TW201942675A - Photosensitive resin composition, cured film, laminate, method for manufacturing these, semiconductor device, and thermal base generator used in these - Google Patents

Abstract

Provided are: a photosensitive resin composition that includes a specific thermal base generator, at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, and a photosensitizer, the total content of acid groups and acid-generating groups included in the polymer precursor and the photosensitizer being 0.5 mmol/g or less; a cured film; a laminate; a method for manufacturing these; a semiconductor device; and a thermal base generator used in these.

Description

Photosensitive resin composition, cured film, laminated body, method for manufacturing the same, semiconductor device, and hot alkali generator used for the same

The present invention relates to a photosensitive resin composition, a cured film, a laminated body, a method for manufacturing the same, a semiconductor device, and a hot alkali generator used for the same.

Polyimide resins and polybenzoxazole resins are excellent in heat resistance and insulation properties, and are therefore suitable for various applications (for example, see Non-Patent Documents 1 and 2). This use is not particularly limited, and a semiconductor device for mounting is used as an example, and it can be used as a material of an insulating film and a sealing material or a coating thereof. It is also used as a base film and a cover film of a flexible substrate.
The polyfluorene imine resin and the like generally have low solubility in a solvent. Therefore, in many cases, a method in which the precursor before the cyclization reaction is specifically a polymer precursor such as a polyfluorene imine precursor and a polybenzoxazole precursor is dissolved in a solvent. Thereby, excellent handleability can be achieved, and it becomes possible to apply and process in various forms, such as a board | substrate, when manufacturing each said product. Thereafter, the polymer precursor is cyclized by heating to form a hardened product. In addition to the high heat resistance and insulation properties of polyimide resins, etc., from the viewpoint of excellent manufacturing flexibility, it is expected to gradually develop applications in this industry.

There is a resin which is proposed based on a material to be a film using the above characteristics (Patent Document 1). This photosensitive resin composition contains (A) a polyimide precursor, (B) a specific plasticizer, and (C) a photosensitizer. It is described that it is possible to provide a product which is flexible, has no warpage, and exhibits flame retardancy.
In order to provide an insulating resin or the like for a redistribution layer, a thermosetting resin composition containing a specific tertiary amine compound and a thermosetting resin hardened by alkali cyclization has been proposed (Patent Document 2). It is described that the cyclization reaction can be performed at a low temperature by this, and the stability is excellent. Furthermore, a photosensitive resin composition has been proposed which contains a compound having an anion portion, a heterocyclic polymer-containing precursor, and a radical polymerizable compound in consideration of being an insulating film for a redistribution layer, which contains an anion The compound of this moiety has a specific quaternary ammonium (cationic moiety) and a radical initiation energy (Patent Document 3). It is described that a cyclization reaction can be performed at a low temperature and that it has excellent resolvability in exposure and development.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-109590
[Patent Document 2] International Publication No. 2015/199220
[Patent Document 3] Japanese Patent Application Publication No. 2016-027357
[Non-patent literature]

[Non-Patent Document 1] Science & technology Co., Ltd. "Highly functionalized polyimide in applied technology" April 2008
[Non-Patent Document 2] Yamoto Kakimoto / Chief Editor, CMC Technical library "Basic and Development of Polyimide Materials" Issued in November 2011

According to the above-mentioned technology, it is possible to provide a photosensitive resin composition which is suitable for interlayer insulation films, redistribution layers, and the like and is cyclized at a low temperature, and is excellent in stability and resolution. On the other hand, as the development speed of semiconductor devices is further accelerating, from the consideration of strengthening some performance improvements, it is strongly required to improve the overall performance. Therefore, the present invention is intended to provide a photosensitive resin composition and a cured film, a laminated body, a method for producing a cured film, a method for producing a laminated body, a semiconductor device, and a semiconductor device in view of its use in an interlayer insulating film, a redistribution layer, and the like. A thermal alkali generator. Here, the photosensitive resin composition satisfies the performance requirements for the photosensitive resin composition to a high standard, that is, storage stability, mechanical properties, developing solution solubility and lithography in unexposed areas, and overall Excellent.

Based on the above-mentioned problems, the present inventors have repeatedly studied and experimented on a composition containing a polymer precursor from various viewpoints, such as formulations, blending, and preparation conditions for overall performance improvement. As a result, it was found that the hot alkali generating agent used in combination with the polymer precursor is not limited to a specific substance, thereby solving the above-mentioned problems, and completed the present invention. Specifically, the above-mentioned problems are solved by the following methods <1> and <2> to <23>.

<1> A photosensitive resin composition containing at least one type of hot alkali generation selected from the group consisting of a hot alkali generator represented by the following formula (B1) and a hot alkali generator represented by the formula (B2) Agent
At least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; and a photosensitizer,
The total content of the acid group and the acid generating group contained in the polymer precursor and the photosensitizer is 0.5 mmol / g or less.
[Chemical Formula 1]

In the formulae (B1) and (B2), R ¹ , R ^2, and R ³ are each independently an organic group, a halogen atom, or a hydrogen atom that does not have a tertiary amine structure; wherein R ¹ and R ^{2 are} not both A hydrogen atom and R ¹ , R ² and R ³ do not have a carboxyl group.
<2> The photosensitive resin composition according to the above <1>, wherein the alkali generation temperature of the thermal alkali generator is 120 ° C or higher and 200 ° C or lower.
<3> The photosensitive resin composition as described in said <1> or <2> whose pKa of the said thermal alkali generator is larger than 7.
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the polymer precursor includes a polyimide precursor.
<5> The photosensitive resin composition according to <4>, wherein the polyfluorene imide precursor is represented by the following formula (1);
[Chemical Formula 2]

In Formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or Monovalent organic group.
<6> The photosensitive resin composition according to any one of <1> to <5>, in which the molar absorption coefficient of the thermal alkali generator at a wavelength of 365 nm is 100 l / (mol · cm) or less.
<7> The photosensitive resin composition according to any one of <1> to <6>, wherein the hot base generator contains a hot base having a base whose pKa of the conjugate acid is 10 or more by heating. Agent.
<8> The photosensitive resin composition according to any one of <1> to <7>, wherein the photosensitive agent contains a photopolymerization initiator.
<9> The photosensitive resin composition according to any one of <1> to <8>, which is used for development using a developing solution containing an organic solvent of 90% by mass or more.
<10> The photosensitive resin composition according to any one of <1> to <9>, which is used for forming an interlayer insulating film for a redistribution layer.
<11> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <10>.
<12> The cured film according to <11>, wherein the film thickness is 1 to 30 μm.
<13> A laminated body comprising the hardened film according to <11> or <12> in two or more layers.
<14> A laminated body comprising a cured film of 3 to 7 or more layers according to <11> or <12>.
<15> The laminated body according to <13> or <14>, which has a metal layer between the cured films.
<16> A method for producing a cured film, comprising a film forming process of applying the photosensitive resin composition according to any one of <1> to <10> to a substrate to form a film.
<17> The method for producing a cured film according to <16>, which comprises an exposure process for exposing the film and a development process for developing the film.
<18> The method for producing a cured film according to <17>, wherein the developer used in the development includes an organic solvent of 90% by mass or more.
<19> The method for producing a cured film according to any one of <16> to <18>, including a process of heating the film at 80 to 450 ° C.
<20> A method for producing a laminated body, the method for producing a cured film according to any one of <16> to <19> a plurality of times.
<21> A semiconductor device comprising the cured film according to the item <11> or <12> or the multilayer body according to any one of the items <13> to <15>.
<22> A hot alkali generator, which is represented by the following formula (B1) or (B2);
[Chemical Formula 3]

In the formulae (B1) and (B2), R ¹ , R ^2, and R ³ are each independently an organic group, a halogen atom, or a hydrogen atom that does not have a tertiary amine structure, wherein R ¹ and R ^{2 are} not both A hydrogen atom and R ¹ , R ² and R ³ do not have a carboxyl group.
<23> The hot alkali generator according to <22>, which is a photosensitive resin composition for developing using a developer containing 90% by mass or more of an organic solvent.
[Inventive effect]

The photosensitive resin composition of the present invention is required to be used in an interlayer insulating film, a redistribution layer, and the like, and has excellent storage stability, mechanical characteristics, developer solution solubility in unexposed areas, and lithography in general. In addition, it is possible to provide a cured film, a laminated body, a method for producing a cured film, a method for producing a laminated body, a semiconductor device, and a thermal alkali generator using the photosensitive resin composition.

Hereinafter, the content of this invention is demonstrated in detail. In addition, in this specification, "~" means using the meaning which includes the numerical value described before and after 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.
Regarding the labels of the groups (atomic groups) in this specification, the unrecorded and unsubstituted labels include both those having no substituents and those having substituents. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) without a substituent, but also an alkyl group (substituted alkyl group) with a substituent.
As long as "exposure" is not specifically limited in this specification, in addition to exposure using light, drawing using a particle beam such as an electron beam and an ion beam is also included in the exposure. In addition, as the light used for the exposure, actinic rays such as bright line spectrum of a mercury lamp, excimer laser, extreme ultraviolet (EUV light), X-rays, and electron beams, or radiation are generally mentioned.
In this specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", and "(meth) acrylic" means "acrylic" and "methacrylic" Either or any one of them, and "(meth) acrylfluorenyl" means either or both of "acrylfluorenyl" and "methacrylfluorenyl".
In this specification, the term "process" is not only an independent process. Even if it cannot be clearly distinguished from other processes, as long as the expected effect of the process can be achieved, it is also included in this term.
In this specification, solid content means the mass percentage of the component other than a solvent with respect to the total mass of a composition. The temperature in this specification is 23 ° C unless otherwise specified.
In this specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined based on gel permeation chromatography (GPC measurement), and are defined as styrene conversion values. 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 protective column HZ-L, TSKgel Super HZM-M, and TSKgel Super can be used as the column HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise stated, the eluent was measured by THF (tetrahydrofuran). In addition, unless otherwise stated, the detection was performed using a wavelength 254 nm detector using UV rays (ultraviolet rays).

