TW201942198A - Photosensitive resin composition, cured film, laminate, and application of these - Google Patents

Abstract

Provided are: a photosensitive resin composition including at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, and an acid having a single bond of nitrogen and sulfur; a method for manufacturing the photosensitive resin composition; a cured film; a laminate; a method for manufacturing the cured film; a method for manufacturing the laminate; a semiconductor device; and a preservation stabilizer.

Description

Photosensitive resin composition, method for producing photosensitive resin composition, cured film, laminated body, method for producing cured film, method for producing laminated body, and semiconductor device

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

Polyfluorene resins and polybenzoxazole resins have excellent heat resistance and insulation properties, and are therefore used in various applications (for example, see Non-Patent Documents 1 and 2). The use thereof is not particularly limited, and if a semiconductor device for mounting is used as an example, a material for a passenger insulating film or a sealing material, or the use as a protective film thereof may be mentioned. It is also used as a base film or a cover film of a flexible substrate.
Generally, the polyamidoimide resin and the like have low solubility in a solvent. Therefore, a method is often used in which a polymer precursor before the cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor is dissolved in a solvent. Thereby, excellent handleability can be achieved, and when manufacturing each of the products described above, it can be applied to a substrate or the like in various forms and processed. The polymer precursor can then be cyclized with heat to form a hardened product. In addition to the high performance of polyimide resins, etc., from the viewpoint of excellent manufacturing adaptability, more and more industrial application development is expected.

It has been tried to apply a protective film using a polyfluorene resin or the like as an interlayer insulating film by utilizing the above characteristics. For example, in the technique of Patent Document 1, a negative photosensitive resin composition containing a polyfluorene imide precursor having a (meth) acryloxy group and a photopolymerization initiator in a predetermined amount is used. Accordingly, it is described that a hardened body having a high transparency and a high Young's modulus after heat curing can be obtained as a resin composition.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] International Publication No. 2013/168675
[Non-patent literature]

[Non-Patent Document 1] Science & Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008
[Non-Patent Document 2] Released in November 2011 by Kakimoto Yamin / Supervisor, CMC Technical library "Base and Development of Polyimide Materials"

According to the above technique, a cured body having a high Young's modulus can be obtained by curing to be suitable for an interlayer insulating film or the like. However, when it is used as such an insulating film, various characteristic items remain to be further studied. For example, further studies are required on the adhesion between a resin and a layer of a metal material made of a metal, a metal oxide, or the like. As described above, the polymer precursor can be hardened by heating. However, due to its characteristics, the polymer precursor is easily hardened during storage and may lack the stability of the resin. On the other hand, when a formulation that suppresses the cyclization of the precursor is used to prevent hardening, on the other hand, the hardenability is deteriorated and the characteristics required during film formation may not be satisfied.
Accordingly, an object of the present invention is to provide a photosensitive resin composition and a photosensitive resin composition that have good adhesion to a layer of a metal material, and can maintain sufficient hardenability and achieve excellent storage stability. Method, hardened film, laminated body, method of manufacturing hardened film, method of manufacturing laminated body, semiconductor device, and storage stabilizer.

Based on the above-mentioned problems, the present inventors have repeatedly conducted research and experiments on a composition including a polymer precursor from various viewpoints such as its components, addition amounts, and preparation conditions. As a result, they have found that the use of a specific acid having a single bond of sulfur and nitrogen in combination with the polymer precursor can solve the above-mentioned problems, and completed the present invention. Specifically, the above-mentioned problems are solved by the following means <1> and <2> to <26>.

<1> A photosensitive resin composition comprising at least one polymer precursor selected from the group consisting of a polyfluorene imide precursor and a polybenzoxazole precursor, and a polymer having a single bond of nitrogen and sulfur. acid.
<2> The photosensitive resin composition according to <1>, wherein the acid has a pka of 0 or more and 4.0 or less.
<3> The photosensitive resin composition according to <1> or <2>, wherein the ClogP of the logarithm of the water / octanol partition coefficient of the acid is -2.1 or more and 1.2 or less.
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the molecular weight of the acid is 300 or less.
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the acid has a cyclic structure.
<6> The photosensitive resin composition according to any one of <1> to <4>, wherein the acid has a sultamylamine structure.
<7> The photosensitive resin composition according to any one of <1> to <4>, wherein the acid is represented by any one of the following formulae (S1) to (S4);
[Chemical Formula 1]

In the formulae (S1) to (S4), L ¹¹ represents a single bond or a linking group, L ¹² represents a linking group, R ¹¹ represents a hydrogen atom or a substituent, R ²¹ represents a substituent, R ³¹ represents a substituent, and R ⁴¹ Represents a hydrogen atom or a substituent, R ⁴² represents a substituent, and R ⁴³ represents OH, NH ₂ or N ₃ .
<8> The photosensitive resin composition according to any one of <1> to <4>, wherein the acid is represented by the following formula (S1-1);
[Chemical Formula 2]

In the formula (S1-1), R ¹² is a hydrogen atom or a substituent, and R ¹³ and R ¹⁴ are each independently a hydrogen atom or a substituent.
<9> The photosensitive resin composition according to any one of <1> to <8>, further comprising at least one of a photopolymerization initiator, a radical polymerizable compound, and a solvent.
<10> The photosensitive resin composition according to any one of <1> to <9>, which is used to form an interlayer insulating film for a redistribution layer.
<11> A method for producing a photosensitive resin composition, comprising adding nitrogen and at least one polymer precursor selected from the group consisting of a polyfluorene imide precursor and a polybenzoxazole precursor. The process of sulfur single bond acid.
<12> The method for producing a photosensitive resin composition according to <11>, wherein the acid is added to the synthesis of the polymer precursor.
<13> The manufacturing method of the photosensitive resin composition as described in <11> or <12> whose pka of the said acid is 0 or more and 4.0 or less.
<14> The method for producing a photosensitive resin composition according to any one of <11> to <13>, wherein the ClogP of the acid is -2.1 or more and 1.2 or less.
<15> The method for producing a photosensitive resin composition according to any one of <11> to <14>, wherein the molecular weight of the acid is 300 or less.
<16> The method for producing a photosensitive resin composition according to any one of <11> to <15>, wherein the acid is represented by any one of the following formulae (S1) to (S4);
[Chemical Formula 3]

In the formulae (S1) to (S4), L ¹¹ represents a single bond or a linking group, L ¹² represents a linking group, R ¹¹ represents a hydrogen atom or a substituent, R ²¹ represents a substituent, R ³¹ represents a substituent, and R ⁴¹ Represents a hydrogen atom or a substituent, R ⁴² represents a substituent, and R ⁴³ represents OH, NH ₂ or N ₃ .
<17> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <10>.
<18> The cured film according to <17>, wherein the film thickness is 1 to 30 μm.
<19> A laminated body comprising the hardened film according to <17> or <18> in two or more layers.
<20> The laminated body according to <19>, which has a metal layer between the cured films.
<21> A method for producing a cured film, comprising a film formation process, applying the photosensitive resin composition according to any one of <1> to <10> to a substrate to form a film.
<22> The method for producing a cured film according to <21>, which comprises an exposure process for exposing the film and a development process for developing the film.
<23> The method for producing a cured film according to <22>, wherein the developer used for the development includes an organic solvent of 90% by mass or more.
<24> The method for producing a cured film according to <22> or <23>, which includes a process of heating the film after the development process described above.
<25> A method for producing a laminated body, wherein the method for producing a cured film according to any one of <21> to <24> is performed a plurality of times.
<26> A semiconductor device having the cured film according to <17> or <18> or the laminated body according to <19> or <20>.
[Inventive effect]

According to the photosensitive resin composition of the present invention, the cured film has good adhesion to the metal material layer, can maintain sufficient hardenability, and achieves excellent storage stability. Furthermore, it is possible to provide a method for producing a photosensitive resin composition having this effect, a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, a semiconductor device, and a storage stabilizer.

Hereinafter, the content of this invention is demonstrated in detail. In addition, in this specification, "~" is used with the meaning which included the numerical value described before and after that as a lower limit value and an upper limit value.

The description of the constituent elements in the present invention described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment.
In the description of the group (atomic group) in this specification, the unlabeled and unsubstituted labels include those having no substituent and those having a substituent. For example, "alkyl" includes not only alkyl groups (unsubstituted alkyl groups) without substituents, but also alkyl groups (substituted alkyl groups) with substituents.
Regarding "exposure" in this specification, unless otherwise specified, not only exposure using light, but also drawing using particle beams such as electron beams and ion beams is also included in the exposure. In addition, as the light used for the exposure, bright line spectrum of a mercury lamp, extreme ultraviolet rays (EUV light) typified by excimer laser light, actinic rays such as X-rays, and electron beams, or radiation may be mentioned.
In this specification, "(meth) acrylate" means both or any of "acrylate" and "methyl acrylate", and "(meth) acrylic" means both "acrylic" and "methacrylic" In either case, "(meth) acrylfluorenyl" means both or both of "acrylfluorenyl" and "methacrylfluorenyl".
In this specification, the term "process" includes not only independent processes, but even if it cannot be clearly distinguished from other processes, as long as the intended role of the process is achieved, it is also included in this term.
In the present specification, the solid content refers to the mass percentage of other components other than the solvent with respect to the total mass of the composition. The temperature is 23 ° C unless otherwise specified.
In this specification, unless otherwise stated, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene conversion values based on gel permeation chromatography (GPC measurement). In this specification, for example, HLC-8220 (manufactured by TOSOH CORPORATION) can be used as the weight average molecular weight (Mw) and the number average molecular weight (Mn), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, and TSKgel Super can be used as columns. HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). The eluent was measured using THF (tetrahydrofuran) unless otherwise specified. In addition, unless otherwise stated, detection was performed using a UV ray (ultraviolet) wavelength 254 nm detector.

The photosensitive resin composition of the present invention (hereinafter, sometimes simply referred to as "the composition of the present invention" or "the resin composition of the present invention") is characterized by containing a material selected from the group consisting of polyimide precursors and polybenzoxane At least one polymer precursor in the group of azole precursors and an acid having a single bond of nitrogen and sulfur (hereinafter, this is referred to as a “specific acid”). Thereby, good storage stability and adhesiveness can be achieved.
When the photosensitive resin composition containing a polyfluorene imide precursor or a polybenzoxazole precursor is stored for a long time, a ring-closure reaction is likely to occur. On the other hand, when hardening, it is necessary to appropriately cyclize. Therefore, the storage stability of a photosensitive resin composition containing a polyfluorene imide precursor or a polybenzoxazole precursor becomes an important issue.
On the other hand, a cured film in which the photosensitive resin composition is cured is hygroscopic. Therefore, the adhesion between the substrate and the cured film can be reduced by the absorbed moisture. Such a decrease in adhesion becomes a problem when, for example, a redistribution layer is formed in a semiconductor device.
On the other hand, in the present invention, by adding a specific acid to the photosensitive resin composition, the hardening reaction caused by cyclization is not excessively hindered, and the ring closure reaction with time of the polymer precursor can be suppressed. In addition, stability during storage can be improved. Furthermore, it is possible to prevent moisture absorption of the photosensitive resin composition by the action of the specific acid described above, and it is possible to optimize the adhesion to the substrate during curing.

＜ Specific acid ＞
The photosensitive resin composition of this invention contains the acid (specific acid) which has a single bond of nitrogen and sulfur. The specific acid contains a single bond (NS) of nitrogen and sulfur, but this type of bond has an appropriate acidity in order to increase the acidity of a hydrogen atom replaced by a nitrogen atom. Furthermore, in the present invention, it is preferable to have a -NS (= O) ₂ -structure. With such a configuration, the acidity of the hydrogen atom replaced by the nitrogen atom is further increased, and therefore, the effect of the present invention is more effectively exhibited.
The pka of the specific acid is preferably 0 or more and 4.0 or less. The lower limit value is preferably -10 or more, more preferably -5 or more, and more preferably 1 or more. The upper limit is preferably 3.8 or less, and more preferably 3.7 or less. By setting the pKa to 1 or more, the effect of improving the stability of the film physical properties can be more effectively exhibited. By setting the pKa to be 4.0 or less, hydrolysis in the resist solution is suppressed, and the storage stability at room temperature is more effectively exhibited. Sexual effects. In particular, it is preferable to set the pKa in the range of 1.0 to 2.0 to more effectively suppress corrosion of copper.
Here, pKa indicates the pKa in the aqueous solution, and examples thereof include those described in Chemical Handbook (II) (Revised 4th Edition, 1993, edited by the Japan Chemical Society, Maruzen. Inc.). The lower the value, the greater the acid strength. Specifically, the pKa in the aqueous solution can be an infinitely diluted aqueous solution, and can be measured by measuring the acid dissociation constant at 25 ° C. In addition, the following software package 1 can be used to calculate and obtain the value of a database based on the Hammett's substituent constant and known literature values. The pKa value in this specification means a value obtained by calculation using the software package.
Software Suite 1: Advanced Chemistry Development (ACD / Labs) software V8.14 supports Solaris systems (1994-2007 ACD / Labs)

Regarding the specific acid, the ClogP is preferably -2.1 or more and 1.2 or less. As the lower limit, -2.1 or more is preferable, -1.75 or more is more preferable, and -1.50 or more is more preferable. As an upper limit, 1.2 or less is preferable, 1.18 or less is more preferable, and 1.16 or less is more preferable. Since ClogP is in the above range, it has the effect of improving in-plane uniformity and adhesion at the time of coating.
In the present specification, "ClogP" refers to logP (log [water / octanol partition coefficient]) obtained by calculation and prediction from a chemical structure. ClogP in this manual uses the value calculated with Chem Draw Pro 12.0.

The molecular weight of the specific acid is preferably 300 or less.
The specific acid is preferably stable to light having a wavelength of 365 nm.

