WO2017043474A1

WO2017043474A1 - Method for producing heterocycle-containing polymer precursor material, and application thereof

Info

Publication number: WO2017043474A1
Application number: PCT/JP2016/076131
Authority: WO
Inventors: 健志川端; 一郎小山; 悠岩井; 渋谷　明規
Original assignee: 富士フイルム株式会社
Priority date: 2015-09-11
Filing date: 2016-09-06
Publication date: 2017-03-16
Also published as: JP6531178B2; JPWO2017043474A1

Abstract

To provide: a method for producing a heterocycle-containing polymer precursor material which exhibits excellent preservation stability; a heterocycle-containing polymer precursor material; a composition; and a photosensitive resin composition. A method for producing a heterocycle-containing polymer precursor material which includes: adding a polymerization inhibitor to a composition comprising a heterocycle-containing polymer precursor and a first solvent, or adding a first solvent and a polymerization inhibitor to a composition comprising a heterocycle-containing polymer precursor; and adding a second solvent to the composition to which the polymerization inhibitor was added, and precipitating the heterocycle-containing polymer precursor and polymerization inhibitor in the second solvent, wherein the heterocycle-containing polymer precursor is selected from a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group.

Description

Method for producing heterocyclic ring-containing polymer precursor material and application thereof

The present invention relates to a method for producing a heterocyclic-containing polymer precursor material. The present invention also relates to a heterocyclic ring-containing polymer precursor material, and a composition and a photosensitive resin composition containing the heterocyclic ring-containing polymer. Furthermore, it is related with the cured film using the said photosensitive resin composition, the manufacturing method of a cured film, and a semiconductor device.

Thermosetting resins that are cured by cyclization, such as polyimide resins, are used for insulating layers of semiconductor devices because they are excellent in heat resistance and insulation.
Moreover, since polyimide resin has low solubility in a solvent, it is used in the state of a precursor (polyimide precursor) before the cyclization reaction, applied to a substrate, etc., and then heated to cyclize the polyimide precursor. A cured film is formed.

For example, Patent Document 1 was obtained by reacting an energy ray-curable alkaline aqueous solution-soluble resin (b) with a polyimide resin (a) obtained by a reaction between a tetracarboxylic dianhydride and a diamine compound. A photosensitive alkaline aqueous solution-soluble polyimide resin (A) is disclosed.

Patent Document 2 discloses that the photosensitive resin composition is (a) aromatic tetracarboxylic dianhydrides mainly composed of biphenyltetracarboxylic dianhydrides or bisethertetracarboxylic dianhydrides; A soluble polyimide obtained from a diamine mainly composed of a diamine represented by the formula (1), (b) a compound having a carbon-carbon double bond, and (c) a photosensitizer having a photoreactive initiator as an essential component. Resin composition. (In the formula, R ¹ represents a direct or divalent organic group, R ² represents —COOH or —OH, an integer of s = 0 to 4, and an integer of t = 1 to 4.)

Equation (1) is disclosed.

Furthermore, Patent Document 3 includes (A) a soluble polyimide containing a polymerizable functional group and containing a carboxyl group and / or a hydroxyl group, (B) a (meth) acrylic compound, and (C) a polymerization inhibitor, A photosensitive resin composition containing at least one additive selected from the group consisting of a stabilizer and an antioxidant as an essential component is disclosed.