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 a hot alkali produced by the formula (B1) Agent and at least one type of hot alkali generator (hereinafter sometimes referred to as "specific hot alkali generator") in the group of hot alkali generator represented by formula (B2), selected from the group consisting of polyimide precursors And at least one polymer precursor and photosensitizer in the group of polybenzoxazole precursors, the total content of acid groups and acid generating groups contained in the polymer precursor and photosensitizer (hereinafter, sometimes This amount is referred to as "amount of acid groups and the like") is 0.5 mmol / g or less. By adopting this structure, a photosensitive resin composition which is excellent in storage stability, mechanical properties, developer solubility in unexposed areas, and lithography in general can be obtained. The reasons for solving the above problems include the following, including presumption.
By reducing the amount of acid groups and the like contained in the polymer precursor and the like in the photosensitive resin composition, it can be a material that can be developed more quickly in an organic solvent with a low polarity. A thermosetting film formed from a photosensitive resin composition that can be developed by an organic solvent generally has low hygroscopicity, and has excellent adhesion to a substrate and excellent device reliability. On the other hand, since the amount of acid groups and the like in the polymer precursor is small, if a basic compound is present in the composition, the cyclization reaction of the polymer precursor proceeds easily. As a result, storage stability is reduced. In the present invention, by using a specific thermal alkali generator having a structure that is substantially neutral before thermal decomposition and generates bases after thermal decomposition, it is possible to maintain heating based on a polymer precursor contained in the photosensitive resin composition. It has good curability and stably stores the photosensitive resin composition. In addition, it is preferable that the specific thermal alkali generator is nonionic, whereby the organic solvent developability of the resin composition can be made more excellent.

<Specific thermal alkali generator>
The photosensitive resin composition of this invention contains the hot alkali generator (specific hot alkali generator) represented by Formula (B1) or Formula (B2).
[Chemical Formula 4]

In the formulae (B1) and (B2), R ¹ , R ^2, and R ³ are each independently an organic group, a halogen atom, or a hydrogen atom that does not have a tertiary amine structure. However, R ¹ and R ² will not be hydrogen atoms at the same time. R ¹ , R ² and R ³ do not have a carboxyl group.
The tertiary amine structure in this specification refers to a structure in which all three bonding bonds of a trivalent nitrogen atom are covalently bonded to a carbon atom of a hydrocarbon system. Therefore, it is not limited when the carbon atom to be bonded is a carbon atom that is a carbonyl group, that is, when a carbon atom is formed together with a nitrogen atom. In the present invention, the organic group contained in the specific thermal alkali generator does not have a tertiary amine structure. When the resist solution is stored, the amination reaction of the polymer in the solution is suppressed, and the resist The liquid has excellent storage stability. In addition, each substituent does not have a carboxyl group, whereby the solubility in an organic solvent is excellent, and the developability is excellent.

In the formulae (B1) and (B2), at least one of R ¹ , R ^2, and R ³ preferably includes a cyclic structure, and more preferably, at least two of them include a cyclic structure. The cyclic structure may be any of a monocyclic ring and a fused ring, and a monocyclic ring or a fused ring of two monocyclic rings is preferred. A single ring is preferably 5 rings or 6 rings, and 6 rings is more preferred. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and a cyclohexane ring is more preferable. By including a cyclic structure in this way, the solubility in an organic solvent becomes high, and the basicity and boiling point of the amine generated by thermal decomposition are high, so that the amination reaction of the polymer is more effectively promoted.

More specifically, R ¹ and R ² are a hydrogen atom, an alkyl group (carbon number 1 to 24 is preferable, 2 to 18 is more preferable, 3 to 12 is more preferable), and an alkenyl group (carbon number 2 to 24) For the better, 2 to 18 is more preferable, 3 to 12 is more preferable), aryl (carbon number 6 to 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable) or aryl Alkyl (7 to 25 carbons is preferred, 7 to 19 is more preferred, and 7 to 12 is more preferred) is more preferred. These groups may have the substituent T mentioned later within the range which exhibits the effect of this invention. R ¹ and R ² may be bonded to each other to form a ring. As the formed ring, a 4- to 7-membered nitrogen-containing heterocyclic ring is preferred. R ¹ and R ² may be a chain having a substituent T in some cases, or may be a cyclic, linear or branched alkyl group (carbon numbers 1 to 24 are preferred, 2 to 18 are More preferably, 3-12 is further preferred) is more preferred, and a cycloalkyl group having a substituent T is sometimes preferred (carbon number of 3-24 is preferred, 3-18 is more preferred, 3-12 is further preferred) More preferably, a cyclohexyl group having a substituent T is further preferred.

Examples of R ³ include an alkyl group (carbon number 1 to 24 is preferred, 2 to 18 is more preferred, 3 to 12 is more preferred), and an aryl group (carbon number 6 to 22 is preferred, 6 to 18 is More preferably, 6 to 10 are further preferred), alkenyl (2 to 24 carbons are preferred, 2 to 12 are more preferred, 2 to 6 are more preferred), arylalkyl (7 to 23 carbons) For the better, 7 to 19 is more preferable, and 7 to 12 is more preferable.) Aralkenyl (carbon number of 8 to 24 is preferable, 8 to 20 is more preferable, and 8 to 16 is more preferable). Oxygen (carbon number 1 to 24 is preferred, 2 to 18 is more preferred, 3 to 12 is more preferred), aryloxy (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 6 12 is further preferred) or arylalkoxy (carbon number 7 to 23 is preferred, 7 to 19 is more preferred, 7 to 12 is further preferred). Among them, cycloalkyl (3 to 24 carbons is preferred, 3 to 18 is more preferred, and 3 to 12 are more preferred), arylalkenyl, and arylalkoxy are more preferred. R ³ may be further substituted with a substituent T within a range in which the effects of the present invention are exerted.

The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
[Chemical Formula 5]

In the formula, R ¹¹ and R ¹² and R ³¹ and R ³² are the same as R ¹ and R ² in the formula (B1), respectively.
R ¹³ is alkyl (carbon number 1 to 24 is preferred, 2 to 18 is more preferred, 3 to 12 is more preferred), alkenyl (carbon number 2 to 24 is preferred, 2 to 18 is more preferred, 3-12 is further preferred), aryl (6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), arylalkyl (7-23 is preferred) (7 to 19 is more preferable, and 7 to 12 is more preferable), and it may have a substituent T in a range where the effect of the present invention is exerted. Among them, R ¹³ is preferably an arylalkyl group.

R ³³ and R ³⁴ are each independently a hydrogen atom, an alkyl group (carbon number 1 to 12 is preferred, 1 to 8 is more preferred, 1 to 3 is more preferred), and an alkenyl group (carbon number 2 to 12 is more preferred) Better, 2 to 8 is more preferred, 2 to 3 is further preferred), aryl (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 10 is further preferred), arylalkyl (The carbon number is 7 to 23, 7 to 19 is more preferable, and 7 to 11 is more preferable.) A hydrogen atom is more preferable.

R ³⁵ is alkyl (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, 3 to 8 is more preferred), alkenyl (carbon number 2 to 12 is preferred, 2 to 12 is more preferred, 3 to 8 is more preferred), aryl (6 to 22 carbons is preferred, 6 to 18 is more preferred, 6 to 12 is more preferred), arylalkyl (7 to 23 carbons is preferred) 7 to 19 is more preferable, and 7 to 12 is more preferable), and aryl is more preferable.

It is also preferable that the compound represented by the formula (B1-1) is a compound represented by the formula (B1-1a).
[Chemical Formula 6]

Are as defined in the definition of R ¹¹ and the formula (B1-1) R ¹² is R ¹¹ and R ^{12 is.}
R ¹⁵ and R ¹⁶ are a hydrogen atom, an alkyl group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is more preferred), an alkenyl group (carbon number 2 to 12 is preferred, 2 ～ 6 is more preferable, 2 ～ 3 is more preferable), aryl group (carbon number is 6-22 is preferable, 6-18 is more preferable, 6-10 is more preferable), arylalkyl group (carbon number 7 to 23 are preferred, 7 to 19 are more preferred, and 7 to 11 are further preferred), and a hydrogen atom or a methyl group is more preferred.
R ¹⁷ is an alkyl group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, 3 to 8 is more preferred), alkenyl (carbon number 2 to 12 is preferred, 2 to 12 is more preferred, 3 to 8 is more preferred), aryl (6 to 22 carbons is preferred, 6 to 18 is more preferred, 6 to 12 is more preferred), arylalkyl (7 to 23 carbons is preferred) 7 to 19 is more preferable, and 7 to 12 is more preferable. Among them, aryl is more preferable.

The molecular weight of the specific hot alkali generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. As a lower limit, 100 or more is preferable, 200 or more is more preferable, and 300 or more is more preferable. The molecular weight of the specific thermal alkali generator is in the above range, whereby the solubility in an organic solvent is excellent, and the developability is not deteriorated. In addition, the decomposition products after thermal decomposition are unlikely to remain in the thermosetting film, and the reliability of the device is not impaired.

The alkali generating temperature of the specific hot alkali generator is preferably 120 ° C or higher and 200 ° C or lower, more preferably 130 ° C or higher and 180 ° C or lower, and more preferably 140 ° C or higher and 170 ° C or lower. By controlling this temperature, it is possible to more reliably promote the hardening of the cyclization based on the polymer precursor. The alkali generation temperature was measured in accordance with the description in Examples described later.
The difference between the base generation temperature of the specific hot alkali generator and the maximum temperature when the polymer precursor is cyclized and heated (maximum temperature-base generation temperature) is preferably 5 ° C or higher and 100 ° C or lower, 10 The temperature is more preferably from 80 ° C to 80 ° C, and more preferably from 15 ° C to 60 ° C. Depending on whether it is within this range, the mechanical properties are further improved.

The pKa of the conjugate acid of a specific hot base generator generated by heating is preferably 10 or more, more preferably 11 or more, and more preferably 12 or more. The upper limit is actually 15 or less. This basicity is strong, whereby the curability of the polymer precursor is more effective.

The pKa of the specific hot alkali generator is preferably greater than 7, more preferably greater than 8, and more preferably greater than 9. The upper limit is actually 12 or less. The pKa is set to the above range, whereby the basicity of the hot alkali generator is weakened during storage, and the polymer precursor is not hardened, and the stability thereof is further increased.
It is preferable that the specific thermal alkali generator contains a neutral molecule. Neutral means that the electric property is neutral, and a base which is not an anion or formed by a cation is more preferable. Each atom in the molecule is connected by covalent bonding, and a compound having a total electricity price of zero is preferable.
The measurement method of pKa was measured according to the method described in the Example mentioned later.