The specific acid preferably has a cyclic structure. By having a cyclic structure, the solubility in a solvent is improved, and the stackability with a polymer tends to be further improved.
The specific acid preferably has a sultamidine structure.

The specific acid is preferably represented by any one of the following formulae (S1) to (S4).
[Chemical Formula 4]

In the formulae (S1) to (S4), L ¹¹ represents a single bond or a linking group, L ¹² represents a linking group, R ¹¹ represents a hydrogen atom or a substituent, R ²¹ represents a substituent, R ³¹ represents a substituent, and R ⁴¹ Represents a hydrogen atom or a substituent, R ⁴² represents a substituent, and R ⁴³ represents OH, NH ₂ or N ₃ .

The linking group of L ¹¹ is preferably an aromatic linking group (aromatic hydrocarbon linking group, compound aromatic linking group) or an alkylene group. The aromatic linking group may have a substituent T described later. The number of carbon atoms is preferably 1 to 22, more preferably 1 to 18, and even more preferably 1 to 10. Specific examples of the aromatic linking group include a linking group having a ring Aro or a ring Arh described in a polymer precursor described later, and more specifically, an AR described in a polymer precursor described later. -1 to AR-10 linking group. Among them, a phenylene group which may have a substituent T (especially, a linking structure of AR-3 described below) is particularly preferred. The alkylene group may have a substituent T. The number of carbon atoms is preferably 1 to 12, 1 to 6 is more preferred, 1 to 3 is more preferred, and ethylene having a substituent T is particularly preferred.
The linking group of L ^{12 is} a linking group L described later, an alkylene group or a carbonyl group is more preferred, and a carbonyl group is further preferred. The alkylene group may have a substituent T described later, with 1 to 12 carbon atoms being preferred, 1 to 6 being more preferred, and 1 to 3 being even more preferred, and a methylene group which may have a substituent T being particularly preferred.
L ¹¹ and L ¹² may be bonded to each other to form a ring. As the ring formed here, a ring having 1 to 6 carbon atoms is preferable, and a nitrogen-containing heterocyclic ring having 3 to 7 members is preferable.
The substituent of R ^{11 is} an aromatic group (carbon number 1 to 22 is preferred, 1 to 18 is more preferred, and 1 to 10 is more preferred. Specific examples include groups having a ring Aro or a ring Arh described later) Or an alkyl group (1 to 12 carbon atoms is preferred, 1 to 6 is more preferred, and 1 to 3 is even more preferred. Specific examples include Alk described later). Among them, R ¹¹ is preferably a hydrogen atom.
The substituent of R ^{21 is} an aromatic group (carbon number 1 to 22 is more preferable, 1 to 18 is more preferable, and 1 to 10 is more preferable. Specific examples include a group having a ring Aro or a ring Arh described later) Or an alkyl group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is more preferred, specific examples include alkyl Alk described later), and an aromatic group having a substituent T is preferred. The phenyl group is more preferable, and the phenyl group which may have a substituent T is further more preferable. The optional T-based carboxyl or nitro group is preferred here.
-SO ₂ NH _{2 of the} formula (S3) may be -SO ₂ NHR ²² or -SO ₂ NR ²² R ²³ . Here, R ²² and R ²³ are each independently a substituent T, an aromatic group (carbon number 1 to 22 is preferred, 1 to 18 is more preferred, 1 to 10 is further preferred, and specific examples include The group of ring Aro or ring Arh described below) may be chain or cyclic, and may be a linear or branched alkyl group (carbon numbers 1 to 24 are preferred, 1 to 12 are more preferred, and 1 to 6 are Further preferred) is preferred. R ²² and R ²³ may be bonded to each other to form a ring. As the ring formed here, a ring having 1 to 6 carbon atoms is preferable, and a nitrogen-containing heterocyclic ring having 3 to 7 members is more preferable.
The substituent of R ^{31 is} an aromatic group (carbon number 1 to 22 is preferred, 1 to 18 is more preferred, and 1 to 10 is more preferred. Specific examples include groups having a ring Aro or a ring Arh described later) Or an alkyl group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is more preferred, specific examples include alkyl Alk described later), and an aromatic group having a substituent T is preferred. The phenyl group is more preferable, and the phenyl group which may have a substituent T is further more preferable. The optional T-based carboxyl group is preferred here.
R ⁴¹ is preferably a hydrogen atom. Examples of the substituent of R ⁴¹ include R ⁴² .
R ⁴² is preferably a substituent T, an alkyl group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, and 1 to 6 is more preferred. Specific examples include alkyl Alk described later) or aromatic. The group (carbon number 1 to 22 is preferred, 1 to 18 is more preferred, and 1 to 10 is more preferred. Specific examples include a group having a ring Aro or a ring Arh described later). A cycloalkyl group ( The number of carbon atoms is preferably 3 to 24, 3 to 12 is more preferable, 3 to 6 is more preferable, and cyclohexyl is more preferable.
R ⁴¹ and R ⁴² may be bonded to each other to form a ring. As the ring formed here, a ring having 1 to 6 carbon atoms is preferable, and a nitrogen-containing heterocyclic ring having 3 to 7 members is more preferable.
The substituent T may be substituted by each group via a linking group L described below. The same applies to the following formulae (S1-1), (S1-2), (S4) to (S6).
R ⁴³ represents OH, NH ₂ or N ₃ , with OH being preferred.

The formula (S1) is preferably the formula (S1-1).
[Chemical Formula 5]

In the formula (S1-1), R ¹² is a hydrogen atom or a substituent, and R ¹³ and R ¹⁴ are each independently a hydrogen atom or a substituent. When R ¹³ and R ¹⁴ are a substituent, R ¹³ and R ¹⁴ may be bonded or condensed with each other to form a ring.

R ¹² is the same as the preferred range of R ^11.
When R ¹³ and R ¹⁴ are substituents, an aromatic group (carbon number 1 to 22 is preferred, 1 to 18 is more preferred, and 1 to 10 is more preferred. Specific examples include a ring Aro or a ring Arh described below. Group) or an alkyl group (carbon number of 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is further preferred, and specific examples include Alk described later). As the ring formed by bonding or condensing R ¹³ and R ¹⁴ , an aromatic hydrocarbon ring (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 10 is more preferred, and specific examples are listed below. Ring Aro, benzene ring is more preferred) or aromatic heterocyclic ring (carbon number 3 to 24 is preferred, 3 to 12 is more preferred, 3 to 6 is more preferred, and specific examples include those constituting the ring Arh described below) ring).

The formula (S1-1) is more preferably the following formula (S1-2).
[Chemical Formula 6]

In formula (S1-2), R ¹² has the same meaning as R ¹² in formula (S1-1).
R ¹⁵ to R ¹⁸ are each independently a hydrogen atom or a substituent (for example, the substituent T). When R ¹⁵ and R ¹⁶ are substituents, R ¹⁵ and R ¹⁶ may be bonded or condensed with each other to form a ring. When R ¹⁶ and R ¹⁷ are substituents, R ¹⁶ and R ¹⁷ may be bonded or condensed with each other to form a ring. When R ¹⁷ and R ¹⁸ are substituents, R ¹⁷ and R ¹⁸ may be bonded or condensed with each other to form a ring. The preferred ring formed by R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ is the same as the ring formed by R ¹³ and R ¹⁴ .

As another preferred embodiment of the present invention, a compound having a specific acid system having a ring structure is preferred. Examples of the ring structure include aromatic hydrocarbon rings (6 to 22 carbon atoms are preferred, 6 to 18 carbon atoms are more preferred, 6 to 10 molecules are more preferred, and specific examples include ring Aro, and benzene rings are more preferred.) Aromatic heterocycles (3 to 24 carbons are preferred, 3 to 12 are more preferred, and 3 to 6 are more preferred. Specific examples include ring Arh), or alicyclics (for example, 3 to 24 carbons) It is more preferable, 3 to 12 is more preferable, and 3 to 6 is more preferable. As a specific example, a cyclohexane ring is preferable. The alicyclic ring exemplified herein is referred to as Acy). The ring Aro, the ring Arh, and the ring Acy may have a substituent T as long as the effects of the present invention are exhibited. The ring structure exemplified here is collectively referred to as tCy. As described above, the reason why the effect of the present invention is exhibited by using an acid having a ring structure is that the stackability with a polymer is improved.

An acid having a ring structure is preferably represented by any one of the following formulae (S5) to (S8).
[Chemical Formula 7]

In the formulae (S5) to (S8), Cy represents a group of a ring structure, and the ring tCy is more preferable. The ring Cy has a substituent T within a range in which the effects of the present invention can be exhibited.
In formulae (S5) and (S8), L ¹² , R ⁴¹ and R ⁴³ have the same meanings as those defined by formulae (S1) and (S4), respectively, and the preferred ranges are also the same.
-SO ₂ NH _{2 in} formula (S6) may be -SO ₂ NHR ²² or -SO ₂ NR ²² R ²³ . Here, R ²² and R ²³ are each independently a substituent T, an aromatic group (carbon number 1 to 22 is preferred, 1 to 18 is more preferred, 1 to 10 is further preferred, and specific examples include The group of ring Aro or ring Arh described below) may be chain or cyclic, and may be a linear or branched alkyl group (carbon numbers 1 to 24 are preferred, 1 to 12 are more preferred, and 1 to 6 are Further preferred) is preferred. R ²² and R ²³ may be bonded to each other to form a ring. As the ring formed here, a ring having 1 to 6 carbon atoms is preferable, and a nitrogen-containing heterocyclic ring having 3 to 7 members is more preferable.

Examples of the substituent T include an alkyl group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, and 1 to 6 is particularly preferred), and an alkenyl group (carbon number 2 to 24 is preferred, 2 to 12 is More preferably, 2 to 6 are particularly preferred), alkoxy (1 to 12 carbons is preferred, 1 to 6 is more preferred, 1 to 3 is even more preferred), and aryl (6 to 22 carbons is more preferred) 6 to 18 are more preferred, 6 to 10 are further preferred), heteroaryl (carbon number of 1 to 12 is preferred, 1 to 6 are more preferred, 1 to 4 are further preferred; as heteroatoms, Examples include nitrogen atom, oxygen atom, sulfur atom), arylalkyl (7 to 23 carbon is more preferable, 7 to 19 is more preferable, 7 to 11 is more preferable), hydroxyl group, amine group (carbon number 0 to 24 is preferred, 0 to 12 is more preferred, 0 to 6 is particularly preferred), a thiol group, a carboxyl group, a nitro group, and a fluorenyl group (2 to 12 carbons are preferred, 2 to 6 are more preferred, 2 to 3 are particularly preferred), oxo (2 to 12 carbons are preferred, 2 to 6 are more preferred, 2 to 3 are particularly preferred), arylfluorenyl (7 to 23 carbons are preferred, 7 19 to 19 are more preferred, 7 to 11 are particularly preferred), arylfluorenyloxy (7 to 23 carbons are preferred, 7 to 19 are more preferred, 7 to 11 are particularly preferred), (meth) acrylic acid , (Meth) Bing Xixi group, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), an oxo group (= O), imino (= NR ^N), alkylene (= C (R ^N ) ₂ ) and so on. The alkylene chain of the substituent T may have a hetero atom interposed therebetween. The alkyl group, alkenyl group, aryl group, and arylalkyl group which the substituent T has may further substitute other substituents.
R ^N is a hydrogen atom or an organic group. As the organic group, an alkyl group (1 to 12 carbons is preferred, 1 to 6 is more preferred, 1 to 3 is more preferred), and an aryl group (6 to 22 carbons is preferred, 6 to 18 is more preferred) Preferably, 6 to 10 is further preferred), or arylalkyl (7 to 23 carbons is preferred, 7 to 19 is more preferred, 7 to 11 is further preferred) is more preferred.

Regarding the linking group L, an alkylene group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, and 1 to 3 is more preferred), an alkenyl group (carbon number 2 to 12 is preferred, 2 to 2 6 is more preferred), arylene (6 to 22 carbons is preferred, 6 to 18 is more preferred, 6 to 10 is more preferred), heteroarylene (carbons 1 to 12 are preferred, 1 -6 is more preferred, and 1-4 is even more preferred. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom), an oxygen atom, a sulfur atom, a carbonyl group, -NR ^N- , or a group related to the combination thereof. . In addition to the hydrogen atom, the number of atoms constituting the linking group L is preferably from 1 to 24, more preferably from 1 to 12, and particularly preferably from 1 to 6. The number of atoms to which the linking group is connected is preferably 10 or less, and more preferably 8 or less. The lower limit is 1 or more.

As specific examples of the specific acid, the following compounds can be exemplified, but the present invention is not limited thereto.
[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

The content of the specific acid in the photosensitive resin composition is preferably 0.10% by mass or more, more preferably 0.15% by mass or more, and still more preferably 0.20% by mass or more. The upper limit is preferably 2.0% by mass or less, more preferably 1.8% by mass or less, and even more preferably 1.6% by mass or less.
With respect to 100 parts by mass of the polymer precursor, the content of the specific acid is preferably 0.15 parts by mass or more, more preferably 0.18 parts by mass or more, and still more preferably 0.20 parts by mass or more. The upper limit is preferably 2.5 parts by mass or less, more preferably 2.25 parts by mass or less, and even more preferably 2.0 parts by mass or less.
When the amount is in the above range, the effect of a specific acid can be sufficiently exerted, and further, storage stability is preferred.
The specific acid may be used singly or in combination. When plural kinds are used, the total amount is within the above range. The specific acid may be used in combination with other acids. For example, use in combination with acetic acid is not prevented.
Among the acids contained in the composition of the present invention, the specific acid described above preferably occupies the main component of the acid other than the polymer precursor, more preferably 80% by mass or more, and more preferably 90% by mass or more. 95% by mass or more is further preferable, and 99% by mass or more is further preferable.