Patent Document 4 discloses the following steps: (A) coating of a substrate with a photopolymerizable composition comprising a polymer (a) and a photoinitiator (b), (B) an i-line region (about 360). Used, consisting of imagewise exposure of the coated substrate to UV radiation within -370 nm), (C) removal of unexposed portions with solvent, and (D) conditioning of exposed and developed material Polymer (a) has the formula I:

[In the formula, an arrow indicates a structural isomer, X represents a tetravalent group of an aromatic tetracarboxylic acid, Y represents a divalent aliphatic group, a cyclic aliphatic group, or a monocyclic or polycyclic aromatic group. Represents a group, A represents —COO—, —CONH— or

Wherein R ₂ and R ₃ independently of each other represent an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 1 to 6 carbon atoms, and R ₁ represents photopolymerization. Represents at least 50% of all X groups represent oxydiphthalic acid groups, or at least 50% of all Y groups represent all four groups for two amine nitrogen atoms. And an aromatic diamine group substituted by an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, independently of each other at the ortho position of The manufacturing method of the relief image which is a polyimide precursor containing the repeating structural unit represented by these.

Further, in Patent Document 5, (A) the following formula (1):

{Wherein X ₁ is a tetravalent organic group having 6 to 40 carbon atoms, Y ₁ is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 150. , R ₁ and R ₂ are each independently a hydrogen atom, or the following formula (2) or (3):

(Wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10)
-R ₆ (3)
(Wherein R ₆ is a monovalent group selected from an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, or an aromatic group having 6 to 30 carbon atoms.)
A monovalent organic group represented by the above formula (2) and a monovalent organic group represented by the above formula (3) for all of R ₁ and R _2. Is 80 mol% or more, and the ratio of the monovalent organic group represented by the above formula (3) to all of R ₁ and R ₂ is 20 mol% to 80 mol%. }
A polyimide precursor having a structure represented by: 100 parts by mass; and (B) a photopolymerization initiator: 0.1 part by mass to 20 parts by mass;
A negative photosensitive resin composition containing

International Publication WO2008 / 007635 Publication JP 2003-330190 A JP 2004-325980 A Japanese Unexamined Patent Publication No. 07-005688 International Publication WO2013 / 168675

However, when this inventor examined the conventional polyimide precursor, it turned out that storage stability may be inferior. That is, it has been found that among heterocyclic-containing polymer precursors such as polyimide precursors, those having a polymerizable group may undergo polymerization to increase in viscosity over time.
The object of the present invention is to provide a method for producing a heterocyclic-containing polymer precursor material having excellent storage stability over time. Furthermore, it aims at providing the manufacturing method of a heterocyclic-containing polymer precursor material, a composition, a photosensitive resin composition, a cured film, a cured film, and a semiconductor device.

Under such circumstances, as a result of intensive studies by the present inventors, it has been found that the above-mentioned problems can be solved by blending a polymerization inhibitor with a heterocyclic ring-containing polymer under predetermined conditions.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <23>.
<1> A polymerization inhibitor is blended into a composition containing a heterocyclic ring-containing polymer precursor and a first solvent, or a first solvent and a polymerization inhibitor are blended into a composition containing a heterocyclic ring-containing polymer precursor. Blending, and
Blending a second solvent with the composition containing the polymerization inhibitor, and precipitating the heterocyclic ring-containing polymer precursor and the polymerization inhibitor in the second solvent,
The method for producing a heterocyclic ring-containing polymer precursor material, wherein the heterocyclic ring-containing polymer precursor is selected from a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group.
<2> The method for producing a heterocyclic-containing polymer precursor material according to <1>, wherein the amount of the polymerization inhibitor to be blended is 0.001 to 10% by mass of the heterocyclic-containing polymer precursor.
<3> The method for producing a heterocyclic-containing polymer precursor material according to <1> or <2>, wherein the heterocyclic-containing polymer precursor is dissolved in an amount of 5% by mass or more at 25 ° C. with respect to the first solvent.
<4> The method for producing a heterocyclic-containing polymer precursor material according to any one of <1> to <3>, wherein the polymerization inhibitor is dissolved in an amount of 5% by mass or more at 25 ° C. in the first solvent.
<5> The method for producing a heterocyclic-containing polymer precursor material according to any one of <1> to <4>, wherein the first solvent is tetrahydrofuran.
<6> The above production method comprises blending a first solvent and a polymerization inhibitor into a composition containing the above heterocycle-containing polymer precursor, and the complex according to any one of <1> to <5> A method for producing a ring-containing polymer precursor material.
<7> The production method includes blending a polymerization inhibitor into a composition containing the heterocyclic ring-containing polymer precursor and the first solvent, and the heterocyclic ring-containing polymer precursor and the first solvent. The method for producing a heterocyclic ring-containing polymer precursor material according to any one of <1> to <5>, wherein the composition containing is a synthetic reaction liquid for a heterocyclic ring-containing polymer precursor.
<8> The method for producing a heterocyclic-containing polymer precursor material according to any one of <1> to <7>, wherein the second solvent is water or alcohol.
<9> The <1> to <8>, wherein the heterocyclic-containing polymer precursor includes a repeating unit represented by the following formula (2) or a repeating unit represented by the following formula (3): A process for producing a heterocycle-containing polymer precursor material of
Formula (2)