The specific thermal alkali generator contained in the photosensitive resin composition used in the present invention has a molar absorption coefficient of the thermal alkali generator at a wavelength of 365 nm of preferably 500 l / (mol • cm) or less, and 300 l / (Mol · cm) or less is more preferable, and 100 l / (mol · cm) or less is more preferable. The lower limit is actually 50 l / (mol · cm) or more. UV-2600 (manufactured by Shimadzu Corporation) was used as a measuring device for the Moire absorption coefficient. The measurement was performed on three samples, and a value obtained by arithmetically averaging the results was used. The other contents follow the details described in JISK0115: 2004 (Japanese Industrial Standard). In the present invention, as described above, a hot alkali generator that suppresses absorption of light (i-rays) at a wavelength of 365 nm is preferably used. Thereby, it is possible to achieve more excellent mechanical characteristics without deteriorating the light transmittance and photolithography during exposure.

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 more preferred), hydroxyalkyl (1 to 12 carbons is Preferably, 1 to 6 are more preferred, 1 to 3 are further preferred), aryl (6 to 22 carbons are preferred, 6 to 18 are more preferred, 6 to 10 are further preferred), heteroaryl (The number of carbon atoms is preferably from 1 to 12, more preferably from 1 to 6, and even more preferably from 1 to 4; examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom), and an arylalkyl group (with a carbon number of from 7 to 7) 23 is better, 7 to 19 is better, 7 to 11 is more preferred), hydroxyl group, primary or secondary amine group (carbon number may be 0 to 24, 0 to 12, or 0 to 12) 6), quaternary ammonium group (carbon number can be 3-24, 3-12 can also be 3-6), thiol group, fluorenyl group (carbon number 2-12 is preferred, 2-6 For better, 2 ~ 3 is especially good), alkoxy (carbon number is 2 ~ 12 is better, 2 ~ 6 is more preferable, 2 ~ 3 is especially good), Fangyang (Carbon number 7 to 23 is preferred, 7 to 19 is more preferred, 7 to 11 is particularly preferred), aryloxy (carbon number 7 to 23 is preferred, 7 to 19 is more preferred, 7 to 11 is particularly preferred (Better), (meth) acrylfluorenyl, (meth) acrylfluorenyloxy, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), pendant oxygen group (= O), imide group ( It may be = NH), alkylene (= C (R ^N ) ₂ ), and the like. A hetero atom may be interposed between the alkylene chain of the substituent T. The alkyl group, alkenyl group, aryl group, and arylalkyl group which the substituent T has may be further substituted with another substituent.

R ^N is a hydrogen atom or an organic group. The organic group is an alkyl group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, and 1 to 3 is more preferred), and an aryl group (carbon number 6 to 22 is preferred, 6 to 18 is More 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 more preferred) is more preferred.

Examples of the specific thermal alkali generator include the compounds shown in the examples.

In the photosensitive resin composition, the content of the specific thermal alkali generator is preferably 0.1% by mass or more in the solid content, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more. The upper limit is preferably 5 mass% or less, more preferably 4 mass% or less, and even more preferably 3 mass% or less.
With respect to 100 parts by mass of the polymer precursor, 0.1 parts by mass or more is preferable, 0.3 parts by mass or more is more preferable, and 0.5 parts by mass or more is more preferable. The upper limit is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less.
By setting the amount to the above range, it is possible to sufficiently exert the function of a specific thermal alkali generator, and to suppress the amount of residue of the thermally decomposed matter to such an extent that it does not affect the reliability of the device, and is therefore preferred.
The specific thermal alkali generator may be used singly or in combination. When plural types are used, the total amount is within the above range.
The specific thermal alkali generator may be used in combination with other thermal alkali generators or not.
As an embodiment of the present invention, the content of the specific thermal alkali generator in the thermal alkali generator contained in the photosensitive resin composition of the present invention is preferably 50% by mass or more, and more preferably 80% by mass or more. 90% by mass or more is further preferred, 95% by mass or more is further preferred, and 99% by mass or more is further preferred.

＜ Polymer precursor ＞
The photosensitive resin composition of the present invention contains at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. The total content of the acid group and the acid generating group contained in the polymer precursor is preferably 0.5 mmol / g or less. As the polymer precursor, a polyimide precursor is more preferable, and a polyimide precursor containing a structural unit represented by the following formula (1) is 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 7]

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. It is preferable that -C (= O) -A ¹ -R ¹¹⁴ and -C (= O) -A ² -R ¹¹³ are groups having no acid group and acid generating group, respectively.

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 containing 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 the like A combination group is preferred, and an aromatic group having 6 to 20 carbon atoms is more preferred.
It is preferred that R ¹¹¹ is derived from a diamine. Examples of the diamine used in the production of the polyfluorene imide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. The diamine may be used alone or in combination of two or more.
Specifically, the diamine includes a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination including these. The group is more preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of the aromatic group include the following aromatic groups.

[Chemical Formula 8]

In the formula, A is a single bond or is selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which can be substituted with a fluorine atom, -O-, -C (= O)-, -S-, -S (= O) _2- , -NHCO- and groups in combinations thereof are preferred, single bond or selected from alkylene groups of 1 to 3 carbon atoms, -O-, -C (= O)-, which can be substituted with 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} - 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; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4, 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4, 4'-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'-diamine Benzene, 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'-di Amino p-terphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-amine Phenoxy) phenyl] fluorene, bis [4- (2-aminophenoxy) phenyl] fluorene, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis ( 4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylphosphonium, 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'-diamine Octafluorobiphenyl, 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'-tetraaminodi Phenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4- Aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylfluorene, 3,3 ', 5,5'-tetramethyl-4,4'-diamine Diphenylmethane, ethyl 2- (3 ', 5'-diaminobenzyloxy) acrylate, 2,4-diaminocumene and 2,5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis ( 3-aminopropyl) tetramethyldisilaxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, di Aminobenzidine aniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) deca Pentane, 1,7-bis (4-aminophenyl) tetradefluorofluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2- Bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoro Propane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino-2-trifluoro Methylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethyl) Phenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylphosphonium, 4,4'-bis (3-amino-5-tri Fluoromethylphenoxy) diphenylphosphonium, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ', 5, 5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2 ', 5,5 At least one diamine among ', 6,6'-hexafluorobenzidine and 4,4'-diamino tetraphenyl.

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

[Chemical Formula 9]

In addition, as a preferable example, a diamine having at least two or more alkylene glycol units in the main chain may be mentioned. A diamine containing two or more of ethylene glycol chains and propylene glycol chains in one molecule, or a diamine, 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), 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 10]

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 a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (= O)-, -S-, -S (= O) _2- , -NHCO- And groups selected from these combinations. The definition of the preferred range is the same as the definition of A in the above AR-8.

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 11]

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; methyl, fluoromethyl, difluoromethyl, or trifluoromethyl. base.
Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and 1 to 10 carbon atoms (preferably 1 carbon atom) ~ 6) Fluorinated alkyl and the like.
[Chemical Formula 12]

R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, fluoromethyl, difluoromethyl, or trifluoromethyl.
As a diamine compound imparting a structure of the formula (51) or (61). Examples 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 of these may be used, or two or more of them 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 13]

The definition of R ^{112 is} the same as the definition of A in the above-mentioned AR-8, 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 removing the acid dianhydride group from the tetracarboxylic dianhydride. Tetracarboxylic dianhydride may be used alone, or two or more of them may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
[Chemical Formula 14]

R ¹¹⁵ represents a tetravalent organic group. The same definition as R ¹¹⁵ R ¹¹⁵ are as defined in formula (1).

As specific examples of tetracarboxylic dianhydride, selected from the group consisting of pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-Diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonium tetracarboxylic dianhydride, 3,3 ', 4,4'-dibenzoyl Ketotetracarboxylic 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 2,2-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-di Phenyl) ethane dianhydride, pyromellitic dianhydride, and alkyl derivatives of 1 to 6 carbon and alkoxy derivatives of 1 to 6 carbon At least one of them.

Moreover, as a preferable example, tetracarboxylic dianhydride (DAA-1)-(DAA-5) shown below are mentioned.
[Chemical Formula 15]

R ¹¹³ and R ¹¹⁴ in the formula (1) each independently represent a hydrogen atom or a monovalent organic group. At least one of R ¹¹³ and R ¹¹⁴ preferably contains a radical polymerizable group, and more preferably two contains a radical polymerizable group. The radical polymerizable group is a group capable of performing a cross-linking reaction by the action of a radical, and as a preferable example, a group having an ethylenically unsaturated bond can be mentioned.
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 16]

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 are 1 to 12 are preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred). (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.
Particularly preferably, R ²⁰⁰ is methyl, and R ²⁰¹ is ethylene.

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 number of carbon atoms of the alkyl group is preferably 1 to 30 (3 or more in the case of a ring). The alkyl group may be any of linear, branched, and cyclic. Examples of linear or branched alkyl include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl , Octadecyl, isopropyl, isobutyl, second butyl, third 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, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and fluorene. Fluorenyl, dicyclohexyl and pinenyl. Among these, cyclohexyl is the most preferable from the viewpoint of achieving high sensitivity. Moreover, as an alkyl group substituted by the aromatic group, the linear alkyl group substituted by the aromatic group mentioned later is preferable.
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 a lead ring. , Fluorene ring, fused pentaphenyl ring, acenaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, chrysene ring, bitriphenylene ring, fluorene ring, biphenyl ring, etc. have aromatic Group of hydrocarbon rings.
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, and pyridazine Ring, three wells ring, indazine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinine Oxoline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, morphine ring, acridine ring, phenanthroline ring, thion ring, chromene ring, koushankou Xanthene ring, phenoxathiine ring, phenothiazine ring or phenazine ring have aromatic heterocyclic groups.

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 less. The upper limit is not specified, but it is actually 50% by mass or less.

In addition, for the purpose of improving adhesion to a substrate, an aliphatic group having a siloxane structure and a constitutional 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 constituent unit represented by the formula (1) is preferably a constituent unit represented by the formula (1-A).
[Chemical Formula 17]

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

In the polyimide precursor, the structural unit represented by the formula (1) may be one type, or two or more types. Moreover, the structural isomer of the structural unit represented by Formula (1) may be included. In addition, the polyfluorene imide precursor may include other types of constituent units in addition to the constituent units 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 the total constituent units are exemplified by the formula (1). Polyimide precursors that make up the unit. The upper limit is actually 100 mol% or less.