Although a specific acid may be added to the photosensitive resin composition at any timing, for example, it may be added during or after the synthesis of the polymer precursor described later, or when the composition is prepared. Among them, it is preferable to add it in the synthesis of the polymer precursor. Here, the term “synthesis” refers to, for example, the point in time when a process including a polymer precursor synthesis process and a purification process is passed. In the synthesis, a polymer precursor drying process can also be performed. By blending in this way, the specific acid is more uniformly dispersed in the polymer precursor, and the effect of the present invention is more effectively exerted.

＜ Polymer precursor ＞
The photosensitive resin composition of the present invention includes at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. As the polymer precursor, a polyfluorene imide precursor is more preferable, and a polyfluorene imide containing a structural unit represented by the following formula (1) is more preferable.

＜ Polyimide precursors ＞＞
The polyfluorene imide precursor preferably contains a structural unit represented by the following formula (1). By adopting such a structure, a composition having more excellent film strength can be obtained.
[Chemical Formula 16]

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

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and an aromatic group, an aromatic heterocyclic group, or a group including a combination thereof. The number of carbon atoms is 2 to 20 straight-chain aliphatic groups, 3 to 20 carbon chain branched aliphatic groups, 3 to 20 carbon ring aliphatic groups, 6 to 20 aromatic groups, or combinations thereof The group is more preferable, and the aromatic group having 6 to 20 carbon atoms is more preferable.
R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyfluorene imide precursor include a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine. The diamine may be used alone or in combination of two or more.
Specifically, the diamine is a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or the like. Combinations of groups are preferred, and diamines containing groups of 6 to 20 aromatic groups are more preferred. Examples of the aromatic group include the following.

[Chemical Formula 17]

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

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1 1,6-diaminocyclohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diamine ring Hexane 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 isophorone diamine; methyldiamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4 , 4'-diaminodiphenylphosphonium and 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylsulfide and 3,3'-diaminodiphenylsulfide, 4 , 4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4 -Diaminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 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) fluorene, bis (4-amino-3-hydroxyphenyl) fluorene, 4,4'-diamine pair Terphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) Phenyl] phenyl] fluorene, bis [4- (2-aminophenoxy) phenyl] fluorene, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-amine Phenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylhydrazone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3 ' -Dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluoro Biphenyl, 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) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylhydrazone, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenyl Methane, 2- (3 ', 5'-diaminobenzyloxy) ethyl methacrylate, 2,4-diaminocumene and 2,5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-methyl Phenyldiamine, bis (3-aminopropyl) tetramethyldisilaxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-amine Phenyl) ethane, diaminophenylanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis (4-aminophenyl) Hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4- Phenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoro Propane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethyl Phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amine 2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino -3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylhydrazone, 4,4'-bis (3-amine Methyl-5-trifluoromethylphenoxy) diphenylhydrazone, 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' At least one diamine among 5,5 ', 6,6'-hexafluorobenzidine and 4,4'-diaminotetraphenyl.

Diamines (DA-1) to (DA-18) shown below are also preferred.

[Chemical Formula 18]

In addition, as a preferable example, a diamine having at least 2 or more alkanediol units in the main chain can be mentioned. A diamine containing one or both of two or more ethylene glycol chains and propylene glycol chains in one molecule is more preferred, and a diamine containing no aromatic ring is more preferred. Specific examples include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are the product names, manufactured by HUNTSMAN CORPORATION), 1- (2- (2- (2-aminopropyloxy) Group) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) propane-2-yl) oxy) propane-2-amine, etc., but It is not limited to these.
JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE ( (Registered trademark) EDR-176 structure.

[Chemical Formula 19]

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

From the viewpoint of the flexibility of the obtained cured film, R ¹¹¹ is preferably represented by -Ar ⁰ -L ⁰ -Ar ^0- . Among them, Ar ^{0 is} each independently an aromatic hydrocarbon group (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 10 is particularly preferred), and phenylene is more preferred. L ⁰ represents an aliphatic hydrocarbon group of 1 to 10 carbon atoms selected from a single bond, which may be substituted by a fluorine atom, -O-, -C (= O)-, -S-, -S (= O) _2- , -NHCO- and groups of combinations thereof. The meaning of the preferable range is the same as that of the above-mentioned A.

From the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, a divalent organic group represented by the formula (61) is more preferred from the viewpoint of i-ray transmittance and availability.
[Chemical Formula 20]

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, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group. base.
Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and 1 to 10 carbon atoms (1 to 6 carbon atoms are preferred). Good) fluorinated alkyl and the like.
[Chemical Formula 21]

R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.
Examples of the diamine compound having a structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4, 4'-diaminobiphenyl, 2,2'-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. One kind of these may be used or two or more kinds may be used in combination.

R ¹¹⁵ in formula (1) represents a tetravalent organic group. As the tetravalent organic group, a group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred.
[Chemical Formula 22]

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

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in formula (1) include tetracarboxylic acid residues remaining after the acid dianhydride group is removed from the tetracarboxylic dianhydride. Tetracarboxylic dianhydride may be used alone, or two or more of them may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
[Chemical Formula 23]

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

Specific examples of the tetracarboxylic dianhydride include those selected from pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 3,3 ', 4,4'-Diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylfluorenetetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone Tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3, 3 ', 4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2 , 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2, 2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3 , 3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 3,4 , 9,10-fluorenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10- Phenanthrene tetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxylic acid) Phenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride and at least one of these alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms One.

Moreover, as a preferable example, tetracarboxylic dianhydride (DAA-1)-(DAA-5) shown below are mentioned.
[Chemical Formula 24]

R ¹¹³ and R ¹¹⁴ in the formula (1) each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a radical polymerizable group, and it is more preferable that both contain a radical polymerizable group. The radically polymerizable group is a group capable of undergoing a cross-linking reaction by the action of a radical, and a preferable example includes a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acrylfluorenyl group, and a group represented by the following formula (III).

[Chemical Formula 25]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferred.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH _2- , or a (poly) oxyalkylene group having 4 to 30 carbon atoms (as an alkylene group, carbon Numbers 1 to 12 are preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred; repeating numbers 1 to 12 are preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred). In addition, (poly) oxyalkylene means oxyalkylene or polyoxyalkylene.
Examples of preferred R ²⁰¹ include ethylene, propyl, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, and hexamethylene. And octamethylene, dodecylmethylene, -CH ₂ CH (OH) CH _2- , and ethylene, propyl, trimethylene, and -CH ₂ CH (OH) CH ₂ -are more preferred.
It is particularly preferred that R ²⁰⁰ is methyl and R ²⁰¹ is ethyl.

As a preferred embodiment of the polyfluorene imide precursor in the present invention, an aliphatic group having 1, 2 or 3, preferably 1 acid group as a monovalent organic group of R ¹¹³ or R ^{114 may be} mentioned Groups, aromatic groups, and arylalkyl groups. Specific examples include an aromatic group having 6 to 20 carbon atoms in the acid group and an aryl alkyl group having 7 to 25 carbon atoms in the acid group. More specific examples include a phenyl group having an acidic group and a benzyl group having an acidic group. An acidic hydroxyl group is preferred. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group.
As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent capable of improving the solubility of the developing solution is preferably used.
From the viewpoint of solubility with respect to an aqueous developer, R ¹¹³ or R ¹¹⁴ is more preferably a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, and a 4-hydroxybenzyl group.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group are preferred, and an alkyl group substituted with an aromatic group is more preferred.
The carbon number of the alkyl group is preferably 1 to 30 (3 or more when it is cyclic). The alkyl group may be any of linear, branched, and cyclic. Examples of the linear or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecane Octadecyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, norbornyl, pinenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, fluorenyldifluorenyl, and dicyclohexyl. And pinenyl. Among them, cyclohexyl is the most preferable from the viewpoints of both the balance and high sensitivity. The alkyl group substituted with an aromatic group is preferably a linear alkyl group substituted with an aromatic group, which will be described later. (Alk is exemplified here as Alk)
Examples of the aromatic group include an aromatic hydrocarbon group and an aromatic heterocyclic group.
Specific examples of the aromatic hydrocarbon group include a substituted or unsubstituted benzene ring, a naphthalene ring, a pentalene ring, an indene ring, a fluorene ring, a heptalene ring, and benzene. Acene ring, fluorene ring, fused pentaphenyl ring, acenaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, chrysene ring, triphenylene ring, fluorene ring , Biphenyl ring and other aromatic hydrocarbon ring groups. (The aromatic hydrocarbon ring exemplified here is referred to as a ring Aro)
Examples of the aromatic heterocyclic group include substituted or unsubstituted pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, Pyridazine ring, three wells ring, indazine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline Porphyrin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, morphine ring, acridine ring, morpholine ring, thion ring, chromene ring, fluorene ring, phenoxaline ring, phenothiazine A group of an aromatic heterocyclic ring such as a ring or an phenazine ring. (The aromatic heterocyclic ring exemplified here is referred to as a ring Arh)

It is also preferable that the polyfluorene imide precursor has a fluorine atom in the structural unit. The fluorine atom content in the polyfluorene imide precursor is preferably 10% by mass or more, and more preferably 20% by mass or more. There is no particular upper limit, but it is actually 50% by mass or less.

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

The structural unit represented by the formula (1) is preferably a structural unit represented by the formula (1-A).
[Chemical Formula 26]

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

In the polyfluorene imide precursor, the structural unit represented by the formula (1) may be one type, or may be two or more types. Moreover, the structural isomer of the structural unit represented by Formula (1) may not be included. In addition, the polyfluorene imide precursor may include other types of structural units in addition to the structural unit of the formula (1).

As one embodiment of the polyimide precursor in the present invention, 50 mol% or more, 70 mol% or more, and especially 90 mol% or more of all the structural units can be exemplified by the formula (1). Polyimide precursors of structural units. The upper limit is actually 100 mol% or less.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
The polydispersity of the polyimide precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

The polyfluorene imide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. A dicarboxylic acid or a dicarboxylic acid derivative is preferably halogenated using a halogenating agent and reacted with a diamine.
In the method for producing a polyimide precursor, it is preferable to use an organic solvent during the reaction. The organic solvent may be one kind, or two or more kinds.
The organic solvent can be preferably determined depending on the raw materials, but examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

A process that includes precipitating a solid during the manufacture of the polyimide precursor is preferred. Specifically, a polyfluorene imide precursor in the reaction solution is precipitated in water, and a polyfluorene imide precursor such as tetrahydrofuran is dissolved in a soluble solvent, whereby a solid can be precipitated.

＜ Precursor of polybenzoxazole ＞＞
The polybenzoxazole precursor preferably contains a structural unit represented by the following formula (2).
[Chemical Formula 27]

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

R ¹²¹ represents a divalent organic group. The divalent organic group includes an aliphatic group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, and 1 to 6 is particularly preferred) and an aromatic group (carbon number 6 to 22 is preferred, 6 -14 is more preferred, and 6-12 are particularly preferred) at least one of the groups is more preferred. Examples of the aromatic group constituting R ¹²¹ include examples of R ¹¹¹ in the formula (1). As the aliphatic group, a linear aliphatic group is preferred. R ¹²¹ is preferably derived from 4,4'-oxobenzophenazine chloride.
In formula (2), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the above formula (1), and a preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferred ranges are also the same.

The polybenzoxazole precursor contains other types of structural units in addition to the structural unit of the formula (2).
It is preferable that the precursor contains a diamine residue represented by the following formula (SL) as another type of structural unit from the viewpoint of suppressing occurrence of warping of the cured film accompanying the closed loop.

[Chemical Formula 28]

Z has a structure and b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R ^2s is 1 to 10 carbon atoms Hydrocarbyl (preferably 1 to 6 carbons, more preferably 1 to 3 carbons), at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group (preferably 6 to 22 carbons) , More preferably 6 to 18 carbons, particularly preferably 6 to 10 carbons), and the remainder are hydrogen atoms or 1 to 30 carbons (preferably 1 to 18 carbons, more preferably 1 to 12 carbons) Particularly preferred are organic groups having 1 to 6 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be a block polymerization or a random polymerization. In the Z part, the a structure is preferably 5 to 95 mole%, the b structure is 95 to 5 mole%, and the a + b is 100 mole%.

In the formula (SL), as preferable Z, examples in which R ^5s and R ^6s in the b structure are phenyl groups are mentioned. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by a gel permeation chromatography generally used. By setting the molecular weight to the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure is reduced, and the effect of suppressing warpage and the effect of improving solubility can be taken into consideration.

When the precursor contains a diamine residue represented by the formula (SL) as a structural unit of another kind, from the standpoint of improving alkali solubility, it also includes the remaining four A carboxylic acid residue is preferable as a structural unit. Examples of such a tetracarboxylic acid residue include an example of R ¹¹⁵ in formula (1).

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

The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the composition. 50% by mass or more is further preferred, 60% by mass or more is further preferred, and 70% by mass or more is further preferred. The content of the polymer precursor in the photosensitive resin composition of the present invention is more preferably 99.5% by mass or less, more preferably 99% by mass or less, and more preferably 98% by mass or less based on the total solid content of the composition. 95% by mass or less is further preferred, and 95% by mass or less is further preferred.
The photosensitive resin composition of the present invention may contain only one kind of polymer precursor, or may contain two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

<Solvent>
The photosensitive resin composition of the present invention preferably contains a solvent. The solvent can be any known solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, fluorenes, and amidines.
As the esters, preferred examples include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkoxyacetic acid alkyl esters (such as methyl alkoxyacetate, alkoxyacetic acid Ethyl acetate, butyl alkoxyacetate (such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3 -Alkoxy propionate alkyl esters (e.g. methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g. methyl 3-methoxypropionate, 3-methoxypropionate Acid ethyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g. methyl 2-alkoxypropionate, Ethyl 2-alkoxypropionate, 2-alkoxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-propoxypropionate Ester, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy-2-methylpropane Methyl ester and ethyl 2-alkoxy-2-methylpropionate (eg methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.) ), Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.
Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve acetic acid. Ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetate, etc.
Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.
Examples of the aromatic hydrocarbons include toluene, xylene, anisole, and limonene.
As a fluorene, for example, dimethyl fluorene is preferable.
Preferred examples of the amines include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethyl Methylformamide and the like.