Formula (3)

In formula (2), A ¹ and A ² each independently represent an oxygen atom or NH,
R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, R ¹¹³ and R ^At least one of ¹¹⁴ is a polymerizable group;
In Formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represents a hydrogen atom or a monovalent organic group. And at least one of R ¹²³ and R ¹²⁴ is a polymerizable group.
<10> The heterocyclic ring-containing polymer according to <9>, wherein both R ¹¹³ and R ¹¹⁴ in the above formula (2) and both R ¹²³ and R ¹²⁴ in the above formula (3) are polymerizable groups. A method for producing a precursor material.
<11> The method for producing a heterocyclic-containing polymer precursor material according to any one of <1> to <10>, wherein the polymerization inhibitor has a phenolic hydroxyl group.
<12> a heterocyclic-containing polymer precursor material selected from a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group,
The rate of change between the mass of the polymerization inhibitor in the heterocycle-containing polymer precursor material obtained by dividing the heterocycle-containing polymer precursor material into four parts, and the mass of the polymerization inhibitor in the entire heterocycle-containing polymer precursor material, respectively, Heterocycle-containing polymer precursor material that is ± 10% or less.
<13> The heterocycle-containing polymer precursor material according to <12>, wherein the heterocycle-containing polymer precursor material contains a polymerization inhibitor in a proportion of 0.001 to 10% by mass.
<14> A composition comprising the heterocyclic-containing polymer precursor material according to <12> or <13>.
<15> A photosensitive resin composition comprising the heterocyclic ring-containing polymer precursor material according to <12> or <13> and a photopolymerization initiator.
<16> A cured film obtained by curing the photosensitive resin composition according to <15>.
<17> The cured film according to <16>, which is an interlayer insulating film for a rewiring layer.
<18> A method for producing a cured film, comprising a step of applying the photosensitive resin composition according to <15> to a substrate, and a step of curing the photosensitive resin composition applied to the substrate.
<19> A semiconductor device having the cured film according to <16> or <17>.
<20> A heterocyclic-containing polymer precursor material obtained by the method for producing a heterocyclic-containing polymer precursor material according to any one of <1> to <11>.
<21> A heterocyclic-containing polymer precursor material selected from a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group, and any 4 of the heterocyclic-containing polymer precursor materials Heterocycle-containing polymer in which the rate of change between the mass of the polymerization inhibitor in a sample collected from each place 1 g and the mass of the polymerization inhibitor in the whole heterocyclic-containing polymer precursor material is ± 10% or less, respectively. Precursor material.
<22> In a sample obtained by collecting 1 g of each of four heterocyclic ring-containing polymer precursor materials obtained by the method for producing a heterocyclic ring-containing polymer precursor material according to any one of <1> to <11> A heterocycle-containing polymer precursor material in which the rate of change between the mass of the polymerization inhibitor and the mass of the polymerization inhibitor in the entire heterocycle-containing polymer precursor material is ± 10% or less, respectively.
<23> The heterocyclic-containing polymer precursor according to any one of <20> to <22>, wherein the amount of the polymerization inhibitor is a ratio of 0.001 to 10% by mass of the heterocyclic-containing polymer precursor material. Body material.