The weight average molecular weight (Mw) of the polyfluorene imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still 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. It is preferably obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting the dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
In the method for producing a polyimide precursor, an organic solvent is preferably used during the reaction. The organic solvent may be one kind, or two or more kinds.
The organic solvent can be appropriately set depending on the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

When manufacturing a polyimide precursor, a process including precipitation of solids is preferred. Specifically, the polyfluorene imide precursor in the reaction solution is precipitated in water and dissolved in a solvent capable of dissolving the polyfluorene imide precursor, such as tetrahydrofuran, so that solids can be precipitated.

＜ Polybenzoxazole precursor ＞＞
The polybenzoxazole precursor preferably contains a structural unit represented by the following formula (2).
[Chemical Formula 18]

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. As the divalent organic group, an aliphatic group (carbon number 1 to 24 is preferable, 1 to 12 is more preferable, and 1 to 6 is particularly preferable) and an aromatic group (carbon number 6 to 22 is more preferable) 6 to 14 are more preferred, and 6 to 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 (3), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, its definition is the same as that of R ¹¹⁵ in the formula (1), and its preferred range is also the same. R ¹²² is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and their definitions are the same as those of R ¹¹³ and R ¹¹⁴ in the above formula (1), and their preferred ranges are also the same. It is preferable that -OR ¹²⁴ and -OR ¹²³ are a group which does not have an acid group and an acid generating group, respectively.

The polybenzoxazole precursor may include other types of constituent units in addition to the constituent units of the formula (2).
In view of being able to suppress the warpage of the cured film accompanying the ring closure, it is preferable that the precursor contains a diamine residue represented by the following formula (SL) as another kind of constituent unit.

[Chemical Formula 19]

Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R ^2s is 1 to 10 carbon atoms. Hydrocarbyl (preferably 1 to 6 carbons, more preferably 1 to 3 carbons), and 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 6 to 10 carbons), and the remainder being hydrogen atoms or carbons 1 to 30 (preferably 1 to 18 carbons, more preferably 1 to 12 carbons) Organic groups having 1 to 6 carbon atoms may be the same as or different from each other. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z portion, the a structure is preferably 5 to 95 mole%, the b structure is 95 to 5 mole%, and a + b is 100 mole%.

In the formula (SL), examples of preferred Z include those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by gel permeation chromatography generally used. By setting the molecular weight to the above range, it is possible to have both the effect of reducing the coefficient of elasticity after dehydration and ring closure of the polybenzoxazole precursor, the effect of suppressing warpage, and the effect of improving solubility.

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 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 with respect to 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 preferably 99.5% by mass or less, more preferably 99% by mass or less, and more preferably 98% by mass or less with respect to the total solid content of the composition. It is preferable that the content is 95 mass% or less, and the content is 95 mass% or less.
The photosensitive resin composition of the present invention may include one kind of polymer precursor, or may include two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

<Solvent>
The photosensitive resin composition of the present invention preferably contains a solvent. The solvent can be any known one. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, fluorenes, and amidines.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. , Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, alkyl Ethoxyacetate, butyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), 3-alkoxypropanoic acid alkyl esters (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., 2-alkane Methyloxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)) Methyl 2-alkoxy-2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethyl Ethoxy-2-methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl 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 B. Acid esters, 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.
As the amines, preferred are N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-di Methylformamide and the like.

Regarding the solvent, it is also preferable to mix two or more forms from the viewpoint of improving the coating surface shape.
In the present invention, it includes 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 both 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 content of the solvent may be adjusted according to 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, the total is preferably in the above range.

<Photosensitizer>
In the present invention, a photosensitive agent is contained in the photosensitive resin composition. The total content of the acid group and the acid generating group contained in the photosensitizer is preferably 0.5 mmol / g or less. Examples of the photosensitizer include a photopolymerization initiator, a photohardening accelerator, and a sensitizing dye.
In the present invention, the total amount of the photosensitive agent is preferably 1 to 10% by mass of the photosensitive resin composition. The photosensitizer is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80 to 100% by mass of a photopolymerization initiator.

<< Photoinitiator >>
The photosensitive resin composition used in the present invention may contain a 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 photoradical polymerization initiator that is sensitive to light from the ultraviolet region to the visible region is preferred. In addition, it may be an active agent that generates some action with a photo-excited sensitizer and generates an active radical.
The photoradical polymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 moles in a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of a compound can be measured by a well-known method. For example, it is preferable to perform measurement at a concentration of 0.01 g / L by using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian Corporation) and using an ethyl acetate solvent.

The photosensitive resin composition contains a photoradical polymerization initiator, and 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. Because it is hardened by free radicals, the solubility in the light-irradiated portion can be reduced. Therefore, for example, there is an advantage that, by exposing the photosensitive resin composition layer through a light mask having a pattern that shields only the electrode portion, regions having different solubility can be easily produced according to the pattern of the electrode.

As the photoradical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triple well skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), fluorenyl phosphine compounds such as fluorenylphosphine oxide, and hexaarylbisimidazole Oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo-based compounds, azide compounds, and Metal compounds, organic boron compounds, iron aromatic hydrocarbon complexes, and the like. For details of these, 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 is exemplified, and the content is incorporated into this 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 (trade 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 with a maximum absorption wavelength matching a wavelength light source such as 365 nm or 405 nm can also be used.
Examples of the fluorenylphosphine-based initiator include 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide and the like. In addition, IRGACURE-819 or IRGACURE-TPO (trade name: both manufactured by BASF) can be used as commercially available products.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

As a photoradical polymerization initiator, an oxime compound is more preferably mentioned. By using an oxime compound, exposure latitude can be further effectively improved. Among the oxime compounds, exposure latitude (exposure margin) is wide, and it also functions as a hardening accelerator, which is particularly preferable.
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 examples of the oxime compound include compounds having the following structure, 3-benzyloxyiminobutane-2-one, 3-ethoxyiminobutane-2-one, and 3 -Propanyloxyiminobutane-2-one, 2-Ethyloxyiminopentane-3-one, 2-Ethyloxyimino-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 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 20]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, JP 2012-014052) Photo radical polymerization initiator 2) described in the publication. In addition, TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), ADEKAARKLS NCI-831, and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. Moreover, DFI-091 (made by DAITO CHEMIX Co., Ltd.) can also be used.
Furthermore, 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 having a thioaryl group shown in Japanese Patent Application Laid-Open No. 2009-191061. Compounds etc.

From the standpoint of exposure sensitivity, the photoradical polymerization initiator is selected from the group consisting of trihalomethyl triple well compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, and fluorenyl groups. Phosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triarylimidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadienyl group -Benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.
More preferred photoradical polymerization initiators are trihalomethyl triple well compounds, α-amino ketone compounds, fluorenyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, oniums Salt compound, benzophenone compound, acetophenone compound, selected from the group consisting of trihalomethyl three well compounds, α-amino ketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds At least one of the compounds is further preferred, and the use of a metallocene compound or an oxime compound is further preferred, and an oxime compound is further preferred.
In addition, as the photoradical polymerization initiator, benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), and other N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, Aromatic ketones such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-acetone-1, alkyl anthraquinones, and quinones formed by condensing an aromatic ring, Benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyldimethylketal, and the like. A compound represented by the following formula (I) can also be used.
[Chemical Formula 21]

In the 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, Carbon interrupted by an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, cyclopentyl, cyclohexyl, an alkenyl group having 2 to 12 carbon atoms, and one or more oxygen atoms At least one substituted phenyl or biphenyl group of an alkyl group of 2 to 18 and an alkyl group of 1 to 4 carbons, and R ^I01 is a group represented by formula (II), or is the same as R ^I00 The groups, R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.
[Chemical Formula 22]

In the formula, R ^I05 to R ^I07 are the same 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 the photopolymerization initiator is contained, 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 only one kind, or may contain two or more kinds. When two or more photopolymerization initiators are contained, the total amount is preferably in the above range.

＜＜ Light hardening accelerator ＞＞
The photosensitive resin composition used in the present invention may contain a photohardening accelerator. The photo-hardening accelerator in the present invention is preferably a person that generates bases by photoexposure (photobase generator). It does not show activity under normal conditions of normal temperature and normal pressure, but if it is irradiated with electromagnetic waves as an external stimulus, Those that produce bases (basic substances) are particularly preferred. The base generated by exposure serves as a catalyst when the polymer precursor is hardened by heating, so it can be preferably used.
In this invention, a well-known thing can be used as a photohardening accelerator. Examples include ionic compounds such as migrating metal compound complexes, those having a structure such as an ammonium salt, those that are potentialized by the formation of a base with a hydrazone moiety and a carboxylic acid, and ionic compounds that are neutralized by forming a base with a base component, Non-ionic compounds in which a base component is potentially formed by a urethane bond, an oxime bond, or the like, such as a urethane derivative, an oxime ester derivative, or a sulfonium compound.

Examples of the photohardening accelerator of the present invention include a photohardening 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 A photohardening accelerator having a urethane structure as disclosed in Japanese Patent Application Publication No. 2006-189591 and Japanese Patent Application Publication No. 2008-247747, and disclosed in Japanese Patent Application Publication No. 2007-249013 and Japanese Patent Application Publication No. 2008-003581. Photocuring accelerators having such an oxime structure and aminoformamoxime structure are not limited thereto, and other known structures of photocuring accelerators can be used.

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 paragraphs 0022 to 0069 of Japanese Patent Laid-Open No. 2013-194205. Examples of the compounds described, 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.

As commercial 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 within the above range.

＜< Sensitization Pigment >＞
The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electronically excited state. The sensitized dye in an electronically excited state is brought into contact with a thermal hardening accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, and the like, thereby causing the effects of electron transfer, energy transfer, and heat generation. Thereby, the thermal curing accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator are chemically changed and decomposed. For details of the sensitizing dye, refer to the descriptions in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and incorporate the contents 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 more preferably 0.1 to 15% by mass relative to the total solid content of the photosensitive resin composition of the present invention. Preferably, 0.5 to 10% by mass is further preferred. The sensitizing dye may be used singly or in combination of two or more kinds.

＜ Thermal radical polymerization initiator ＞
The photosensitive resin composition of this invention can contain a thermal radical polymerization initiator in the range which does not deviate from the meaning of this invention.
A thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and starts or promotes a polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymer precursor can be polymerized together with the cyclization of the polymer precursor, and thus a higher degree of 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 the thermal radical polymerization initiator is contained, the content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 5 to the total solid content of the photosensitive resin composition of the present invention. -15% by 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.