From the standpoint of improving the properties of the coating surface, it is also preferable that the solvent is a mixture of two or more types.
In the present invention, it is selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, and butyl acetate. Esters, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethylsulfinium, ethylcarbitol acetate, butylcarbidine One kind of solvent or a mixed solvent 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 sulfene and γ-butyrolactone.

From the viewpoint of coatability, the content of the solvent is preferably set to an amount of 5 to 80% by mass of the total solid content concentration of the photosensitive resin composition of the present invention, and more preferably set to an amount of 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and it is more preferable that the amount is 40 to 70% by mass. The solvent content may be adjusted by the desired thickness and coating method.
The solvent may contain only one kind or two or more kinds. When two or more solvents are contained, it is preferable that the total is within the above range.

<Photopolymerization initiator>
The photopolymerization initiator is preferably a photoradical polymerization initiator.
The photo-radical polymerization initiator that can be used in the present invention is not particularly limited, and can be appropriately selected from known photo-radical polymerization initiators. For example, a photo-radical polymerization initiator having photosensitivity from the ultraviolet region to light in the visible region is preferred. In addition, it may be an active agent that generates an active radical by having any action with a photo-excited sensitizer.
It is preferred that the photoradical polymerization initiator contains at least one compound having an absorption coefficient of about 50 moles in a range of about 300 to 800 nm (330 to 500 nm is preferred). The molar absorption coefficient of a compound can be measured using a well-known method. For example, a UV-visible spectrometer (Cary-5 spectrophotometer, manufactured by Varian Corporation) is preferably used for measurement at a concentration of 0.01 g / L using an ethyl acetate solvent.

After the photosensitive resin composition contains a photoradical polymerization initiator, the photosensitive resin composition of the present invention is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then caused by light irradiation. The generated free radicals are hardened and can reduce the solubility in the light-irradiated portion. Therefore, there is an advantage that, for example, by exposing the photosensitive resin composition layer through a photomask having a pattern that covers only the electrode portion, regions having different solubility can be easily manufactured according to the pattern of the electrode.

As the photoradical polymerization initiator, a known compound can be arbitrarily used. Examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), fluorenyl phosphine compounds such as fluorenylphosphine oxide, hexaarylbisimidazole, Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, amine acetophenone compounds, hydroxyacetophenone, azo-based compounds, azide compounds, methane Metal compounds, organic boron compounds, iron aromatic hydrocarbon complexes, and the like. For the details, refer to the descriptions in paragraphs 0165 to 0182 of Japanese Patent Application Laid-Open No. 2016-027357, and incorporate the contents into this specification.

As the ketone compound, for example, a compound described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611 can be exemplified, and the content is incorporated into the present specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a fluorenylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and a fluorenylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: all manufactured by BASF Corporation) can be used.
As the aminoacetophenone-based initiator, commercially available IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all manufactured by BASF Corporation) can be used.
As the aminoacetophenone-based initiator, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 can be used in which the absorption maximum wavelength is matched to a wavelength light source such as 365 nm or 405 nm.
Examples of the fluorenylphosphine-based initiator include 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide and the like. In addition, IRGACURE-819 and IRGACURE-TPO (product names: both manufactured by BASF) can be used as commercially available products.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

As the photoradical polymerization initiator, an oxime compound is more preferable. By using an oxime compound, exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also functions as a photobase generator.
As specific examples of the oxime compound, a compound described in JP 2001-233842, a compound described in JP 2000-080068, and a compound described in JP 2006-342166 can be used. .
Preferred oxime compounds include, for example, compounds having the following structures, 3-benzyloxyiminobutane-2-one, 3-acetamidoiminobutane-2-one, 3- Propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Imino-1-phenylpropane-1-one and the like. In the photosensitive resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of> C = NOC (= O)-in the molecule.
[Chemical Formula 29]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA OPTOMER N-1919 (made by ADEKA CORPORATION, Japanese Patent Application Publication No. 2012-014052) are also preferably used. Photo radical polymerization initiator 2) described in the publication. In addition, TR-PBG-304 (Changzhou Power Electronics New Materials Co., Ltd. Corporation), ADEKA ARCLS NCI-831, and ADEKA ARCLS NCI-930 (manufactured by ADEKA Corporation) can also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.
In addition, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds described in Japanese Patent Application No. 2014-500852, paragraph 0345, and Japanese Patent Laid-Open No. 24-36. Compound (C-3) and the like described in paragraph 0101 of 2013-164471.
Examples of the preferred oxime compound include an oxime compound having a specific substituent shown in Japanese Patent Application Laid-Open No. 2007-269779, and an oxime compound having a thioaryl group shown in Japanese Patent Application Laid-Open No. 2009-191061. .

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, and fluorenylphosphines. Compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene- Iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.
Further preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, fluorenylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium salts. Compound, benzophenone compound, acetophenone compound, at least selected from the group consisting of trihalomethyltriazine compound, α-aminoketone compound, oxime compound, triarylimidazole dimer, and benzophenone compound One compound is further preferred, the use of a metallocene compound or an oxime compound is further preferred, and the oxime compound is further preferred.
In addition, as the photoradical polymerization initiator, N, N'-tetrakis, such as benzophenone and N, N'-tetramethyl-4,4'-diaminobenzophenone (myrrhenone), can also be used. Alkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1,2-methyl Aromatic ketones such as -1- [4- (methylthio) phenyl] -2-morpholinyl-acetone-1, and quinones and benzoin alkyl groups which are condensed with aromatic rings such as alkyl anthraquinone Benzoin ether compounds such as ether, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyldimethylketal, and the like. In addition, a compound represented by the following formula (I) can also be used.
[Chemical Formula 30]

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, a phenyl group, At least at least one of a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms. 1 substituted phenyl or biphenyl group, R ^I01 is a group represented by formula (II) or the same group as R ^I00 , and R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbon atoms, An alkoxy or halogen atom having 1 to 12 carbon atoms.
[Chemical Formula 31]

In the formula, R ^I05 to R ^I07 have the same meanings as R ^I02 to R ^{I04 in} the formula (I).

As the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used.

When a photopolymerization initiator is included, the content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% with respect to the total solid content of the photosensitive resin composition of the present invention. The mass% is more preferably 1.0 to 10 mass%. The photopolymerization initiator may contain one kind or two or more kinds. When two or more kinds of photopolymerization initiators are contained, the total thereof is preferably in the above range.

<Polymerizable compound>
<<< radical polymerizable compound >>
It is preferable that the photosensitive resin composition of this invention contains a radically polymerizable compound.
As the radically polymerizable compound, a compound having a radically polymerizable group can be used. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as vinylphenyl, vinyl, (meth) acryl, and allyl. The radical polymerizable group is preferably a (meth) propenyl group.

The number of radical polymerizable groups in the radical polymerizable compound may be one, or may be two or more, but the radical polymerizable compound preferably has two or more radical polymerizable groups, and has three The above is even better. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

The molecular weight of the radically polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more.

From the viewpoint of developability, the photosensitive resin composition of the present invention preferably contains at least one bifunctional or more radical polymerizable compound containing two or more polymerizable groups, and contains at least one trifunctional or more radical polymerization. Sexual compounds are more preferred. Moreover, it may be a mixture of a bifunctional radically polymerizable compound and a trifunctional or more radically polymerizable compound. The functional group number of the radical polymerizable compound refers to the number of radical polymerizable groups in one molecule.

Specific examples of the radically polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amines thereof. Ester of unsaturated carboxylic acid and polyhydric alcohol compound and ammonium of unsaturated carboxylic acid and polyamine compound are preferable. In addition, it is also preferable to use an addition reaction product of an unsaturated carboxylic acid ester or amidoamine having a nucleophilic substituent such as a hydroxyl group, an amine group, and a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and Dehydration condensation reactants of functional or polyfunctional carboxylic acids. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amidoamine having an electrophilic substituent such as an isocyanate group and an epoxy group with a monofunctional or polyfunctional alcohol, an amidine, or a thiol is also preferable. Further preferred are substitution reactions of unsaturated carboxylic acid esters or amidoamines, monofunctional or polyfunctional alcohols, amidoamines, and thiols with detachable substituents such as halo and tosylsulfonyloxy. . As another example, instead of the unsaturated carboxylic acid described above, a group of compounds substituted with vinyl phenol derivatives such as unsaturated phosphonic acid and styrene, vinyl ethers, and allyl ethers may be used. As a specific example, reference can be made to the descriptions in paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357, which are incorporated into this specification.

In addition, as the radical polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples of this include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, and pentaerythritol tri (methyl) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri ( After the addition of ethylene oxide or propylene oxide to polyfunctional alcohols, such as propylene glycoloxypropyl) ether, tris (propylene glycoloxyethyl) isocyanurate, glycerol, and trimethylolethane ( (Meth) acrylic compounds such as those described in JP 48-041708, JP 50-006034, and JP 51-037193 Esters, polyester acrylates described in JP 48-064183, JP 49-043191, and JP 52-030490, as epoxy resins and (meth) acrylic acid Polyfunctionals such as epoxy acrylates of reaction products Acrylate or methacrylate and a mixture of these. The compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also preferred. Further, polyfunctional (meth) acrylates obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth) acrylate, in a polyfunctional carboxylic acid can also be mentioned.
In addition, as a preferable radical polymerizable compound other than the above, it is also possible to use those compounds described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216, and the like A compound or cardo resin having two or more cyclic and ethylenically unsaturated groups.
In addition, as another example, Japanese Unexamined Patent Publication No. 46-043946, Japanese Unexamined Patent Publication No. 1-040337, Japanese Unexamined Patent Publication No. 1-040336, and Japanese Unexamined Patent Publication No. 02 A vinylphosphonic acid-based compound and the like described in JP-025493. In addition, a compound containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. 61-022048 can also be used. It can also be used as a photopolymerizable monomer and oligomer introduced in the Journal of the Adhesion Society of Japan vol. 20, No. 7, pages 300 to 308 (1984). .

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Laid-Open No. 2015-034964 are also preferably used, and these contents are incorporated in this specification.

In addition, as described in Japanese Patent Application Laid-Open No. 10-062986, formula (1) and formula (2), together with specific examples thereof, are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol (meth) acrylic acid Esterified compounds can also be used as radical polymerizable compounds.

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

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

As a commercially available product of a radically polymerizable compound, for example, SR-494, a four-functional acrylate having four ethoxy chains, and a bifunctional methyl group having four ethoxy chains, are available from Sartomer Company Inc. Acrylic acid esters are SR-209, 231, 239 manufactured by Sartomer Company Inc., 6-functional acrylic acid esters having 6 penteneoxy chains, namely DPCA-60, produced by Nippon Kayaku Co., Ltd. The trifunctional acrylate of the oxygen chain is TPA-330, the urethane oligomer UAS-10, UAB-140 (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), and the like.

Examples of the radically polymerizable compound include the aminomethyl compounds described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765. Ester acrylates or those having an ethylene oxide system 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. Also preferred are skeleton urethane compounds. In addition, as the radical polymerizable compound, JP-A-63-277653, JP-A-63-260909, and JP-A-105238 can be used as having a amine group in the molecule. Structure or thioether structure.

The radical polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxyl group or a phosphate group. The radical polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. An unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to carry an acid radical. A radical polymerizable compound is more preferable. Among the radically polymerizable compounds which react an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride and have an acid group, a compound in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol is particularly preferred. 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 preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radically polymerizable compound is in the above range, the manufacturing and handling properties are excellent, and further the developability is excellent. In addition, the polymerizability was good.

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

<<< Polymerizable compounds other than the above radical polymerizable compounds >>
The photosensitive resin composition of this invention can contain the polymerizable compound other than the said radically polymerizable compound. Examples of the polymerizable compound other than the above radical polymerizable compound include compounds having a hydroxymethyl group, an alkoxymethyl group, or a fluorenylmethyl group; epoxy compounds; oxetane compounds; and benzoxane Azine compounds.

(Compounds with hydroxymethyl, alkoxymethyl or methoxymethyl)
As the compound having a hydroxymethyl group, an alkoxymethyl group, or a fluorenylmethyl group, a compound represented by the following formulae (AM1), (AM4), and (AM5) is preferable.

[Chemical Formula 32]

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

[Chemical Formula 33]

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

[Chemical Formula 34]

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

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

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

(Epoxy compounds (compounds having epoxy groups))
As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a cross-linking reaction at a temperature of 200 ° C or lower, and a dehydration reaction due to cross-linking does not occur, and thus film shrinkage is difficult to occur. Therefore, containing an epoxy compound can effectively suppress low-temperature curing and warping of the composition.

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 is one in which the number of structural units of ethylene oxide is 2 or more, and the number of structural units is preferably 2 to 15.

Examples of the epoxy compound include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkanediol type epoxy resins such as propylene glycol diglycidyl ether; and polyalkylene dipropylene glycols such as polypropylene glycol diglycidyl ether. Alcohol-type epoxy resins; epoxy-containing silicones, such as polymethyl (glycidyloxypropyl) siloxane; but the system is not limited to these. Specific examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, and 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) ) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (above are trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark) ) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above are trade names, manufactured by ADEKA CORPORATION), etc. Among these, a polyethylene oxide-based epoxy resin is preferable from the viewpoint of suppressing warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E are preferred because they contain polyethylene oxide groups.

(Oxetane compounds (compounds having an oxetanyl group))
Examples of the oxetane compound include a compound having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis { [(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4- Phthalic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like. As a specific example, Aron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) made by TOAGOSEI CO., LTD. Can be preferably used, and these can be used alone or in combination of two or more kinds. .