According to the present invention, it is possible to provide a heterocyclic-containing polymer precursor material having excellent storage stability. Moreover, it became possible to provide a heterocyclic ring-containing polymer precursor material, a composition, a photosensitive resin composition, a cured film, a method for producing a cured film, and a semiconductor device.

It is the schematic which shows the structure of one Embodiment of a semiconductor device.

The description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, “active light” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. In this specification, “exposure” means not only exposure using far ultraviolet rays, X-rays, EUV light typified by mercury lamps and excimer lasers, but also particle beams such as electron beams and ion beams, unless otherwise specified. Include drawing in the exposure.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents both and / or “acrylate” and “methacrylate”, and “(meth) allyl” means both “allyl” and “methallyl”, or “(Meth) acryl” represents either “acryl” and “methacryl” or any one, and “(meth) acryloyl” represents both “acryloyl” and “methacryloyl”, or Represents either.
In this specification, the term “process” not only means an independent process, but also if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes, include.
In this specification, solid content concentration is the mass percentage of the mass of the other component except a solvent with respect to the total mass of a composition. Moreover, solid content concentration says the density | concentration in 25 degreeC unless there is particular mention.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene converted values by gel permeation chromatography (GPC) measurement unless otherwise specified. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel. It can be determined by using Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, the eluent was measured using THF (tetrahydrofuran). Unless otherwise specified, detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector.

In the method for producing a heterocyclic ring-containing polymer precursor material of the present invention, a polymerization inhibitor is blended with a composition containing a heterocyclic ring-containing polymer precursor and a first solvent, or a heterocyclic ring-containing polymer precursor is added. Blending a first solvent and a polymerization inhibitor into the composition comprising, and
Blending a second solvent with the composition containing the polymerization inhibitor, and precipitating the heterocyclic ring-containing polymer precursor and the polymerization inhibitor in the second solvent,
The heterocyclic ring-containing polymer precursor is selected from a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group.
By setting it as such a structure, the heterocyclic-containing polymer precursor material excellent in storage stability is obtained.

Polymerization may proceed during storage of a heterocyclic ring-containing polymer having a polymerizable group. Here, in order to suppress the progress of the polymerization, it is conceivable to add a polymerization inhibitor. However, as a result of investigation by the present inventor, as shown in Examples described later, even when a polymerization inhibitor is added during the synthesis process of the heterocyclic ring-containing polymer, the storage stability of the obtained heterocyclic-containing polymer precursor is obtained. Was inferior. Furthermore, it is assumed that an unexpected reaction proceeds when a polymerization inhibitor is blended. On the other hand, it was found that even when a polymerization inhibitor was added to the dried solid heterocyclic-containing polymer precursor, the storage stability was also inferior. When this reason was examined, it was found that even when a polymerization inhibitor was added to the dried solid heterocyclic-containing polymer, the polymerization inhibitor was not uniformly present in the heterocyclic-containing polymer precursor. .
In the present invention, after adding a solvent to the heterocyclic-containing polymer precursor in addition to the polymerization inhibitor, the heterocyclic-containing polymer precursor is precipitated in a substantially uniform manner by precipitating the heterocyclic-containing polymer precursor. The present inventors have found that a heterocyclic-containing polymer precursor material excellent in storage stability can be obtained, and thus completed the present invention.
That is, in the heterocyclic-containing polymer precursor material obtained by the production method of the present invention, the polymerization inhibitor is present almost uniformly in the polymer. In addition, the heterocycle-containing polymer precursor material obtained by the method for producing a heterocycle-containing polymer precursor material of the present invention does not impair sensitivity even though it contains a polymerization inhibitor. Therefore, the photosensitive resin composition using the heterocyclic-containing polymer precursor material of the present invention also has an advantage of high sensitivity.
Hereinafter, the present invention will be described in detail.