<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) acrylfluorenyl, and allyl. The radical polymerizable group is preferably a (meth) acrylfluorenyl group.

The number of radically polymerizable groups in the radically polymerizable compound may be one, or may be two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and has three or more For the 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 radically polymerizable compound is preferably 100 or more.

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

Specific examples of the radical polymerizable compound include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), an ester thereof, and amines. It is preferably an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, and an amine of an unsaturated carboxylic acid and a polyamine compound. In addition, it is also preferable to use an addition reaction product of an unsaturated carboxylic acid ester or amidoamine having an affinity substituent such as a hydroxyl group, an amine group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and Dehydration fused reactants of functional or polyfunctional carboxylic acids and the like. In addition, unsaturated carboxylic acid esters or amidoamines having an electrophilic substituent such as an isocyanate group or an epoxy group, and an addition reaction product of a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group or toluene Substituted reactants of unsaturated carboxylic acid esters or amidoamines having detachable substituents such as sulfonyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. As another example, instead of the unsaturated carboxylic acid, a compound group substituted with a vinyl benzene derivative such as unsaturated phosphonic acid, styrene, vinyl ether, allyl ether, or the like can be used. As a specific example, the descriptions in paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357 can be referred to, and the contents are incorporated into this specification.

A compound having a boiling point of 100 ° C. or higher under normal pressure is also preferred as the radical polymerizable monomer. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, and neopentaerythritol tri ( (Meth) acrylates, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, hexanediol (methyl ) Acrylates, trimethylolpropane tris (propylene ethoxypropyl) ether, tris (propylene ethoxyethyl) isotricyanate, glycerol or trimethylolethane, etc. in polyfunctional alcohols Compounds that are (meth) acrylated after addition of ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. 51-037193 The (meth) acrylic acid urethanes described therein, the polyester acrylates described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490 Many epoxy acrylates are the reaction products of epoxy resin and (meth) acrylic acid. Acrylate or methacrylate can, and mixtures of these. In addition, the compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also suitable. Furthermore, polyfunctional (meth) acrylate etc. obtained by making a polyfunctional carboxylic acid react with the compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth) acrylate, etc. are mentioned.
Moreover, as a preferable radically polymerizable compound other than the above, it is also possible to use a ring having a ring described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent No. 4364216, and the like. A compound or a cardo resin having two or more groups containing an ethylenically unsaturated bond.
Furthermore, 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 the specific unsaturated compounds described in Japanese Unexamined Patent Publication No. 2-040336 can be cited. A vinylphosphonic acid 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. Furthermore, the "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used as the introducer of the photopolymerizable monomer and oligomer.

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

In addition, the following compounds described in Japanese Patent Application Laid-Open No. 10-062986 as formulas (1) and (2) together with specific examples thereof can also be used as radical polymerizable compounds. The compounds are added to polyfunctional alcohols. Compounds formed by (meth) acrylic acid after forming ethylene oxide or propylene oxide.

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

As the radically 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 as a commercial product) -310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and such (meth) acrylfluorenyl groups are preferably bonded via an ethylene glycol residue or a propylene glycol residue. It is also possible to use their oligo type.

As a commercially available product of a radically polymerizable compound, for example, SR-494, which is a tetrafunctional acrylate having four ethoxyl chains, and difunctional, which has four vinyloxy chains, manufactured by Sartomer Company, Inc. SR-209, 231, 239 made by Sartomer Company, Inc. of methyl acrylate, DPCA-60, a 6-functional acrylate having 6 pentyloxy chains, and 3 different isopropyl acrylates, manufactured by Nippon Kayaku Co., Ltd. TPA-330 trifunctional acrylate with extended butoxy chain, urethane oligomer UAS-10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T , UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), Etc.

As the radical polymerizable compound, there are those described in Japanese Patent Application Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Application No. 2-032293, and Japanese Patent Application No. 2-016765. Urethane acrylates are 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. Oxyethane-based urethane compounds are also preferred. Further, as the radical polymerizable compound, it is also possible to use an amine group in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 1-105238. Structure or sulfide structure.

From the viewpoint of suppressing warpage due to the control of the elastic coefficient 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, (Meth) acrylic acid such as N-hydroxymethyl (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. Derivatives, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate Allyl compounds such as esters. 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 compound other than the above radical polymerizable compound >>
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 radical polymerizable compound include compounds having a methylol group, an alkoxymethyl group, or a fluorenylmethyl group; an epoxy compound; an oxetane compound; and a benzopyrene compound.

(Compounds with methylol, alkoxymethyl, or trimethylol)
As the compound having a methylol group, an alkoxymethyl group, or a fluorenylmethyl group, a compound represented by the following formula (AM1), (AM4), or (AM5) is preferable.

[Chemical Formula 23]

(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 24]

(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 25]

(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 hydrogen An 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 trade 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 trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX -290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2, 6-dimethoxymethyl-p-cresol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc.

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 trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.).

(Epoxy compounds (compounds having epoxy groups))
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy undergoes a crosslinking reaction based on a temperature of 200 ° C or lower, and it is difficult to cause film shrinkage because it does not cause a dehydration reaction from crosslinking. Therefore, by containing an epoxy compound, low-temperature hardening and warping of a composition can be suppressed effectively.

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

Examples of the epoxy compound include polyalkylene glycol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Epoxy group-containing epoxy resins such as alkyl glycol type epoxy resins and polymethyl (glycidyloxypropyl) siloxanes are not limited thereto. 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, EPICLONEXA-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 names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above are trade names, manufactured by ADEKA CORPORATION), and the like. 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-hydroxymethoxybutane, 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) manufactured by TOAGOSEI CO., LTD. Can be preferably used, and these can be used alone or in combination. More than two.

(Benzo-Horiguchi compounds (compounds with a benzoxazolyl group))
The benzo-oral-well compound is preferred because it is hardened due to a cross-linking reaction derived from a ring-opening addition reaction, which does not generate outgassing when it hardens, and further reduces thermal contraction and suppresses warping.

Preferable examples of the benzo-orthodontic well compound include Ba-type benzo-orthodontic well, Bm-type benzo-orthodontic well (the above is a trade name, manufactured by Shikoku Chemicals Corporation), and benzo-ortho-polystyrene resin. Yankou well adducts, novolac-type dihydrobenzo hydrazone well compounds. These may 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 further 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 at the same time, the total amount is preferably 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 transfer of metal ions 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, tetrazole Ring, pyridine ring, pyridazine ring, pyrimidine ring, pyracene ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, three well rings), with sulfur Urea and mercapto 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.

Moreover, an ion trapping agent that captures anions such as halogen ions 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 26]

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 further preferred.
The migration inhibitor may be only one, or may be two or more. When there are two or more kinds of migration inhibitors, it is preferable that the total thereof is within 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-third-butyl-p-cresol, catechol, p-third-butylcatechol, 1,4 benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-third butylphenol), 2,2-'methylenebis (4-methyl 6-Third-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitroso diphenylamine, N-phenylnaphthylamine, ethylenediamine Tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-third-butyl-4-methylphenol, 5-nitroso-8-hydroxyquine Porphyrin, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamine) phenol, N- Nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3,5-third 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 also be used.
[Chemical Formula 27]

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 more preferably 0.02 to 3% by mass relative to the total solid content of the photosensitive resin composition of the present invention. 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 adhesion improver ＞
The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for an electrode, wiring, or the like. Examples of the metal adhesion improving agent include a silane coupling agent.

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 Compounds described in paragraphs 0060 to 0061 of 2014-191252, compounds described in paragraphs 0045 to 0052 of JP 2014-041264, and 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. Moreover, it is also preferable to use the following compounds as a silane coupling agent. In the following formula, Et represents an ethyl group.
[Chemical Formula 28]

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

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymer precursor. By making it more than the said lower limit value, the adhesiveness of the hardened film after a hardening process and a metal layer becomes favorable, and by making it below the said upper limit value, the heat resistance and mechanical characteristics of the hardened film after a hardening process become favorable. The metal adhesion improver may be only one kind, or two or more kinds. When two or more kinds are used, it is preferable that the total is within the above range.

＜ Other additives ＞
As long as the photosensitive resin composition of the present invention does not impair the effects of the present invention, various additives such as a chain transfer agent, a surfactant, a higher fatty acid derivative, an inorganic particle, a hardener, and a hardening catalyst can be added as needed. , Fillers, antioxidants, ultraviolet absorbers, aggregation 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.

＜〈 chain transfer agent 〉＞
The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the 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 compound group having SH, PH, SiH, and GeH in a molecule is used. The radicals are generated by supplying hydrogen to low-active radicals, or by deprotonation after oxidation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles) can be preferably used. Class, etc.).

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 more preferably 1 to 10% by mass relative to the total solid content of the photosensitive resin composition of the present invention. 1 to 5 mass% is more preferred. 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 range is preferably the above range.

＜ Interfacial Active Agents ＞＞
From the viewpoint of improving 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 silicon-based surfactant can be used. The following surfactants are also preferred.
[Chemical Formula 29]

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

<< Higher Fatty Acid Derivatives >>
In order to prevent polymerization caused by oxygen, the photosensitive resin composition of the present invention may add a higher fatty acid derivative such as behenic acid or ammonium behenate to locally exist during the drying process after coating. On 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, or may be two or more. When there are two or more types of higher fatty acid derivatives, the total range is preferably the above range.

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

From the standpoint of insulation, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and less than 0.5 mass ppm. Further preferred. 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 that are 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 can be selected. The raw materials of the photosensitive resin composition are filtered by a filter, and the inside of the apparatus is lined with polytetrafluoroethylene, and distillation is performed under conditions that minimize contamination.

Considering the use as a semiconductor material, the photosensitive resin composition of the present invention has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and further less than 200 mass ppm from the viewpoint of wiring corrosion. Better. Among them, the presence of halogen ions is 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 of the photosensitive resin composition of the present invention, a conventionally known storage container can be used. In addition, as a storage container, for the purpose of suppressing impurities from being mixed into the raw materials or the composition, it is also preferable to use a multi-layer bottle composed of six types of six-layer resin and a six-layer resin bottle having 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.
In addition, for the purpose of removing foreign matters such as garbage and particles in the composition, it is preferable to perform filtration using a filter. 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 polytetrafluoroethylene, polyethylene or nylon. The filter may be previously cleaned with an organic solvent. In the filtration process of the filter, a plurality of filters can be used in parallel or in series. When using multiple filters, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be circular filtering. In addition, filtration may be performed after pressurization. When filtering after pressurization, the pressure for pressurizing is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine a filter and an impurity removal treatment using an adsorbent. 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.