(Benzoxazine compounds (compounds having a benzoxazolyl group))
The benzoxazine compound is preferably a cross-linking reaction caused by a ring-opening addition reaction, from the point that it does not generate outgassing during hardening, further reduces thermal shrinkage, and suppresses warping.

Preferred examples of the benzoxazine compound include Ba-type benzoxazine, Bm-type benzoxazine (the above is the product name, manufactured by SHIKOKU CHEMICALS CORPORATION), and benzoxazine addition of polyhydroxystyrene resin Substance, phenol novolak type dihydroxybenzoxazine compound. These can be used alone or in combination of two or more.

When a polymerizable compound is contained, its content is preferably more than 0% by mass and 60% by mass or less based on the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 50% by mass or less, and more preferably 30% by mass or less.
The polymerizable compound may be used singly or in combination of two or more kinds. When two or more kinds are used simultaneously, it is preferable that the total amount thereof falls within the above range.

<Migration inhibitor>
It is preferable that the photosensitive resin composition of the present invention further contains a migration inhibitor. By including a migration inhibitor, the migration of metal ions originating from the metal layer (metal wiring) into the photosensitive resin composition layer can be effectively suppressed.
The migration inhibitor is not particularly limited, and examples thereof include a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, and tetrazole). Ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea Compounds and thiol compounds, hindered phenol compounds, salicylic acid derivative compounds, hydrazine derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

In addition, an ion trapping agent that captures anions such as a halide ion can also be used.

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

Specific examples of the migration inhibitor include the following compounds.
[Chemical Formula 35]

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the photosensitive resin composition is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0% by mass is more preferable.
The migration inhibitor may be only one type, or may be two or more types. When there are two or more kinds of migration inhibitors, the total amount is preferably in the above range.

<Polymerization inhibitor>
The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.
As the polymerization inhibitor, for example, hydroquinone, 4-methoxyphenol, di-tertiary-butyl-p-cresol, gallicol, p-tertiary-butyl-catechol, 1,4- Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6 -Tertiary butyl phenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitroso diphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1 , 2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tertiary butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso -N- (1-naphthyl) hydroxyamine ammonium salt, bis (4-hydroxy-3,5-tert-butyl) phenylmethane and the like. In addition, the polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Laid-Open No. 2015-127817 and the compounds described in paragraphs 031 to 0046 of International Publication No. 2015/125469 can also be used.
The following compounds (Me is methyl) can be used.
[Chemical Formula 36]

When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, and 0.02 to 3% by mass relative to the total solid content of the photosensitive resin composition of the present invention. More preferably, 0.05 to 2.5% by mass is further preferred.
The polymerization inhibitor may be only one kind, or two or more kinds. When there are two or more kinds of polymerization inhibitors, the total is preferably in the above range.

＜ Metal Adhesive Improver ＞
The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used in an electrode, wiring, or the like. Examples of the metal adhesion improver include a silane coupling agent and the like.

Examples of the silane coupling agent include compounds described in paragraphs 0061 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, and Japanese Patent Laid-Open No. 2014 The compounds described in paragraphs 0060 to 0061 of Japanese Patent Publication No. -191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and the compounds described in paragraph 0055 of International Publication No. 2014/097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.
[Chemical Formula 37]

In addition, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and thioethers described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 Compound.

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 with respect to 100 parts by mass of the polymer precursor. By setting the upper limit value or more, the adhesion between the cured film and the metal layer after the hardening process becomes good. By setting the upper limit value or less, the heat resistance and mechanical properties of the hardened film after the hardening process are improved. The characteristics become good. The metal adhesion improver may be only one kind, or two or more kinds. In the case of using two or more kinds, it is preferable that the total is within the above range.

＜ Hot alkali generators ＞
The photosensitive resin composition of the present invention may contain a hot alkali generator. The thermophotochemical alkali generating agent is preferably one which generates alkali by heat.
The salt of a thermal alkali generator based on a quaternary ammonium cation and a carboxylate anion is preferred. The quaternary ammonium cation is preferably represented by any one of the following formulae (Y1-1) to (Y1-4).
[Chemical Formula 38]

R ^Y1 represents an organic group having n ^Y valence (n ^Y is an integer of 1 to 12), and an n ^Y valence hydrocarbon group is preferred. Examples of the hydrocarbon group include an n ^Y- valent group containing an alkane (carbon number 1 to 12 is more preferable, 1 to 6 is more preferable, and 1 to 3 is more preferable), and an n ^Y- valent group containing an alkene (carbon number 2 to 12 are preferred, 2 to 6 are more preferred, and 2 to 3 are further preferred), n ^Y- valent groups containing aromatic hydrocarbons (carbon number 6 to 22 are preferred, 6 to 18 are more preferred, 6 to 10 are further preferred) or a combination of these. Among them, R ^Y1 based aromatic hydrocarbon groups are preferred. As long as the effect of the present invention is not impaired, R ^Y1 may have the aforementioned substituent T.
R ^Y2 to R ^Y5 each independently represents a hydrogen atom or a hydrocarbon group (carbon number 1 to 36 is more preferable, 1 to 24 is more preferable, 1 to 12 is more preferable), and alkyl group (carbon number 1 to 36 is more preferable) 1 to 24 is more preferred, 1 to 23 is more preferred), alkenyl (2 to 36 carbons is preferred, 2 to 24 is more preferred, 2 to 23 is more preferred), alkynyl (carbon number 1 to 36 is preferred, 1 to 24 is more preferred, 1 to 23 is further preferred), aryl (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 10 is further preferred) Is better. The alkyl group, alkenyl group, and alkynyl group may be cyclic or chain-shaped, and when they are chain-shaped, they may be linear or branched, or may have a substituent T.
R ^Y6 is alkyl (carbon number 1 to 36 is preferred, 2 to 24 is more preferred, 4 to 18 is more preferred), alkenyl (carbon number 2 to 36 is preferred, 2 to 24 is more preferred, 4 to 18 is more preferred), alkynyl (2 to 36 carbons is preferred, 2 to 24 is more preferred, 4 to 18 is more preferred), aryl (6 to 22 carbons is preferred, 6 -18 is more preferred, and 6-10 is more preferred). The alkyl group, alkenyl group, and alkynyl group may be cyclic or chain-shaped, and when they are chain-shaped, they may be linear or branched. In the alkyl group, alkenyl group, alkynyl group, and aryl group, a linking group containing a hetero atom may be interposed between the groups (for example, the linking group L has a hetero atom). For example, oligoalkylene (the number of carbons in the structural unit is preferably 1 to 12, more preferably 1 to 6 and even more preferably 1 to 3. The repeating number system is preferably 2 to 100, and 2 to 60 is more preferred, and 2-30 is more preferred).
n ^Y represents an integer of 1 to 12, an integer of 1 to 6 is more preferable, and an integer of 1 to 3 is more preferable.
n ^X represents an integer of 1 to 12, an integer of 1 to 6 is preferred, and an integer of 1 to 3 is further preferred.
Two or more of R ^Y2 to R ^Y6 may be bonded to each other to form a ring.

R ^Y7 ~ R ^Y16 the same meaning as R ^N (R ^N may have a substituent group T). However, none of R ^Y7 to R ^Y9 is a hydrogen atom. In the formula (Y1-2), R ^Y7 and R ^Y8 are carboxyalkyl groups (carbon number 1 to 12 is more preferable, 1 to 6 is more preferable, 1 to 3 is more preferable; the number of carboxyl groups 1 to 12 is more 1 to 6 is more preferable, and 1 to 3 is more preferable) is more preferable. R ^Y9- based aromatic groups are preferred, and aryl groups (6 to 22 carbons are preferred, 6 to 18 are more preferred, and 6 to 10 are more preferred) are more preferred. Alternatively, an alkoxycarbonyl group substituted by an aromatic group is preferred (alkoxy-based carbon numbers 1 to 12 are preferred, 1 to 6 are more preferred, 1 to 3 are further preferred, and aromatic group-based carbon numbers 6 22 is more preferable, 6 to 18 is more preferable, and 6 to 14 is more preferable. In formula (Y1-3), R ^Y11 and R ^Y13 are preferably hydrogen atoms. _Two substituents of R ^Y14 and R ^Y15 may be combined to form a substituent of the form = C (NR ^N ₂ ) ₂ (= means a nitrogen atom is bonded by a double bond). In formula (Y1-4), R ^Y13 is preferably a hydrogen atom, and R ^Y10 , R ^Y11 , R ^Y12 , and R ^Y16 are alkyl groups (carbon numbers of 1 to 12 are preferred, 1 to 6 are more preferred, and 1 to 3 is further preferred) is better. At this time, it is preferable that R ^Y11 and R ^Y16 , R ^Y10 and R ^{Y12 are} bonded to form a ring and become a double ring. Specific examples include diazine bicyclononene and diazine bicycloundecene.

In this embodiment, a carboxylate anion paired with a quaternary ammonium cation of the above formula (Y1-1), formula (Y1-3), and formula (Y1-4) is preferably represented by the following formula (X1).
[Chemical Formula 39]

In the formula (X1), EWG represents an electron withdrawing group.

The electron-withdrawing group in this embodiment refers to a person whose Hammett substituent constant σm represents a positive value. Here, σm is explained in detail by Tono Takeo, General Journal of Organic Synthetic Chemistry, Vol. 23 No. 8 (1965) p. 631-642. The electron-withdrawing group in this embodiment is not limited to the substituent described in the above-mentioned document.
Examples of substituents in which σm represents a positive value include CF ₃ group (σm = 0.43), CF ₃ CO group (σm = 0.63), HC≡C group (σm = 0.21), and CH ₂ = CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH = CH group (σm = 0.21), PhCO group (σm = 0.34), H ₂ NCOCH ₂ group (σm = 0.06), etc. In addition, Me represents a methyl group, Ac represents an ethenyl group, and Ph represents a phenyl group (hereinafter, the same).

EWG is preferably a group represented by the following formulae (EWG-1) to (EWG-6).
[Chemical Formula 40]

In the formulae (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom and an alkyl group (carbon numbers of 1 to 12 are preferable, 1 to 6 are more preferable, and 1 to 3 are further Preferred), alkenyl (2 to 12 carbons is preferred, 2 to 6 is more preferred, 2 to 3 is more preferred), aryl (6 to 22 carbons is preferred, 6 to 18 is more preferred) 6 to 10 are more preferred), a hydroxyl group, or a carboxyl group. Ar represents an aromatic group (carbon number 6 to 22 is more preferable, 6 to 18 is more preferable, and 6 to 10 is more preferable). When R ^x1 to R ^x3 are an alkyl group, an alkenyl group, or an aryl group, a ring may be formed, and when the ring is formed, the above-mentioned linking group L may be interposed in the middle. The alkyl group, alkenyl group, aryl group, and Ar may be contained within a range that does not impair the effects of the present invention. Among them, Ar particularly preferably has a carboxyl group (preferably 1 to 3). * Indicates the bonding position.
Np represents an integer of 1 to 6, an integer of 1 to 3 is preferred, and 1 or 2 is more preferred.

The molecular weight of the hot alkali generator in the present invention is preferably 100 or more and less than 2000, and more preferably 200 to 1,000.
As specific examples of the hot alkali generating agent in the present invention, in addition to the compounds used in the examples described later, the acidic compounds which generate alkali when heated to 40 ° C or higher as described in International Publication No. 2015/199219 and pKa1 are exemplified. Ammonium salts of 0 to 4 anions and ammonium cations, which are incorporated into this specification.

When a hot alkali generator is used, the content of the hot alkali generator in the composition is preferably 0.01 to 50% by mass based on the total solid content of the composition. The lower limit is more preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. The upper limit is more preferably 10% by mass or less, and even more preferably 5% by mass or less.
As the hot alkali generator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range. Moreover, the composition of this invention can also be set as the structure which does not contain a hot alkali generator substantially. Substantially not included means less than 0.01% by mass and more preferably less than 0.005% by mass with respect to the total solid content of the composition.

＜ Other additives ＞
The photosensitive resin composition of the present invention can be added with various additives, such as a thermal radical polymerization initiator, a thermal acid generator, a sensitizing dye, a chain transfer agent, and an interfacial activity, if necessary, within a range not to impair the effects of the present invention. Agents, higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, agglutination inhibitors, etc. When these additives are added, the total added amount is preferably 3% by mass or less of the solid content of the composition.

＜＜ Photoacid generator ＞＞
The composition of the present invention may contain a photoacid generator. By containing a photoacid generator, an acid is generated in the exposed portion, and the solubility of the exposed portion with respect to the alkaline aqueous solution is increased, and therefore, it can be used as a positive photosensitive resin composition.
Examples of the photoacid generator include quinonediazide compounds, sulfonium salts, sulfonium salts, diazonium salts, and sulfonium salts. Among these, a quinonediazide compound is preferably used from the standpoint that it exhibits an excellent dissolution inhibitory effect, and can obtain a positive composition with high sensitivity and low film loss. In addition, two or more kinds of photoacid generators may be contained. Thereby, it is possible to further increase the ratio of the dissolution speed of the exposed portion and the unexposed portion, and it is possible to obtain a highly sensitive positive-type photosensitive resin composition.
Specifically, it is possible to refer to the descriptions of paragraphs 0209 to 0215 of International Publication No. 2017/110982, and incorporate them into this specification.

The content of the photoacid generator is preferably 3 to 40 parts by mass based on 100 parts by mass of the polymer precursor. By setting the content of the photoacid generator to this range, it is possible to further increase the sensitivity. If necessary, it may contain a sensitizer and the like.
Only one kind of photoacid generator may be used, or two or more kinds may be used. When two or more kinds are used, the total amount is preferably in the above range.