<Method for producing heterocyclic-containing polymer precursor material>
<< Polymerization inhibitor blending process >>
The method for producing a heterocyclic ring-containing polymer precursor material of the present invention includes blending a polymerization inhibitor into a composition containing a heterocyclic ring-containing polymer precursor and a first solvent, or includes a heterocyclic ring-containing polymer precursor. Including a first solvent and a polymerization inhibitor in the composition.
Thus, by the presence of the heterocyclic-containing polymer precursor that has already undergone the synthesis reaction, the first solvent, and the polymerization inhibitor, these components are mixed well, and the polymerization inhibitor is A heterocycle-containing polymer precursor material that is uniformly incorporated into the heterocycle-containing polymer precursor and has excellent storage stability is obtained.
Therefore, in this invention, it is preferable to stir well in the state of the composition in which the heterocyclic ring-containing polymer precursor, the first solvent, and the polymerization inhibitor are present. The stirring speed can be appropriately determined according to the production scale and the stirring form, and can be, for example, about 10 rpm to 6,000 rpm. The stirring time can be about 5 minutes to 1 hour.

As 1st embodiment of the said polymerization inhibitor mixing | blending process, mix | blending a 1st solvent and a polymerization inhibitor with the composition containing a heterocyclic containing polymer precursor is mentioned. Examples of the heterocyclic ring-containing polymer precursor in this case include a solid heterocyclic ring-containing polymer precursor and a precipitate obtained by depositing the heterocyclic ring-containing polymer precursor from a synthesis reaction liquid of the heterocyclic ring-containing polymer precursor.
As 2nd embodiment of the said polymerization inhibitor mixing | blending process, mix | blending a polymerization inhibitor with the composition containing a heterocyclic containing polymer precursor and a 1st solvent is mentioned. In this case, examples of the composition containing the heterocyclic ring-containing polymer precursor and the first solvent include a synthesis reaction liquid of the heterocyclic ring-containing polymer precursor.
As 3rd embodiment of the said polymerization inhibitor mixing | blending process, mix | blending a 1st solvent and a polymerization inhibitor with the composition containing a heterocyclic containing polymer precursor and a 1st solvent is mentioned. Here, the first solvent contained in the composition and the first solvent to be blended may be the same solvent or different solvents. For example, a polymerization inhibitor (corresponding to a composition containing a heterocyclic ring-containing polymer precursor and a first solvent) in a synthesis reaction solution of the heterocyclic ring-containing polymer precursor (corresponding to the first solvent and the polymerization inhibitor). And the like).
The polymerization inhibitor blending step is usually performed at 15 to 40 ° C.

<< first solvent >>
The first solvent used in the present invention normally serves as a good solvent for the heterocycle-containing polymer precursor in the method for producing a heterocycle-containing polymer precursor material of the present invention. In the present invention, preferably, the heterocyclic-containing polymer precursor is dissolved in an amount of 5% by mass or more at 25 ° C. in the first solvent. The upper limit of solubility is not particularly defined, and may be 100% by mass. By setting it as such a structure, a polymerization inhibitor becomes easy to take in into a heterocyclic containing polymer precursor more uniformly.
In the present invention, it is preferable that the polymerization inhibitor dissolves in an amount of 5% by mass or more at 25 ° C. in the first solvent. By setting it as such a structure, a polymerization inhibitor becomes easy to take in into a heterocyclic containing polymer precursor more uniformly. The upper limit of solubility is not particularly defined, and may be 100% by mass.

