'-1 of the same mass part, and the polymer A-2 was changed to polymer A'-2 of the same mass, polymer A-3 was changed to polymer A'-3 of the same mass, and polymer A-4 was changed to polymer of the same mass A'-4, and the evaluation results of resolution, exposure sensitivity, chemical resistance, and resolution (direct exposure) were carried out in the same way, and the evaluation results of each evaluation item in each example were the same as the evaluation results before the change. same.

From the above results, it was found that a pattern excellent in resolution and chemical resistance can be obtained by the photosensitive resin composition of the present invention. The composition for comparison of Comparative Example 1 did not contain a specific sensitizer. It turns out that the resolution of this kind of composition for comparison is inferior. In addition, the composition for comparison of Comparative Example 2 did not contain an organometallic complex. It turns out that the resolution of this kind of composition for comparison is inferior. The composition for comparison of Comparative Example 3 contained only a sensitizer different from the specific sensitizer. It was found that the chemical resistance of the pattern was poor when such a composition for comparison was used.

<Example 101> The photosensitive resin composition used in Example 1 was applied to the surface of the copper thin layer of the resin substrate on which the copper thin layer was formed in a layer by spin coating, and dried at 100° C. for 4 minutes, thereby forming a copper thin layer. After the photosensitive film with a film thickness of 20 μm, exposure was performed with a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-to-space pattern and a line width of 10 μm). After exposure, it heated at 100 degreeC for 4 minutes. After the above heating, the pattern of the layer was obtained by developing with cyclohexanone for 2 minutes and rinsing with PGMEA for 30 seconds. Next, the temperature was increased at a temperature increase rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 120 minutes, thereby forming an interlayer insulating film for a rewiring layer. This interlayer insulating film for rewiring layers is excellent in insulating properties. Moreover, as a result of manufacturing a semiconductor element using these interlayer insulating films for rewiring layers, normal operation was confirmed.

Claims (15)

A photosensitive resin composition comprising: at least one resin selected from the group consisting of polyimide precursor, polybenzoxazole precursor, polyimide and polybenzoxazole; organometallic complexes; and A sensitizer with a condensed ring structure. The photosensitive resin composition according to claim 1, wherein The aforementioned sensitizer contains at least one atom selected from the group consisting of a nitrogen atom and a sulfur atom as a ring member in the condensed ring structure. The photosensitive resin composition according to claim 1 or claim 2, wherein The aforementioned sensitizer includes, as a condensed ring structure, at least one structure selected from the group consisting of an acridine structure, a thioxanthone structure, and an acridine structure. The photosensitive resin composition according to claim 1 or claim 2, wherein Content of the said sensitizer is 0.5-5.0 mass parts with respect to 1 mass part of the said organometallic complex. The photosensitive resin composition according to claim 1 or claim 2, wherein The aforementioned organometallic complex is a metallocene compound. The photosensitive resin composition according to claim 1 or claim 2, wherein The metal contained in the aforementioned organometallic complex is at least one metal selected from the group consisting of titanium, zirconium and hafnium. The photosensitive resin composition according to claim 1 or claim 2, wherein The aforementioned organometallic complex has the ability to initiate photoradical polymerization. A method of manufacturing a pattern, comprising: A film forming process, wherein the photosensitive resin composition described in any one of claim 1 to claim 7 is applied to a substrate to form a photosensitive film; an exposure process, exposing the aforementioned photosensitive film; and In the developing process, the photosensitive film after the exposure is developed to obtain a pattern. The method for manufacturing a pattern as claimed in claim 8, wherein The exposure light used in the aforementioned exposure process includes light with a wavelength of 150-450 nm. The manufacturing method of the pattern as claimed in claim 8, further comprising: In the heating process, the pattern obtained by the aforementioned developing process is heated to harden the pattern. A photosensitive film formed from the photosensitive resin composition according to any one of Claims 1 to 7. A cured product, which is the cured product of the photosensitive film described in claim 11. The cured product according to claim 12, which is used as an interlayer insulating film for a rewiring layer. A layered body comprising two or more layers composed of the cured product according to claim 12 or claim 13, and including a metal layer between any layers composed of the cured product. An element comprising the hardened product of claim 12 or claim 13.