＜＜ Photobase generator ＞＞
The photosensitive resin composition used in the present invention may contain a photobase generator. The photo-hardening accelerator in the present invention is preferably one that generates alkali by exposure (photo-alkali generator), does not show activity under normal conditions of normal temperature and normal pressure, and is generated when electromagnetic wave irradiation and heating are used as external stimuli. Alkali (alkaline substances) is particularly preferred. Since the alkali generated by exposure functions as a catalyst when the polymer precursor is hardened by heating, it can be suitably used.
In this invention, a well-known thing can be used as a photohardening accelerator. For example, it is possible to cite migration metal compound complexes, structures with ammonium salts, and the like, such as those in which the fluorenyl moiety is potentialized by the formation of a carboxylic acid and a salt, and the alkali component is neutralized by the formation of a salt. Non-ionic compounds in which alkali components such as carbamate derivatives, oxime ester derivatives, and fluorenyl compounds, or alkali components such as oxime bonds, are potentialized.

Examples of the light hardening accelerator of the present invention include a light hardening accelerator having a cinnamate structure as disclosed in Japanese Patent Application Laid-Open No. 2009-080452 and International Publication No. 2009/123122, such as Japanese Patent Laid-Open No. 2006- A light hardening accelerator having a urethane structure as disclosed in JP 189591 and Japanese Patent Application Laid-Open No. 2008-247747, as disclosed in Japanese Patent Application Laid-Open No. 2007-249013 and Japanese Patent Application Laid-Open No. 2008-003581. Photocuring accelerators such as an oxime structure and a formazanoxime structure are not limited to these, and other known structures of photocuring accelerators can be used.

In addition, examples of the photohardening accelerator include compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of Japanese Patent Application Laid-Open No. 2012-093746, and 0022 to Japanese Patent Publication No. 2013-194205. The compounds described in paragraph 0069, the compounds described in paragraphs 0026 to 0074 of Japanese Patent Application Laid-Open No. 2013-204019, and the compounds described in paragraph 0052 of International Publication No. 2010/064631 are examples.

As commercially available products for light hardening accelerators, WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB can also be used. -172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.).

When a photohardening accelerator is used, the content of the photohardening accelerator in the composition is preferably 0.1 to 50% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less.
The light hardening accelerator can be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range.

＜＜ Thermal radical polymerization initiator ＞＞
The photosensitive resin composition of the present invention may contain a thermal radical polymerization initiator within a range that does not deviate from the gist of the present invention.
A thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and starts or promotes the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the cyclization of the polymer precursor can be performed, and the polymerization reaction of the polymer precursor can be performed. Therefore, higher heat resistance can be achieved.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-063554.

When a thermal radical polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably, relative to the total solid content of the photosensitive resin composition of the present invention. 5 to 15 mass%. The thermal radical polymerization initiator may contain only one kind, or may contain two or more kinds. When two or more types of thermal radical polymerization initiators are contained, the total is preferably in the above range.

＜＜ Thermal acid generator ＞＞
The photosensitive resin composition of the present invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating, and promotes the cyclization of the polymer precursor to further improve the mechanical properties of the cured film. Examples of the thermal acid generator include compounds described in paragraph 0059 of Japanese Patent Application Laid-Open No. 2013-167742.

The content of the thermal acid generator is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the polymer precursor, and more preferably 0.1 parts by mass or more. By containing 0.01 parts by mass or more of a thermal acid generator, the crosslinking reaction and the cyclization of the polymer precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. From the viewpoint of electrical insulation of the cured film, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.
One type of thermal acid generator may be used, or two or more types may be used. When two or more kinds are used, the total amount is preferably in the above range.

＜< Sensitization Pigment >＞
The photosensitive resin composition of this invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electronically excited state. The sensitized dye in an electronically excited state is brought into contact with a thermal alkali generator, a thermal radical polymerization initiator, a photoradical polymerization initiator, and the like to generate effects such as electron transfer, energy transfer, and heat generation. As a result, the thermal base generator, thermal radical polymerization initiator, and photoradical polymerization initiator cause chemical changes to decompose, and generate radicals, acids, or bases. For details of the sensitizing dye, reference can be made to the descriptions in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and the contents are incorporated into this specification.

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

＜〈 chain transfer agent 〉＞
The photosensitive resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined in, for example, the third edition of the polymer dictionary (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule can be used. These can generate free radicals by supplying hydrogen to low-active free radicals, or can generate free radicals by deprotonation after oxidation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles) can be preferably used. Wait).

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% by mass, and 1 to 10% by mass relative to the total solid content of the photosensitive resin composition of the present invention. More preferably, 1 to 5 mass% is more preferable. The chain transfer agent may be only one kind, or two or more kinds. When there are two or more kinds of chain transfer agents, the total is preferably in the above range.

＜ Interfacial Active Agents ＞＞
From the viewpoint of further improving the coatability, various surfactants can be added to the photosensitive resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferred.
[Chemical Formula 41]

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

<< Higher Fatty Acid Derivatives >>
In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid and behenyl behenate can be added to the photosensitive resin composition of the present invention, and it is locally present in the drying process after coating. The surface of the composition.
When the photosensitive resin composition of this invention has a higher fatty acid derivative, it is preferable that content of a higher fatty acid derivative is 0.1-10 mass% with respect to the total solid content of the photosensitive resin composition of this invention. The higher fatty acid derivative may be only one type, or may be two or more types. When there are two or more types of higher fatty acid derivatives, the total is preferably in the above range.

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

From the viewpoint of insulation 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. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are included, the total of these metals is preferably within the above range.
In addition, as a method for reducing metal impurities inadvertently contained in the photosensitive resin composition of the present invention, as a raw material constituting the photosensitive resin composition of the present invention, a material having a small metal content is selected, and The raw materials of the photosensitive resin composition of the present invention are filtered by a filter, the inside of the device is lined with polytetrachlorovinyl or the like, and distillation is performed under conditions that minimize contamination.

Regarding the photosensitive resin composition of the present invention, if the use as a semiconductor material is considered, from the viewpoint of wiring corrosion, 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 is further preferred. Among them, those present in the state of halide ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of a chlorine atom and a bromine atom, or a chloride ion and a bromine ion is the said range, respectively.

As a storage container for the photosensitive resin composition of the present invention, a conventionally known storage container can be used. In addition, as a storage container, in order to suppress the incorporation of impurities into the raw materials or the composition, it is also preferable to use a multi-layer bottle composed of six kinds of six-layer resins or a bottle having six resins in a seven-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Preparation of composition>
The photosensitive resin composition of this invention can be prepared by mixing each said component. The mixing method is not particularly limited, and can be performed by a conventionally known method. The present invention also provides a method for producing a photosensitive resin composition, the method comprising adding an acid to at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. In the process, the above-mentioned acid has a single bond of nitrogen and sulfur, and is stable with respect to light having a wavelength of 365 nm. It is preferable to add the above-mentioned acid to the synthesis of the polymer precursor.
In addition, for the purpose of removing foreign matters such as garbage and particles in the composition, filtration using a filter is preferred. The pore diameter of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrachloroethylene, polyethylene or nylon. The filter can also be used in advance by organic solvents. In the filtration process of the filter, a plurality of filters may be connected and used in series or in parallel. When using multiple types of filters, filters with different pore sizes or materials can be used in combination. In addition, various materials may be filtered several times. In the case of a plurality of filtrations, the filtration may be circular. In addition, filtration may be performed under pressure. When filtering is performed under pressure, the pressure is preferably 0.05 MPa to 0.3 MPa.
In addition to filtration using a filter, removal of impurities using an adsorbent can also be performed. It is also possible to combine filter filtration and impurity removal treatment using adsorption materials. As the adsorbent, a known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolites, and organic adsorbents such as activated carbon.

<Curing film, laminated body, semiconductor device, and manufacturing method thereof>
Next, a cured film, a laminated body, a semiconductor device, and a manufacturing method thereof will be described.
The cured film of the present invention is obtained by curing the photosensitive resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can also be 1 μm or more. The upper limit value can be 100 μm or less, and can also be 30 μm or less.

The cured film of the present invention can be formed into a laminated body by laminating two or more layers, or even 3 to 7 layers. A laminated system having two or more hardened films of the present invention preferably has a metal layer between the hardened films. Such a metal layer is preferably used as metal wiring such as a redistribution layer.

Examples of the fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and pressure buffer films. Other examples include a process of patterning a sealing film, a substrate material (a base film or a cover film of a flexible printed circuit board, an interlayer insulating film) or an insulating film for mounting as described above by etching. For these uses, see, for example, Science & technology Co., Ltd., "High Functionalization and Application Technology of Polyimide" April 2008, Kakimoto Yamen / Supervisor, CMC Technical Library, Polyimide Material Basic research and development "published in November 2011, Japan Polyimide · Aromatic Polymer Research Society / Edition" Latest Polyimide Basics and Applications "NTS Inc., August 2010, etc.

In addition, the cured film in the present invention can also be used for the production of a layout such as an offset plate or a screen plate, the use of a molded component for etching, the production of a protective varnish and a dielectric layer in electronics, especially microelectronics, and the like.

The method for producing a cured film of the present invention includes a process using the photosensitive resin composition of the present invention. Specifically, the method includes a film forming process (a layered layer forming process), forming a film by applying the photosensitive resin composition of the present invention to a substrate, and a heating process of forming a layer at 80 to 450 ° C. The photosensitive resin composition is heated. Preferably, the method for producing a cured film includes an exposure process for exposing the film after the film formation process (layer formation process) described above, and developing the exposed photosensitive resin composition layer (film, that is, resin layer). Manufacturing method of developing process. A heating process including heating (preferably heating at 80 to 450 ° C.) after the development is performed, so that the exposed resin layer can be further hardened. In addition, as described above, when a photosensitive resin composition is used, the composition can be hardened by exposure in advance, and then desired processing (for example, the following lamination) can be performed as needed, and further hardened by heating.

The manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention. After the hardened film is formed by the above-mentioned hardened film manufacturing method in the method for manufacturing a laminated body of the present invention, it is preferable to perform the following processes in order, that is, the film forming process (layer forming process) and heating process of the photosensitive resin composition Or, when imparting photosensitivity, it is a film formation process (layer formation process), an exposure process, and a development process (further heating process if necessary). In particular, it is preferable to perform a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in the order of the above-mentioned processes. In this manner, a laminated body can be formed by laminating a cured film. In the present invention, a metal layer is particularly preferably provided on a portion where a hardened film is provided, between hardened films, or both.
These details will be described below.

<< Film Formation Process (Layer Formation Process) >>
A manufacturing method of a preferred embodiment of the present invention includes a film forming process (layer forming process) in which a photosensitive resin composition is applied to a substrate to form a film (layered).
The type of substrate can be appropriately determined according to the application. Silicon, silicon nitride, polycrystalline silicon, silicon oxide, amorphous silicon and other semiconductor production substrates, quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, Ni, There are no particular restrictions on metal substrates such as Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, and electrode plates for plasma display panels (PDP). In the present invention, a substrate made of a semiconductor is particularly preferred, and a silicon substrate is more preferred.
When a photosensitive resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes a substrate.
As a means for applying the photosensitive resin composition to a substrate, coating is preferred.
Specifically, as a means of application, a dip coating method, an air knife coating method, a curtain coating method, a wire rod coating method, a gravure coating method, an extrusion coating method, and an inkjet coating can be exemplified. Cloth method, spin coating method, slit coating method, or inkjet method. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, an inkjet coating method, and an inkjet method are more preferred. By appropriately adjusting the solid content concentration or the coating conditions according to the method, a resin layer having a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, a spin coating method, an inkjet coating method, or an inkjet method is preferable. If it is a rectangular substrate, A slit coating method, an inkjet coating method, an inkjet method, or the like is preferred. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

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

＜＜ Exposure Process ＞＞
The manufacturing method of this invention may include the exposure process which exposes the said photosensitive resin composition layer. The exposure amount is not particularly limited as long as the photosensitive resin composition can be cured, and for example, an exposure energy conversion meter at a wavelength of 365 nm is preferably 100 to 10,000 mJ / cm ² and more preferably 200 to 8000 mJ / cm ² .
The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, and 240 to 550 nm is more preferable.
Considering the relationship with the light source, the exposure wavelengths can include (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high pressure mercury lamps, g-rays (wavelength 436nm), h-ray (wavelength 405nm), i-ray line (wavelength 365nm), wide (g-ray, h-ray, i-ray 3 wavelengths), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF Excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beam, etc. Regarding the photosensitive resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferable, and exposure by an i-ray is preferable. Thereby, a particularly high exposure sensitivity can be obtained.

＜＜ Developing Process ＞＞
The manufacturing method of the present invention may include a development process of performing a development process on the exposed photosensitive resin composition layer. The unexposed portions (non-exposed portions) are removed by developing. The development method is not particularly limited as long as a desired pattern can be formed, and for example, a development method such as a liquid-covered method, spray, dipping, or ultrasonic wave can be used.
A developing solution is used for development. As long as the unexposed portion (non-exposed portion) can be removed, the developer can be used without particular restrictions. The developing solution preferably contains an organic solvent, and more preferably the developing solution contains an organic solvent of 90% by mass or more. In the present invention, it is more preferable that the developer contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3.
As for the organic solvent, as the esters, for example, ethyl acetate, n-butyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl Ethyl acetate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (such as methyl alkoxyacetate, Ethyl alkoxyacetate, butyl ethoxyacetate (such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), 3-alkoxypropanoic acid alkyl esters (such as methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (such as methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (eg 2-alkoxypropionate Methyl ester, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkane Methyloxy-2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (e.g. methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2 -Ethyl methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-oxobutanoate, 2-oxo Ethyl butyrate and the like; as the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl Cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Propylene glycol monopropyl ether acetate and the like; as the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl- 2-Pyrrolidone and the like; as the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, and the like are preferably listed; as the fluorenes, dimethyl sulfene is preferably listed.
In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred.
Regarding the developing solution, 50% by mass or more of the total component is preferably an organic solvent, 70% by mass or more of an organic solvent is more preferred, and 90% by mass or more of an organic solvent is more preferably. As for the developer, 100% by mass may be an organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature of the developing solution during development is not particularly limited, and it can usually be performed at 20 to 40 ° C.
After the treatment with the developer, further processing can be performed. Rinse is preferably performed with a solvent different from the developer. For example, it is possible to wash with a solvent contained in the photosensitive resin composition. The rinse time is preferably 5 seconds to 1 minute.