Examples of the first solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetate alkyl (eg, methyl oxyacetate, alkyl oxyacetate, butyl oxyalkyl acetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxy) Methyl acetate, ethyl ethoxyacetate, etc.), alkyl esters of 3-alkyloxypropionic acid (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3- Ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate) Propyl 2-alkyloxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2- Methyl alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), pyruvic acid Methyl, Ethyl rubinate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate And cetates, and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-pyrrolidone, and aromatic hydrocarbons such as toluene, xylene, Suitable examples of anisole, limonene and the like, and sulfoxides include dimethyl sulfoxide.

Of these, ethers and ketones are preferable, tetrahydrofuran and N-methyl-pyrrolidone are more preferable, and tetrahydrofuran is more preferable.

The amount of the first solvent used is, by mass ratio, preferably 1 to 100 times that of the heterocyclic ring-containing polymer precursor, and more preferably 4 to 20 times.
Only 1 type may be used for a 1st solvent and it may use 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Precipitation process >>
In the method for producing a heterocyclic ring-containing polymer precursor material of the present invention, the second solvent is blended in the composition blended with the polymerization inhibitor, and the heterocyclic ring-containing polymer precursor is mixed in the second solvent. And precipitation of the polymerization inhibitor. By setting it as such a structure, the heterocyclic containing polymer precursor material of the state by which the polymerization inhibitor was uniformly taken in in the heterocyclic containing polymer precursor is obtained.
Here, the precipitation means that at least a part of the heterocyclic-containing polymer precursor and at least a part of the polymerization inhibitor present in the first solvent are separated from the first solvent as a solid, Usually, it precipitates in the second solvent. Preferably, 80% by mass or more of the total of the heterocyclic-containing polymer precursor and the polymerization inhibitor present in the first solvent is separated from the first solvent and precipitated in the second solvent. .
In the precipitation, it is not essential to deposit all of the heterocyclic ring-containing polymer precursor and the polymerization inhibitor present in the first solvent in the second solvent. Needless to say, precipitation of a part of the polymerization inhibitor is also included in the scope of the present invention. In the present invention, the total of the heterocyclic-containing polymer precursor and the polymerization inhibitor contained in the composition is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, in the second solvent. Precipitation is preferred.
The precipitation step is usually performed at 15 to 40 ° C.

<< second solvent >>
The second solvent used in the present invention usually serves as a poor solvent for the heterocycle-containing polymer precursor in the method for producing a heterocycle-containing polymer precursor material of the present invention. That is, in the present invention, the second solvent preferably has a lower solubility at 25 ° C. in the heterocyclic ring-containing polymer precursor than the first solvent, and the heterocyclic ring-containing polymer precursor is lower than the first solvent. It is more preferable that the solubility at 25 ° C. is lower by 10% by mass or more. By setting it as such a structure, precipitation of a heterocyclic containing polymer precursor can be advanced more effectively, and the heterocyclic containing polymer precursor material in which the polymerization inhibitor was taken in more uniformly is obtained. The solubility of the second solvent in the heterocyclic ring-containing polymer precursor at 25 ° C. is preferably 5% by mass or less or not dissolved at all.

Examples of the second solvent include water and alcohol (preferably an alcohol having 1 to 4 carbon atoms). Water and methanol are preferable, and water is more preferable.
The amount of the second solvent used is preferably 1 to 1,000 times that of the heterocyclic ring-containing polymer, and more preferably 10 to 500 times. Further, the amount of the second solvent used is preferably 1 to 1,000 times, more preferably 4 to 100 times the amount of the first solvent used.
Only 1 type may be used for a 2nd solvent and it may use 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Heterocycle-containing polymer precursor >>
The heterocyclic ring-containing polymer precursor used in the present invention is selected from a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group.
The polymerizable group is a group that can undergo a crosslinking reaction by the action of actinic rays, radiation, radicals, acids, or bases. Preferred examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, Examples thereof include a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group, and an amino group. The polymerizable group possessed by the heterocyclic ring-containing polymer precursor is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like.