In the present invention, the total content of acid groups and acid generating groups (amount of acid groups and the like [ΣAc]) contained in the polymer precursor and the photosensitizer in the photosensitive resin composition is 0.5 mmol / g or less. The acid group in this specification is a group having 4 or less pKa, and carboxylic acids and sulfonic acids are exemplified. The acid generating group in this specification refers to a group that can generate an acid group in a liquid of the photosensitive resin composition or in a film obtained from the photosensitive resin composition by a process using a photosensitive resin composition such as heating or exposure. For example, the above-mentioned acid group is protected by desorption and the like.
The amount of acid groups and the like in the photosensitive resin composition in the present invention is more preferably 0.4 mmol / g or less, more preferably 0.3 mmol / g or less, and still more preferably 0.2 mmol / g or less. The lower limit value is actually 0.01 mmol / g or more. In the present invention, since the amount of the acid groups and the like is suppressed to be low, it is possible to perform good development with an organic solvent without using an alkali solution. In addition, it is estimated that the resin composition in the above-mentioned Patent Document 1 is alkali-soluble, and therefore the amount of acid groups such as (for example, [0064]), resin, and the like exceeds 2.0 mmol / g.

<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 be 1 μm or more. The upper limit value can be set to 100 μm or less, and can also be set to 30 μm or less.

Two or more layers of the cured film of the present invention may be used as the laminate, and further, 3 to 7 layers may be used as the laminate. It is preferable that the laminated body in the cured film of the present invention having two or more layers has a metal layer between the cured films. Such a metal layer can be preferably used as a metal wiring such as a redistribution layer.

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

The manufacturing method of the cured film of this invention contains the case where the photosensitive resin composition of this invention is used. Specifically, it includes a film forming process (a layered layer forming process) in which the photosensitive resin composition of the present invention is applied to a substrate to form a film, and a photosensitive resin composition in a layered form is in a range of 80 to 450. Heating process at ℃ (preferably 80-350 ℃). The method for manufacturing the cured film may be a manufacturing method having the following processes: an exposure process for exposing the film after the film formation process (layer formation process); a photosensitive resin composition layer (film, That is, the resin layer) is a developing process for developing. After the development, a heating process including heating (preferably heating at 80 to 450 ° C.) (more preferably 80 to 350 ° C.) is performed, so that the exposed resin layer can be further hardened. In addition, as described above, when the photosensitive resin composition is used, the composition is hardened by exposure in advance, and then desired processing (for example, the following lamination) is performed as necessary, whereby it can be 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. According to the manufacturing method of the laminated body of the present invention, according to the above-mentioned method for manufacturing a cured film, after the cured film is formed, the film forming process (layer forming process) and the heating process of the photosensitive resin composition are further performed again, or the photosensitivity is imparted as described above It is better to perform the film formation process (layer formation process), the exposure process, and the development process (further heating process as needed) in order. In particular, it is preferable that the above-mentioned processes are performed a plurality of times (two or more layers) or three to seven times (that is, three to seven layers) in sequence. By laminating the cured film in this manner, a laminated body can be obtained. In the present invention, a metal layer is particularly preferably provided on the portion where the cured film is provided or between the cured films or between the two.
These will be described in detail below.

<< Film Formation Process (Layer Formation Process) >>
A manufacturing method according to a preferred embodiment of the present invention includes a film formation process (layer formation process) in which a photosensitive resin composition is applied to a substrate and formed into a film (layered).
The type of the substrate can be appropriately determined depending on the application, and is not particularly limited to substrates made of semiconductors such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, Reflective film, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, electrode plates for plasma display devices (PDP), etc. In the present invention, a semiconductor manufacturing substrate 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 method of applying the photosensitive resin composition to a substrate, coating is preferred.
Specifically, examples of applicable methods include 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, a spray coating method, and a spin coating method. , Slit coating method and 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, a spray coating method, and an inkjet method are more preferred. By adjusting the appropriate solid content concentration and 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. As long as it is a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, or the like is preferred. If it is a rectangular substrate, a slit coating method or A spray method, an inkjet method, or the like is preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

＜＜ drying process ＞＞
The manufacturing method of the present invention may include a process of drying after removing the solvent after forming the photosensitive resin composition layer 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 the present invention may include an exposure process for exposing the photosensitive resin composition layer. The exposure amount is not particularly limited as long as the photosensitive resin composition can be cured. For example, in terms of exposure energy conversion at a wavelength of 365 nm, 100 to 10,000 mJ / cm ² is more preferable, and 200 to 8000 mJ / cm ² is more preferable.
The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, and 240 to 550 nm is preferable.
In terms of the relationship with the light source, the exposure wavelengths include (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, and g-rays ( Wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (three wavelengths of g, h, and i-rays), (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, in particular, exposure by a high-pressure mercury lamp is preferred, and exposure by i-rays is preferred. Thereby, a particularly high exposure sensitivity can be obtained.

＜＜ Developing Process ＞＞
The manufacturing method of the present invention may include a developing process of developing the exposed photosensitive resin composition layer. Development is performed to remove unexposed portions (non-exposed portions). The development method is not particularly limited as long as a desired pattern can be formed, and for example, a development method such as coating, spraying, dipping, or ultrasound can be used.
The development is performed using a developing solution. The developer can be used without particular limitation as long as it can remove unexposed portions (non-exposed portions). The developing solution preferably contains an organic solvent, and the developing solution preferably contains 90% by mass or more of an organic solvent. In the present invention, it is 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. The ClogP value can be obtained as a calculated value by inputting a structural formula from ChemBioDraw.
Examples of the organic solvent include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, isoamyl acetate, butyl propionate, and isopropyl butyrate. , Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example: alkoxy Methyl acetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxylate Ethyl acetate, etc.)), 3-alkoxypropanoic acid alkyl esters (for example: methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates ( For example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (eg, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate)), methyl 2-alkoxy-2-methylpropionate, and ethyl 2-alkoxy-2-methylpropionate (e.g., 2-methoxy-2-methylpropionate Methyl ester, 2-ethoxy-2-methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, 2- Methyl oxobutyrate, ethyl 2-oxobutyrate, and the like; and as the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, and ethylene glycol monomethyl Diethyl ether, methyl cellulose solvent acetate, ethyl cellulose solvent 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 monomonopropyl ether acetate, and the like; and as the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, and 2-heptanone are preferably cited. , 3-heptanone, N-methyl-2-pyrrolidone, etc .; and as the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. can be preferably listed; Dimethyl fluorene is preferably listed.
In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred.
In the developing solution, more than 50% by mass of an organic solvent is preferred, more than 70% by mass of an organic solvent is more preferred, and more than 90% by mass of an organic solvent is more preferred. The developing solution may be an organic solvent of 100% by mass.
The developer is preferably a non-alkali developer. From such a viewpoint, it is preferable that the developer containing the above-mentioned organic solvent as a main body does not contain an alkali compound. For example, as described in [0064] of Patent Document 1, an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate, and the like can be removed from a preferred developing solution applied to the present invention.

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 processing with a developer, it may be further processed. It is preferable to perform the processing using a different solvent from the developer. For example, the solvent contained in the photosensitive resin composition can be used for rinsing. The rinse time is preferably 5 seconds to 1 minute.

＜＜ Heating Process ＞＞
The manufacturing method of the present invention preferably includes a film forming process (layer forming process), a drying process, or a process of heating in a developing process. During the heating process, a cyclization reaction of a polymer precursor is performed. The composition of the present invention may contain a radically polymerizable compound other than the polymer precursor, but curing of the radically polymerizable compound other than the unreacted polymer precursor can also be performed in this process. The heating temperature (maximum heating temperature) of the layer in the heating process is preferably 50 ° C or higher, more preferably 80 ° C or higher, 140 ° C or higher is further preferred, 160 ° C or higher is further preferred, or 170 ° C or higher Even better. As the upper limit, 500 ° C or lower is more preferred, 450 ° C or lower is more preferred, 350 ° C or lower is further preferred, 250 ° C or lower is further preferred, and 220 ° C or lower is further preferred.
Regarding heating, the temperature at the start of heating up 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 ensure productivity and prevent excessive volatilization of the amine. 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 is called the temperature at the beginning of the process of heating to the highest 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 200 ° C lower than the boiling point of the solvent contained in the photosensitive resin composition. It is preferable that the temperature 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, it is preferable to heat at 180 ° C to 320 ° C, and it is more preferable to heat at 180 ° C to 260 ° C. The reason for this is not clear, but it is considered that by setting the temperature to this temperature, the ethynyl groups of the polymer precursors between the layers undergo a crosslinking reaction with each other.

Heating can be performed in stages. As an example, for example, the following pretreatment process may be performed: heating at 3 ° C / min from 25 ° C to 180 ° C, holding at 180 ° C for 60 minutes, heating at 180 ° C to 200 ° C at 2 ° C / minute, and maintaining at 200 ° C. 120 minutes. As the heating temperature in the pretreatment process, 100 to 200 ° C is preferable, 110 to 190 ° C is more preferable, and 120 to 185 ° C is more preferable. In this pretreatment process, as described in US Pat. No. 9,159,547, it is also preferable to perform treatment while irradiating ultraviolet rays. By such a pretreatment process, the characteristics of the film can be improved. 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, a pretreatment process 1 is performed in a range of 100 to 150 ° C, and then a pretreatment process 2 is performed in a range of 150 to 200 ° C.
Furthermore, cooling may be performed after heating, and the cooling rate at this time is preferably 1 to 5 ° C / minute.