＜＜ Heating Process ＞＞
The manufacturing method of the present invention is preferably a process including heating after a film formation process (layer formation process), a drying process, or a development process. In particular, a process including heating the film after the development process is preferred. Cyclization of polymer precursors occurs during the heating process. The composition of the present invention may contain a radical polymerizable compound other than the polymer precursor, and curing of the radical polymerizable compound other than the unreacted polymer precursor may also be performed in this process. The heating temperature (highest heating temperature) of the layer in the heating step is preferably 50 to 500 ° C, more preferably 80 to 450 ° C, even more preferably 140 to 350 ° C, even more preferably 160 to 250 ° C, and 170 ～ 220 ℃ is the best.
Heating from the temperature at the start of heating to the maximum heating temperature is preferably performed at a temperature increase rate of 1 to 12 ° C / minute, more preferably 2 to 10 ° C / minute, and even more preferably 3 to 10 ° C / minute. By setting the temperature increase rate to 1 ° C / min or more, it is possible to prevent excessive volatilization of the amine while ensuring productivity, and by setting the temperature increase rate to 12 ° C / min or less, the residual stress of the cured film can be reduced.
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 beginning of heating refers to the temperature at the beginning of the process of heating up to the maximum heating temperature. For example, when the photosensitive resin composition is applied to a substrate and dried, the temperature of the dried film (layer) is, for example, 30 to 30 ° lower than the boiling point of the solvent contained in the photosensitive resin composition. It is preferable that the temperature of 200 ° C is gradually increased.
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.
In particular, when forming a multilayer laminate, from the viewpoint of the adhesion between the layers of the cured film, the heating temperature is preferably 180 ° C to 320 ° C, and more preferably 180 ° C to 260 ° C. The reason for this is uncertain, but it is thought that by setting the temperature to this temperature, the ethynyl groups of the polymer precursors in the layers undergo a crosslinking reaction with each other.

Heating can be performed in stages. As an example, the following pretreatment process may be performed: heating from 25 ° C to 180 ° C at 3 ° C / min, holding at 180 ° C for 60 minutes, increasing the temperature from 180 ° C to 200 ° C at 2 ° C / minute, and maintaining 120 ° C at 200 ° C. minute. The heating temperature as the pretreatment process is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and still more preferably 120 to 185 ° C. In this pretreatment process, as described in US Pat. No. 9,159,547, it is also preferable to perform treatment while irradiating ultraviolet rays. The characteristics of the film can be improved by this pretreatment process. The pretreatment process can be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment can be set to two or more steps. For example, the pretreatment process 1 is performed in the range of 100 to 150 ° C, and then the pretreatment process 2 is performed in the range of 150 to 200 ° C.
In addition, cooling may be performed after heating, and a cooling rate at this time is preferably 1 to 5 ° C / minute.

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

＜〈 Metal Layer Formation Process 〉＞
The manufacturing method of the present invention preferably includes a metal layer forming process of forming a metal layer on the surface of the photosensitive resin composition layer after the development process.
The metal layer is not particularly limited. Existing metal species can be used. Examples of the metal layer include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferred, and copper is more preferred.
The method for forming the metal layer is not particularly limited, and a conventional method can be applied. For example, the methods described in Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application No. 2001-521288, Japanese Patent Application Laid-Open No. 2004-214501, and Japanese Patent Application Laid-Open No. 2004-101850 can be used. For example, photolithography, peeling, electrolytic plating, electroless plating, etching, printing, and a method of combining them. More specific examples include a patterning method in which sputtering, photolithography, and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined.
The thickness of the metal layer is preferably 0.1 to 50 μm at the thickest portion, and more preferably 1 to 10 μm.

＜〈 Laminated Process 〉＞
Preferably, the manufacturing method of the present invention further includes a lamination process.
The lamination process includes one of the following series of processes: the above-mentioned film formation process (layer formation process) and heating process are performed again on the surface of the hardened film (resin layer) or metal layer, or the above-mentioned film formation process (layer formation process) is sequentially performed ), The exposure process and the development process. It goes without saying that the lamination process may further include the above-mentioned drying process or heating process.
When the lamination process is further performed after the lamination process, a surface activation treatment process may be further performed after the heating process, the exposure process, or the metal layer formation process. Examples of the surface activation treatment include a plasma treatment.
The lamination process is preferably performed 2 to 5 times, and more preferably 3 to 5 times.
For example, a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer such as a resin layer having a structure of 3 or more and 7 or less is preferable, and 3 or more and 5 or less is more preferable.
That is, in the present invention, in particular, after the metal layer is provided, the film formation process (layer formation process) and heating process of the photosensitive resin composition are sequentially performed so as to cover the metal layer, or the film formation process (layer formation) Manufacturing process), the above-mentioned exposure process, and the above-mentioned developing process process (further heating process as required) are preferred. By alternately laminating the photosensitive resin composition layer (resin) and the metal layer forming process, the photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses a semiconductor device having the cured film or laminated body of the present invention. As specific examples of the semiconductor device in which the photosensitive resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, refer to the descriptions in paragraphs 0213 to 0218 of Japanese Patent Application Laid-Open No. 2016-027357 and the description in FIG. 1. This content is incorporated into this manual.
[Example]

The following examples further illustrate the present invention. The materials, usage amounts, proportions, processing contents, processing steps, etc. shown in the following examples can be changed as long as they do not depart from the spirit 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 quality standards.

<Synthesis of polymer precursor (resin)>
(Synthesis example 1)
[Polyimide precursor composition A- derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and diamine (a) shown below Synthesis of 1]
42.4 g of 4,4'-oxodiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C for 4 hours. . Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 76.0 g of diamine (a) was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes, and the mixture was stirred for 1 hour, followed by 3.0 g of saccharin (B-1), 20 mL of ethanol, and 200 mL of γ-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution, and the polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. for 2 days under reduced pressure. The weight average molecular weight of the obtained powdery polyfluorene imide precursor was 25,600, and the number average molecular weight was 8,600.
Diamine (a)
[Chemical Formula 42]

(Synthesis example 2)
[Synthesis of polyimide precursor composition A-2 derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and diamine (a)]
42.4 g of 4,4'-oxodiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C for 4 hours. . Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 76.0 g of diamine (a) was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes, and the mixture was stirred for 1 hour, followed by 3.0 g of N-cyclohexylaminosulfonic acid (B-2), 20 mL of ethanol, and 200 mL of γ-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution, and the polyimide precursor was precipitated in water and filtered, and dried at 45 ° C for 2 days under reduced pressure. The weight average molecular weight of the obtained powdery polyfluorene imide precursor was 23,600, and the number average molecular weight was 8,200.

(Synthesis example 3)
[Synthesis of polyimide precursor composition A-3 derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and diamine (a)]
42.4 g of 4,4'-oxodiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C for 4 hours. . Next, the reaction mixture was cooled to -10 ° C, and a solution having 34.35 g of dicyclohexylcarbodiimide dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 76.0 g of diamine (a) was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes, and the mixture was stirred for 1 hour, followed by 3.0 g of ethanesulfonic acid (B-c1), 20 mL of ethanol, and 200 mL of γ-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. The obtained reaction solution was precipitated and filtered in 14 L of water, and dried under reduced pressure at 45 ° C for 2 days. The weight average molecular weight of the obtained powdered polyfluorene imide precursor was 25,100, and the number average molecular weight was 8,400.

(Synthesis example 4)
[Synthesis of polyimide precursor composition A-4 derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and diamine (a)]
42.4 g of 4,4'-oxodiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C for 4 hours. . Next, the reaction mixture was cooled to -10 ° C, and a solution having 34.35 g of dicyclohexylcarbodiimide dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 76.0 g of diamine (a) was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes, and the mixture was stirred for 1 hour, and then 20 mL of Ethanol and 200 mL of gamma-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution, and the polyimide precursor was precipitated in water and filtered, and dried at 45 ° C for 2 days under reduced pressure. The weight average molecular weight of the obtained powdery polyfluorene imide precursor was 22,500, and the number average molecular weight was 8,200.

(Synthesis example 5)
[Polyimide precursor composition A- derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diaminodiphenyl ether Synthesis of 5]
42.4 g of 4,4'-oxodiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C for 4 hours. . Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of diisopropylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 25.1 g of 4,4'-diaminodiphenyl ether was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C for 60 minutes, and the mixture 1 was stirred. After an hour, 3.0 g of saccharin (B-1), 20 mL of ethanol, and 200 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution, and the polyimide precursor was precipitated in water and filtered, and dried at 45 ° C for 2 days under reduced pressure. The weight average molecular weight of the obtained powdery polyimide precursor was 23,800, and the number average molecular weight was 8,700.

(Synthesis example 6)
[Polyimide precursor composition A- derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diaminodiphenyl ether Synthesis of 6]
42.4 g of 4,4'-oxodiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C for 4 hours. . Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of diisopropylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 25.1 g of 4,4'-diaminodiphenyl ether was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C for 60 minutes, and the mixture 1 was stirred. After an hour, 3.0 g of N-cyclohexylaminosulfonic acid (B-2), 20 mL of ethanol, and 200 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution, and the polyimide precursor was precipitated in water and filtered, and dried at 45 ° C for 2 days under reduced pressure. The weight average molecular weight of the obtained powdery polyimide precursor was 23,800, and the number average molecular weight was 8,700.

(Synthesis example 7)
[Polyimide precursor composition A- derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diaminodiphenyl ether Synthesis of 7]
42.4 g of 4,4'-oxodiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C for 4 hours. . Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of diisopropylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 25.1 g of 4,4'-diaminodiphenyl ether was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C for 60 minutes, and the mixture 1 was stirred. After hours, 20 mL of ethanol and 200 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution, and the polyimide precursor was precipitated in water and filtered, and dried at 45 ° C for 2 days under reduced pressure. The weight average molecular weight of the obtained powdery polyimide precursor was 25,400, and the number average molecular weight was 8,500.

(Synthesis example 8)
[Synthesis of polyimide precursor composition A-8 derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and diamine (a)]
Mix 21.2 g of 4,4'-oxodiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme, at a temperature of 60 ° C It was stirred for 4 hours. Next, the reaction mixture was cooled to -10 ° C, and while maintaining the temperature at -10 ± 5 ° C, 17.0 g of SOCl _{2 was} added over 60 minutes. After diluting with 50 mL of N-methylpyrrolidone, a solution of 38.0 g of diamine (a) dissolved in 100 mL of N-methylpyrrolidone was added dropwise over 60 minutes at -10 ± 5 ° C. The reaction mixture was stirred for 1 hour, and then 3.0 g of saccharin (B-1) and 20 mL of ethanol were added. The obtained reaction solution was used to precipitate a polyimide precursor in 6 L of water, and the solid was filtered and dissolved in 380 g of tetrahydrofuran. To the obtained reaction solution, 6 L of water was added to precipitate the polyimide precursor in water and the solid was filtered, and dried at 45 ° C for 2 days under reduced pressure. The powdery polyfluorene imide precursor obtained had a weight average molecular weight of 23,900 and a number average molecular weight of 8,000.

(Synthesis example 9)
[Synthesis of Polyimide Precursor Composition A-9 derived from 3,3'4,4'-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl methacrylate, and diamine (a)]
40.2 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C. It took 4 hours. Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 76.0 g of diamine (a) was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes, and the mixture was stirred for 1 hour, followed by 3.0 g of saccharin (B-1), 20 mL of ethanol, and 200 mL of γ-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution, and the polyimide precursor was precipitated in water and filtered, and dried at 45 ° C for 2 days under reduced pressure. The weight average molecular weight of the obtained powdery polyfluorene imide precursor was 24,600, and the number average molecular weight was 8,300.

(Synthesis example 10)
[Polyimide precursor composition derived from 3,3'4,4'-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diaminodiphenyl ether Synthesis of A-10]
40.2 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C. It took 4 hours. Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 25.1 g of 4,4'-diaminodiphenyl ether was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C for 60 minutes, and the mixture 1 was stirred. After an hour, 3.0 g of saccharin (B-1), 20 mL of ethanol, and 200 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution, and the polyimide precursor was precipitated in water and filtered, and dried at 45 ° C for 2 days under reduced pressure. The weight average molecular weight of the obtained powdery polyimide precursor was 22,500, and the number average molecular weight was 8,000.

(Synthesis example 11)
[Derived from 3,3'4,4'-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diaminodiphenyl ether polyfluorene imide precursor composition A Synthesis of -11]
40.2 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C It took 4 hours. Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 25.1 g of 4,4'-diaminodiphenyl ether was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C for 60 minutes, and the mixture 1 was stirred. After hours, 20 mL of ethanol and 200 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution, and the polyimide precursor was precipitated in water and filtered, and dried at 45 ° C for 2 days under reduced pressure. The weight average molecular weight of the obtained powdery polyimide precursor was 25,400, and the number average molecular weight was 8,500.

(Synthesis example 12)
[Synthesis of polyimide precursor composition A-12 derived from pyromellitic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diaminodiphenyl ether]
29.8 g of pyromellitic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C. for 4 hours. Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 25.1 g of 4,4'-diaminodiphenyl ether was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C for 60 minutes, and the mixture 1 was stirred. After an hour, 3.0 g of saccharin (B-1), 20 mL of ethanol, and 200 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution, and the polyimide precursor was precipitated in water and filtered, and dried at 45 ° C for 2 days under reduced pressure. The weight average molecular weight of the obtained powdery polyfluorene imide precursor was 25,200, and the number average molecular weight was 8,800.

(Synthesis example 13)
[Synthesis of polyimide precursor composition A-13 derived from pyromellitic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diaminodiphenyl ether]
29.8 g of pyromellitic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C. for 4 hours. Next, the reaction mixture was cooled to -10 ° C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C over 60 minutes. The mixture was stirred for 30 minutes. Next, a solution in which 25.1 g of 4,4'-diaminodiphenyl ether was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10 ± 5 ° C for 60 minutes, and the mixture 1 was stirred. After an hour, 3.0 g of N-cyclohexylaminosulfonic acid (B-2), 20 mL of ethanol, and 200 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. 14 L of water was added to the obtained reaction solution, and the polyimide precursor was precipitated in water and filtered, and dried at 45 ° C for 2 days under reduced pressure. The weight average molecular weight of the obtained powdery polyfluorene imide precursor was 25,400, and the number average molecular weight was 8,400.

(Synthesis example 14)
[Polyimide precursors derived from pyromellitic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl Synthesis of Composition A-14]
14.9 g of pyromellitic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme were mixed and stirred at a temperature of 60 ° C for 4 hours. Next, the reaction mixture was cooled to -10 ° C, and while maintaining the temperature at -10 ± 5 ° C, 17.0 g of SOCl _{2 was} added over 60 minutes. After diluting with 50 mL of N-methylpyrrolidone, 40.2 g of 4,4'-diamino group was dissolved in 100 mL of N-methylpyrrolidone at -10 ± 5 ° C for 60 minutes. A solution of 2,2'-bis (trifluoromethyl) biphenyl was added dropwise to the reaction mixture, and after stirring the mixture for 1 hour, 3.0 g of saccharin (B-1) and 20 mL of ethanol were added. The polyimide precursor was precipitated in 6 L of water, and the obtained reaction solution was dissolved in 380 g of tetrahydrofuran after filtering the solid. 6 L of water was added to the obtained reaction solution to precipitate the polyimide precursor in water. The solid was filtered again and dried under reduced pressure at 45 ° C for 2 days. The weight average molecular weight of the obtained powdery polyfluorene imide precursor was 23,800, and the number average molecular weight was 8,800.

(Synthesis Example 15)
[Polybenzoxazole precursor composition A-15 derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-oxobenzophenone chloride Synthesis]
28.0 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved by stirring in 200 mL of N-methylpyrrolidone. Next, while maintaining the temperature at 0 to 5 ° C, 25.0 g of 4,4'-oxobenzophenazine chloride was added dropwise over 10 minutes, and the mixture was stirred for 60 minutes. 3.0 g of saccharin (B- 1). 6 L of water was added to the obtained reaction solution to precipitate a polybenzoxazole precursor, and the solid was filtered and dried under reduced pressure at 45 ° C for 2 days. The weight average molecular weight of the obtained powdery polybenzoxazole precursor was 25,000, and the number average molecular weight was 8,500.

<Preparation of photosensitive resin composition>
A coating solution of a photosensitive resin composition was prepared by mixing a resin with the components described in Tables 1 and 2 below to prepare a uniform solution. Each photosensitive resin composition was filtered under pressure by passing through a filter made by ADVANTEC having a pore width of 0.8 μm.

＜ Substrate processing process ＞
For a wafer obtained by electroplating Cu on a silicon wafer (hereinafter referred to as a “Cu wafer”), an oxide film etcher (U621, Hitachi High-Technologies Corporation) was used at a flow rate of O ₂ gas of 500 mL / min. the O ₂ plasma treatment for 60 seconds.
<Photosensitive resin composition layer forming process>
Then, each photosensitive resin composition was applied on a Cu wafer by a spin coating method to form a layer, thereby forming a photosensitive resin composition layer.
＜ Drying process ＞
The Cu wafer having the obtained photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 4 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 20 μm on a silicon wafer.
＜ Exposure Process ＞
Next, a stepper (Nikon NSR 2005 i9C) was used at an exposure wavelength of 365 nm (i-ray) and a binary light mask (a square array of hole patterns, a 200 μm pitch, and a mask size of 100 μm) was used at 400 mJ / cm ² The photosensitive resin composition layer on the Cu wafer was exposed at a high exposure energy.
When the photosensitive resin composition layer is patterned, a larger number of interfaces are generated than when the pattern is not patterned, and a small contact area is generated between the layers when the substrate and the cured film and the metal layer are laminated. In this case, interlayer peeling is more likely to occur, and the effect of the present invention is more apparent.
＜ Development process ＞
The exposed photosensitive resin composition layer on the entire surface was immersed in cyclopentanone for 60 seconds to perform a development treatment.
<Hardening process>
Next, the temperature of the photosensitive resin composition layer after the development process was increased at a temperature increase rate of 5 ° C / minute, and the temperature was maintained at 230 ° C for 3 hours.

＜ Evaluation of storage stability ＞
10 g of the above-mentioned photosensitive resin composition was sealed in a container (material of the container: light-shielding glass, capacity: 100 mL), and allowed to stand for 2 weeks in an environment of 25 ° C. and a relative humidity of 65%. Use an E-type viscometer (TV-25, Toki Sangyo Co., Ltd) to measure the viscosity before and after standing, and calculate the viscosity change rate before and after standing (｜ viscosity after the test-viscosity before the test | / viscosity before the test) .
A: less than 8%
B: more than 8% and less than 10%
C: 10 or more and less than 15%
D: 15% or more

＜ Evaluation of Adhesion ＞
Using a high-acceleration life tester (PC-422R8D, HIRAYAMA Manufacturing Corporation), the cured film was allowed to stand for 1,000 hours at 121 ° C and 100% RH. Using a bonding tester (Condor Sigma, XYZTEC), the peeling force measurement of the substrate and the cured film was performed on a cured film with a pattern angle of 100 μm on a copper (Cu) wafer before and after the test. As a measurement condition, a 200 μm needle was used at room temperature and a peeling speed of 10 μm / s was performed at a distance of 2 μm between the substrate and the needle. The adhesion force before the test was 50 gf (1N was 102.0 gf), and the adhesion force reduction rate before and after ((peel force after test-peel force before test) / peel force before test) was calculated.
A: less than 30%
B: 30% or more and less than 35%
C: more than 35% and less than 40%
D: 40% or more

＜ Copper Corrosiveness ＞
The optical substrate (manufactured by Nikon) and the cross-section SEM (manufactured by Hitachi, Ltd.) were used to observe the copper substrate (blank) without the cured film and the peripheral portion of the pattern on the copper substrate evaluated by the apparatus described above. The following judgments were made by visually confirming discoloration, corrosion, and film thickness variation and unevenness of the substrate interface.
A: No discoloration was observed compared to the blank.
B: Discoloration occurred compared with the blank, and no change in film thickness was observed.
C: Discoloration occurred compared with the blank, and a reduction in film thickness was observed, but no unevenness was observed on the surface.
D: Discoloration occurred compared to the blank, and a decrease in film thickness was observed. Moreover, unevenness was observed on the surface.

[Table 1]
In the polymer precursor item, () refers to the addition of a specific acid during synthesis (same in the following table)
* 1 Radical polymerizable compound
* 2 0.5 parts by mass of B1

[Table 2]

Formulation table of photosensitive resin composition
[table 3]
Those marked with "-" in Tables 1 and 2 are not added (0 parts by mass)
Specific acids (additives)
[Table 4]
[Chemical Formula 43]

Coincidence initiator
[table 5]

Radical polymerizable compound (polymerizable compound)
[TABLE 6]

Solvent
[TABLE 7]
DMSO: dimethyl sulfenyl means that N-methylpyrrolidone lactate s ethyl ester is blended at 128.80 / 32.20, and γ-butyrolactone / DMSO (dimethyl sulfoxide) is blended at 128.80 / 32.20.

Hot alkali generator
[Chemical Formula 44]

Metal adhesion improver (silane coupling agent)
[Chemical Formula 45]

Et: ethyl

Polymerization inhibitor
H-1: 1,4-benzoquinone
H-2: 4-methoxyphenol

Migration inhibitor (anti-corrosive)
I-1: 1,2,4-triazole
I-2: 1H-tetrazole

From the above results, it is understood that the photosensitive resin composition using a polymer precursor and a specific acid in the present invention exhibits sufficient adhesion and achieves high storage stability. On the other hand, in Comparative Examples 2 and 3 in which the acid itself was not used, storage stability was poor (D), and adhesiveness was also insufficient (D). When an acid is used but does not meet specific requirements (Comparative Example 1), the storage stability is low (C), and the result is that the adhesion is insufficient (D). From these results, it is understood that the photosensitive resin composition of the present invention can exhibit excellent performance in the manufacture of semiconductor devices and products thereof.

<Example 100>
The photosensitive resin composition A-1 was subjected to pressure filtration through an ADVANTEC filter having a pore width of 1.0 μm, and then applied to a surface of a resin substrate on which a copper thin layer was formed (3500 rpm, 30 seconds) for application. . The photosensitive resin composition applied to the resin substrate was dried at 100 ° C. for 2 minutes, and then exposed using a stepper (Nikon Corporation, NSR1505i6). The exposure was performed through a mask at an exposure amount of 200 mJ / cm ² at a wavelength of 365 nm. After exposure, baking was performed, development was performed with cyclopentanone for 30 seconds, and PGMEA was developed for 20 seconds to obtain a pattern.
Next, it heated at 230 degreeC for 3 hours, and the interlayer insulation film for redistribution layers was formed. This interlayer insulating film for a redistribution layer has excellent insulation properties.

Claims (26)

A photosensitive resin composition comprising at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and an acid having a single bond of nitrogen and sulfur. The photosensitive resin composition according to item 1 of the patent application scope, wherein The pka of this acid is 0 or more and 4.0 or less. The photosensitive resin composition according to item 1 or item 2 of the scope of patent application, wherein ClogP, which is the logarithm of the water / octanol partition coefficient of this acid, is -2.1 or more and 1.2 or less. The photosensitive resin composition according to item 1 or item 2 of the scope of patent application, wherein The molecular weight of this acid is 300 or less. The photosensitive resin composition according to item 1 or item 2 of the scope of patent application, wherein The acid has a cyclic structure. The photosensitive resin composition according to item 1 or item 2 of the scope of patent application, wherein The acid has a sultamidine structure. The photosensitive resin composition according to any one of claims 1 to 4, wherein the acid is represented by any one of the following formulae (S1) to (S4); In the formulae (S1) to (S4), L ¹¹ represents a single bond or a linking group, L ¹² represents a linking group, R ¹¹ represents a hydrogen atom or a substituent, R ²¹ represents a substituent, R ³¹ represents a substituent, and R ⁴¹ Represents a hydrogen atom or a substituent, R ⁴² represents a substituent, and R ⁴³ represents OH, NH ₂ or N ₃ . The photosensitive resin composition as described in claim 1 or 2, wherein the acid is represented by the following formula (S1-1); In the formula (S1-1), R ¹² is a hydrogen atom or a substituent, and R ¹³ and R ¹⁴ are each independently a hydrogen atom or a substituent. The photosensitive resin composition according to claim 1 or claim 2, further comprising at least one of a photopolymerization initiator, a radical polymerizable compound, and a solvent. The photosensitive resin composition according to item 1 or 2 of the scope of patent application, which is used to form an interlayer insulating film for a redistribution layer. A method for producing a photosensitive resin composition, comprising adding a monomer having nitrogen and sulfur to at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. The process of bond acid. The method for producing a photosensitive resin composition according to item 11 of the scope of patent application, wherein This acid is added to the synthesis of the polymer precursor. The method for producing a photosensitive resin composition according to item 11 or item 12 of the scope of patent application, wherein The pka of this acid is 0 or more and 4.0 or less. The method for producing a photosensitive resin composition according to item 11 or item 12 of the scope of patent application, wherein The ClogP of this acid is -2.1 or more and 1.2 or less. The method for producing a photosensitive resin composition according to item 11 or item 12 of the scope of patent application, wherein The molecular weight of this acid is 300 or less. The method for producing a photosensitive resin composition as described in claim 11 or 12, wherein the acid is represented by any one of the following formulae (S1) to (S4); In the formulae (S1) to (S4), L ¹¹ represents a single bond or a linking group, L ¹² represents a linking group, R ¹¹ represents a hydrogen atom or a substituent, R ²¹ represents a substituent, R ³¹ represents a substituent, and R ⁴¹ Represents a hydrogen atom or a substituent, R ⁴² represents a substituent, and R ⁴³ represents OH, NH ₂ or N ₃ . A cured film obtained by curing the photosensitive resin composition according to any one of the first to tenth of the scope of patent application. The hardened film according to item 17 of the scope of patent application, wherein The film thickness is 1 to 30 μm. A laminated body having two or more hardened films as described in item 17 or item 18 of the scope of patent application. The laminated body according to item 19 of the patent application scope, which has a metal layer between the hardened films. A method for manufacturing a cured film, comprising: a film formation process, applying the photosensitive resin composition described in any one of the first to tenth of the scope of patent application to a substrate to form a film. The method for manufacturing a cured film according to item 21 of the scope of patent application, which comprises an exposure process for exposing the film and a development process for developing the film. The method for manufacturing a cured film according to item 22 of the scope of patent application, wherein The developing solution used for the development contains 90% by mass or more of an organic solvent. The method for manufacturing a hardened film according to item 22 of the scope of application for a patent, which comprises a process of heating the film after the developing process. A method for manufacturing a laminated body, wherein the method for manufacturing a cured film according to any one of the 21st to 24th patent applications is performed multiple times. A semiconductor device having a hardened film described in claim 17 or 18 or a laminated body described in claim 19 or 20.