From the viewpoint of preventing decomposition of the polymer precursor, it is preferable to perform a heating process in a low oxygen concentration atmosphere 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, and existing types of metals can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferred, and copper is further preferred.
The method for forming the metal layer is not particularly limited, and an existing method can be used. For example, the methods described in Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application No. 2001-521288, Japanese Patent Application No. 2004-214501, and Japanese Patent Application No. 2004-101850 can be used. For example, methods such as photolithography, peeling, plating, electroless plating, etching, printing, and a combination thereof can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electroplating can be mentioned.
The thickness of the metal layer is based on the thickest part, preferably 0.1 to 50 μm, 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 refers to performing the above-mentioned film formation process (layer formation process) and heating process on the surface of the cured film (resin layer) or metal layer, or sequentially performing the above-mentioned film formation process (layer formation process) on the photosensitive resin composition, the above-mentioned A series of processes including an exposure process and one of the development processes described above. Of course, the lamination process may also include the above-mentioned drying process and heating process.
When the lamination process is further performed after the lamination process, a surface activation treatment process may be performed after the heating process, after the exposure process, or after the metal layer formation process. An example of the surface activation treatment is a plasma treatment.
The lamination process is preferably performed 2 to 5 times, and more preferably 3 to 5 times.
For example, as the resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, a structure in which the resin layer is 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 forming process (layer forming process) and heating process of the photosensitive resin composition are further performed in order to cover the metal layer, or the photosensitive resin composition is sequentially performed. The film formation process (layer formation process), the exposure process, and the development process process (where necessary, a heating process is also performed) are preferable. 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 the 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. These contents are incorporated into this manual.
In addition, patterning of a sealing film, a substrate material (a base film and a cover film of a flexible printed circuit board, an interlayer insulating film) or an insulating film for mounting as described above is performed by etching or the like. For these uses, see, for example, Science & technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Yamoto Kakimoto / Editor, CMC Technical library "Polyimide Materials""Basics and Development", published in November 2011, Japan Polyimide-Aromatic Polymer Research Society / Edition "Latest Polyimide Basics and Applications" NTS Inc, August 2010, etc.
[Example]

Hereinafter, the present invention will be described in more detail with examples. The materials, usage amounts, proportions, processing contents, processing steps, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Part" and "%" are quality standards as long as they are not particularly limited.

<Synthesis of polymer precursor (resin)>
<Synthesis example 1>
[Polyimide precursor A-1 derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether synthesis]
21.2 g of 4,4'-oxodiphthalic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, 1 mg of water, 250 mL of diglyme , And stirred at a temperature of 60 ° C. for 4 hours, thereby producing a diester of 4,4′-oxo diphthalic dianhydride and 2-hydroxyethyl methacrylate. As a result of measuring the moisture content of the obtained reaction liquid, it contained 133 mass ppm. Next, the reaction mixture was cooled to -10 ° C, and 17.0 g of SOCl _{2 was} added over 60 minutes while maintaining the temperature at -10 ° C. After diluting with 50 mL of N-methylpyrrolidone, 25.1 g of a solution of 4,4'-diaminodiphenyl ether was dissolved in 100 mL of N-methylpyrrolidone, and the solution was passed at -10 ° C. The reaction mixture was added dropwise for 60 minutes, and the mixture was stirred for 2 hours, and then 20 mL of ethanol was added. Next, the polyimide precursor was precipitated in 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyfluorene imide precursor was filtered and dissolved in 380 g of tetrahydrofuran. The polyimide precursor was precipitated from the obtained solution in 6 liters of water and filtered, and dried at 45 ° C. for 3 days under a reduced pressure, thereby obtaining a polyimide precursor of a solid powder. The weight average molecular weight of this polyfluorene imide precursor A-1 was 23,300, and the number average molecular weight was 9,600.

<Synthesis example 2>
[Synthesis of polyimide precursor A-2 derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and diamine (a) shown below]
21.2 g of 4,4'-oxodiphthalic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, 1 mg of water, 250 mL of diglyme Ethylene glycol dimethyl ether), and stirred at 60 ° C for 4 hours, thereby producing 4,4'-oxodiphthalic dianhydride and 2-hydroxyethyl methacrylate. Diester. As a result of measuring the water content of the obtained reaction liquid, it contained 120 mass ppm. Next, the reaction mixture was cooled to -10 ° C, and 17.0 g of SOCl _{2 was} added over 60 minutes while maintaining the temperature at -10 ° C. After diluting with 50 mL of N-methylpyrrolidone, 38.0 g of the hydroxyl group-containing diamine (a) solution shown below was dissolved in 100 mL of N-methylpyrrolidone at -10 ° C. The reaction mixture was added dropwise over 60 minutes, and the mixture was stirred for 2 hours, and then 20 mL of ethanol was added. Next, the polyimide precursor was precipitated in 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyfluorene imide precursor was filtered and dissolved in 380 g of tetrahydrofuran. The polyimide precursor was precipitated from the obtained solution in 6 liters of water and filtered, and dried at 45 ° C. for 3 days under a reduced pressure, thereby obtaining a polyimide precursor as a solid powder. The weight average molecular weight of this polyfluorene imide precursor A-2 was 29,400, the number average molecular weight was 10,800, and the acid value was 5.6 mgKOH / g.
Diamine (a)
[Chemical Formula 30]

<Synthesis example 3>
[Polyimide precursor A-3 derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether synthesis]
21.2 g of 4,4'-oxodiphthalic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, 1 mg of water, 250 mL of diglyme , And stirred at a temperature of 60 ° C. for 4 hours, thereby producing a diester of 4,4′-oxo diphthalic dianhydride and 2-hydroxyethyl methacrylate. As a result of measuring the water content of the obtained reaction liquid, it contained 1,450 mass ppm. Next, the reaction mixture was cooled to -10 ° C, and 17.0 g of SOCl _{2 was} added over 60 minutes while maintaining the temperature at -10 ° C. After diluting with 50 mL of N-methylpyrrolidone, 25.1 g of a solution of 4,4'-diaminodiphenyl ether was dissolved in 100 mL of N-methylpyrrolidone, and the solution was passed at -10 ° C. The reaction mixture was added dropwise for 60 minutes, and the mixture was stirred for 2 hours, and then 20 mL of ethanol was added. Next, the polyimide precursor was precipitated in 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyfluorene imide precursor was filtered and dissolved in 380 g of tetrahydrofuran. The polyimide precursor was precipitated from the obtained solution in 6 liters of water and filtered, and dried at 45 ° C. for 3 days under a reduced pressure, thereby obtaining a polyimide precursor as a solid powder. The polyfluorene imide precursor A-3 had a weight average molecular weight of 22,000 and a number average molecular weight of 10,000.

<Synthesis example 4>
[Polyimide precursor composition derived from 4,4'-oxodiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diaminodiphenyl ether is A- Synthesis of 4]
42.4 g of 4,4'-oxydiphthalic 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. 4 hours. Next, the reaction mixture was cooled to -10 ° C, and a solution of 34.35 g of diisopropyldiimide 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 of 25.1 g of 4,4'-diaminodiphenyl ether 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. A precipitate generated in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. The polyimide precursor was precipitated from the obtained reaction solution in 14 L of water for filtration, and dried at 45 ° C. for 2 days under reduced pressure. The obtained powdery polyimide precursor A-4 had a weight average molecular weight of 23,800 and a number average molecular weight of 8,700.

<Synthesis example 5>
[Polybenzoxazole precursor A- derived from 4,4'-carbonyldibenzoic acid, 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, methacrylic acid chloride Synthesis of 5]
18.5 g of 4,4'-carbonyldibenzoic acid and 250 mL of N-methylpyrrolidone were mixed. Next, the reaction mixture was cooled to -10 ° C, and 17.0 g of SOCl _{2 was} added over 60 minutes while maintaining the temperature at -10 ± 5 ° C. Next, a solution of 21.0 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 100 mL of N-methylpyrrolidone, and the solution was passed at -10 ± 5 ° C. The reaction mixture was added dropwise for 60 minutes, and the mixture was stirred for 2 hours. Next, in the obtained reaction solution, 9.3 g of triethylamine was added under ice-cooling, 12.0 g of methacrylium chloride was added dropwise, and the mixture was further stirred under ice-cooling for 2 hours to obtain polybenzoxazole-containing Precursor solution. Next, the polybenzoxazole precursor was precipitated in 6 liters of water, and the water-polybenzoxazole precursor mixture was stirred at 5000 rpm for 15 minutes. The solid polybenzoxazole precursor was filtered off and dissolved in 380 g of tetrahydrofuran. The obtained solution was added to 6 liters of water, the polybenzoxazole precursor was precipitated, and the water-polybenzoxazole precursor mixture was stirred at 5000 rpm for 15 minutes. The solid of the polybenzoxazole precursor was filtered again, and dried at 45 ° C. for 3 days under reduced pressure. The polybenzoxazole precursor A-5 had a weight average molecular weight of 28,900 and a number average molecular weight of 8,800. The ratio of the components having a molecular weight of 1,000 or less was 0.3% by mass.

<Preparation of photosensitive resin composition>
A polymer precursor was mixed with the components described in Table 1 below to make a uniform solution, thereby preparing a coating liquid of a photosensitive resin composition. Each photosensitive resin composition was passed through a filter made by ADVANTEC CO., LTD, having a pore width of 0.8 μm, and subjected to pressure filtration.

<Temperature of base production>
Weighed 3.0 mg of polymer precursor, and used TGA (TA Instruments, Q500) to increase the temperature by 5% mass at 500 ° C at a temperature increase rate of 20 ° C / min as the alkali generation from the hot alkali generator. The temperature was measured. The pKa of the conjugate acid of the generated base was determined by identifying the decomposed species by LC-MS and calculating the pKa of the structure of the conjugate acid of the decomposed species using the following software package. Package software: Advanced Chemistry Development (ACD / Labs) software V8.14 supports Solaris system (1994-2007 ACD / Labs)

<Amount of acid group etc.>
Regarding each photosensitive resin composition in Examples and Comparative Examples, the total content of acid groups and acid generators (amount of acid groups and the like) contained in the photosensitizer was measured by NMR (nuclear magnetic resonance) method: ΣAc [mmol / g]).

＜ Storage stability ＞
Each photosensitive resin composition was placed at room temperature (25 ° C), and the storage stability was evaluated within a period of time until the precipitate was visually recognized.
A: No precipitation was observed even after 2 weeks.
B: Precipitation was found within 1 to 2 weeks.
C: Precipitation was found within 1 week.
D: Inclusions were found in the preparation stage.

<Mechanical properties (tensile strength)>
Each photosensitive resin composition was applied to a silicon wafer by a spin coating method to form a photosensitive resin composition layer. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 4 minutes to make it a photosensitive resin composition layer having a uniform thickness of 20 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed with a broadband exposure machine (manufactured by USHIO INC .: UX-1000SN-EH01) at an exposure energy of 400 mJ / cm ² to expose the exposed photosensitive resin composition layer (resin Layer) The temperature was raised at a temperature increase rate of 5 ° C / min in a nitrogen atmosphere, and after reaching 230 ° C, heating was performed for 3 hours. The cured resin layer was immersed in a 3% hydrofluoric acid solution, and the resin layer was peeled from the silicon wafer to obtain a resin film.
A tensile strength test was performed on the resin film peeled from the silicon wafer. In the test, a tensile tester (Tensilon) was used, with a crosshead speed of 300 mm / min, a width of 10 mm, and a sample length of 50 mm. Humidity) was measured in accordance with JIS-K6251 (Japanese Industrial Standard). In the evaluation, the elongation at break at the time of each cutting was measured 10 times, and the average value was used. The results were evaluated as follows.
A: Above 60%
B: 50% or more and less than 60%
C: less than 50%

<Developer solubility in unexposed areas>
Each photosensitive resin composition was applied to a silicon wafer by a spin coating method. The silicon wafer to which the photosensitive resin composition was applied was heated with a hot plate at 100 ° C. for 4 minutes, and a photosensitive resin composition layer having a thickness of 20 μm was obtained. The dissolution rate was calculated by immersing the photosensitive resin composition layer in cyclopentanone at 23 ° C. and measuring the time required for complete dissolution. In the test, a resist development analyzer (RDA-790EB manufactured by Litho Tech Japan Corporation) was used. The results were evaluated as follows.
A: 0.55μm / s or more
B: 0.4 μm / s or more and less than 0.55 μm / s
C: less than 0.4 μm / second

＜ Lite shadowing ＞
Each photosensitive resin composition was applied to a silicon wafer by a spin coating method. The silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 4 minutes to form a photosensitive resin composition layer having a thickness of 20 μm on the silicon wafer. Exposure was performed using a stepper (Nikon NSR 2005 i9C). Exposure was performed using i-rays, and at a wavelength of 365 nm, light exposure was performed in 1 μm increments of line and space at a exposure energy of 200, 300, 400, 500, 600, 700, 800 mJ / cm2 from 5 μm to 25 μm. exposure.
The exposed photosensitive resin composition layer was subjected to negative development using cyclopentanone for 60 seconds. The smaller the line width of the obtained photosensitive resin composition layer (pattern), the larger the difference between the solubility of the light-irradiated portion and the light-non-irradiated portion in the developing solution becomes, and a better result is obtained. Moreover, as for the change of the exposure energy, if the change of the line width is small, it means that the exposure latitude is large, which is a better result. The measurement limit is 5 μm. The results were evaluated as follows.
A: 10μm or less
B: More than 10 μm and 20 μm or less
C: A pattern exceeding 20 μm or having a line width with edge sharpness could not be obtained.

[Table 1]

<Photopolymerization initiator (photosensitizer)>
IRGACURE OXE01 (trade name) made by BASF
IRGACURE784 (trade name) made by BASF
IRGACURE OXE01 / IRGACURE784 (both trade names) BASF company blending ratio 1/1 (mass ratio)

ΣAc: Total content of acid groups and acid generating groups in polymer precursors and photosensitizers [mmol / g]

<Radical Polymerizable Compound (Polymerizable Compound)>
SR-209 (brand name) [2-functional] made by ArKema SA
A-TMMT (trade name) [4-functional] manufactured by Shin Nakamura Chemical Co., Ltd.
DPHA (trade name) [6-functional] manufactured by Nippon Kayaku Co., Ltd.

<Solvent>
NMP (N-methylpyrrolidone) / ethyl lactate
BGL (γ-butyrolactone) / DMSO (dimethyl sulfene)
Blending ratio 200/100 (mass ratio)

＜ Hot alkali generators ＞
[Chemical Formula 31]

TGB1:
pKa32, base production temperature 180 ° C, pKa11.4 of the conjugate acid of the base produced, Moire absorption coefficient 40l / (mol • cm)
TGB2:
pKa4, base production temperature 150 ° C, pKa5.1 of the conjugate acid of the generated base, Molar absorption coefficient 0l / (mol • cm)
TGB3:
pKa30, base production temperature 200 ° C, pKa11.4 of the conjugate acid of the base produced, Molar absorption coefficient 20l / (mol • cm)
TGB4:
pKa16.2, base production temperature of 170 ° C, pKa11.4 of the conjugate acid of the base produced, Molar absorption coefficient of 10l / (mol • cm)
TGB5:
pKa30, base production temperature 160 ° C, pKa9 of the conjugate acid of the generated base, Molar absorption coefficient 0l / (mol • cm)
TGB6:
pKa32, base production temperature 190 ° C, pKa10.4 of the base conjugate acid produced, Molar absorption coefficient 0l / (mol • cm)

From the above results, it can be seen that the photosensitive resin composition using the specific hot alkali generator in the present invention showed good storage stability, mechanical properties, developer solution solubility in unexposed areas, and lithography results (B (Above), to learn the facts of overall excellence. On the other hand, when a hot alkali generator (TBG2) (Comparative Example 1) having a tertiary amine structure and a carboxyl group is used, storage stability is poor. When a hot alkali generator (Comparative Example 2) is used, mechanical properties are poor. When a polymer precursor having a high acid value (Comparative Example 3) is used, storage stability, developer solubility in unexposed areas, and lithography are poor.

<Example 100>
The photosensitive resin composition of Example 1 was passed through a filter having a pore width of 0.8 μm and filtered under pressure, and then the photosensitive resin composition was applied to a silicon wafer by a spin coating method. The silicon wafer coated with the photosensitive resin composition was dried on a hot plate at 100 ° C. for 5 minutes to form a photosensitive resin composition layer having a uniform thickness of 15 μm on the silicon wafer. A stepper (NiKon NSR 2005 i9C) was used to expose the photosensitive resin composition layer on the silicon wafer at an exposure energy of 500 mJ / cm ² , and the exposed photosensitive resin composition layer (resin layer) was exposed using cyclopentanone. Development was performed for 60 seconds, thereby forming holes (patterned) having a diameter of 10 μm. Next, the temperature was raised at a temperature increase rate of 10 ° C / min in a nitrogen atmosphere, and after reaching 250 ° C, the temperature was maintained at this temperature for 3 hours. After reaching room temperature, a thin copper layer (metal layer) having a thickness of 2 μm was formed on a part of the surface of the photosensitive resin composition layer by a vapor deposition method so as to cover the pores. Furthermore, the same type of photosensitive resin composition was used again on the surface of the metal layer and the photosensitive resin composition layer, and the same process as described above was performed again from filtering the photosensitive resin composition to heating the patterned film for 3 hours. In order to produce a laminated body composed of a resin layer / metal layer / resin layer.
This resin layer (interlayer insulation film for redistribution layer) is excellent in insulation.
Furthermore, as a result of manufacturing a semiconductor device using this interlayer insulating film for a redistribution layer, it was confirmed that the operation was normal.

no

no

Claims (23)

A photosensitive resin composition comprising: at least one thermal alkali generator selected from the group consisting of a thermal alkali generator represented by the following formula (B1) and a thermal alkali generator group represented by the formula (B2); At least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; and a photosensitizer, the polymer precursor and the acid groups and acids contained in the photosensitizer The total content of generating groups is below 0.5mmol / g; In formula (B1) and formula (B2), R ¹ , R ^2, and R ³ are each independently an organic group, a halogen atom, or a hydrogen atom that does not have a tertiary amine structure, wherein R ¹ and R ^{2 are} not simultaneously Is a hydrogen atom, and R ¹ , R ² and R ³ do not have a carboxyl group. The photosensitive resin composition according to item 1 of the patent application scope, wherein The alkali generation temperature of the hot alkali generator is 120 ° C or higher and 200 ° C or lower. The photosensitive resin composition according to item 1 or item 2 of the scope of patent application, wherein The pKa of the hot alkali generator is greater than 7. The photosensitive resin composition according to item 1 or item 2 of the scope of patent application, wherein The polymer precursor comprises a polyimide precursor. The photosensitive resin composition according to item 4 of the scope of patent application, wherein the polyfluorene imide precursor is represented by the following formula (1); In Formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or Monovalent organic group. The photosensitive resin composition according to item 1 or item 2 of the scope of patent application, wherein The molar absorption coefficient of the hot alkali generator at a wavelength of 365 nm is 100 l / (mol · cm) or less. The photosensitive resin composition according to item 1 or item 2 of the scope of patent application, wherein The hot alkali generator contains a hot alkali generator having a pKa of 10 or more that generates a conjugate acid by heating. The photosensitive resin composition according to item 1 or item 2 of the scope of patent application, wherein The photosensitizer contains a photopolymerization initiator. The photosensitive resin composition according to item 1 or item 2 of the scope of patent application, which is used for development using a developing solution containing an organic solvent of 90% by mass or more. The photosensitive resin composition according to item 1 or item 2 of the scope of patent application, which is used for forming an interlayer insulating film for a redistribution layer. A cured film obtained by curing the photosensitive resin composition described in any one of the scope of claims 1 to 10 of the patent application. The hardened film according to item 11 of the scope of application for a patent has a film thickness of 1 μm to 30 μm. A laminated body having two or more hardened films as described in item 11 or item 12 of the scope of patent application. A laminated body having three to seven or more hardened films as described in item 11 or item 12 of the scope of patent application. The laminated body according to item 13 of the scope of patent application, wherein A metal layer is provided between the cured films. A method for manufacturing a hardened film includes: The film forming process of applying the photosensitive resin composition described in any one of the scope of claims 1 to 10 to a substrate to form a film. The method for manufacturing a cured film according to item 16 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 hardened film according to item 17 of the scope of patent application, wherein The developer used in this development contains 90% by mass or more of an organic solvent. The method for manufacturing a hardened film according to item 16 of the scope of patent application, which includes a process of heating the film at 80 ° C to 450 ° C. A method for manufacturing a laminated body, which performs the method for manufacturing a hardened film according to any one of the 16th to 19th patent applications. A semiconductor device having a hardened film as described in claim 11 or 12, or a laminated body as described in any of claims 13 to 15 in the scope of patent application. A hot alkali generator, which is represented by the following formula (B1) or (B2); In formula (B1) and formula (B2), R ¹ , R ² and R ³ are each independently an organic group, a halogen atom or a hydrogen atom which does not have a tertiary amine structure, wherein R ¹ and R ^{2 are} not simultaneously Is a hydrogen atom, and R ¹ , R ² and R ³ do not have a carboxyl group. The hot alkali generator according to item 22 of the scope of patent application, which is used for a photosensitive resin composition for developing using a developing solution containing 90% by mass or more of an organic solvent.