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
In the formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH (OH) CH ₂ — or a polyoxyalkylene group having 4 to 30 carbon atoms.
Examples of suitable R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, —CH ₂ CH (OH) CH _2- , and ethylene, propylene, trimethylene, and —CH ₂ CH (OH) CH ₂ — are preferred.
Particularly preferably, R ²⁰⁰ is methyl and R ²⁰¹ is ethylene.
Hereinafter, a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group will be described in detail.

<<< Polyimide precursor >>>
The polyimide precursor used in the present invention does not particularly define the structure or the like as long as it contains a polymerizable group and can be made into a polyimide, and is intended to include a polyamideimide precursor. It is preferable that the polyimide precursor used by this invention contains the repeating unit represented by following formula (2).

Formula (2)

In formula (2), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ And R ¹¹⁴ each independently represents a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is a polymerizable group.

A ¹ and A ² in Formula (2) each independently represent an oxygen atom or NH, and preferably an oxygen atom.

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a group containing a cyclic aliphatic group and an aryl group, and a linear or branched aliphatic group having 2 to 20 carbon atoms. A group consisting of a cyclic aliphatic group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a combination thereof is preferable, and a group consisting of an aryl group having 6 to 20 carbon atoms is more preferable. The following are mentioned as an example of an aryl group.

In the formula, A is a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C (═O) —, —S—, —S (= O) ₂ — and —NHCO—, and a group selected from these combinations are preferable, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O—, — It is more preferably a group selected from C (═O) —, —S—, —SO ₂ —, —CH ₂ —, —O—, —S—, —SO ₂ —, —C (CF ₃ _{_{) 2 -, - C (CH}} 3) 2 - and more preferably a divalent group selected from.

R ¹¹¹ is more specifically a diamine residue remaining after removal of the amino group of the diamine. Examples of the diamine include linear or branched aliphatic, cyclic aliphatic or aromatic diamine.
Specific examples include diamine residues remaining after removal of the amino groups of the following diamines.
1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1, 2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, bis (3-amino Cyclohexyl) methane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane and isophoronediamine; m- and p-phenylenediamine, diaminotoluene, 4,4′- and 3,3′-diaminobiphenyl, 4, 4'- and 3,3'-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- And 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4 ' -Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2 -Bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2, 2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3- Amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4′-diaminoparaterphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene 9,10-bis (4-aminophenyl) anthracene, 3,3′-dimethyl-4,4′-diaminodiphenylsulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiph Nylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 4,4′-diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3 ′, 4,4′-tetraaminobiphenyl, 3,3 ′ , 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) Fluorene, 4,4′-dimethyl-3,3′-diaminodiphenylsulfone, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodi Phenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6 -Trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide , Esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, , 5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-a Nophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2 -Bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] Hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4′-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4′-bis (4- Amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylpheno) B) Diphenylsulfone, 4,4′-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoro Propane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,2 ′, 5 At least one diamine selected from 5 ′, 6,6′-hexafluorotolidine and 4,4 ′ ″-diaminoquaterphenyl;

Examples of R ¹¹¹ also include diamine residues remaining after removal of the amino groups of diamines (DA-1) to (DA-18) shown below.

An example of R ¹¹¹ is a diamine residue remaining after removal of the amino group of a diamine having at least two alkylene glycol units in the main chain. Preferred is a diamine residue containing two or more ethylene glycol chains or propylene glycol chains in one molecule, and more preferred is a diamine residue containing no aromatic ring. Examples include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 ( Trade names, manufactured by HUNTSMAN Co., Ltd., 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, 1- (2- (2- (2 -Aminopropoxy) ethoxy) propoxy) propan-2-amine and the like. The structures of Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

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

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

In formula (5), R ¹¹² represents a single bond or a divalent group. The divalent group includes a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO ₂ —, and —NHCO—, and these A group selected from a combination is preferred. R ¹¹² is a single bond or a divalent group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— and —SO ₂ —. More preferably a single bond or —CH ₂ —, —C (CF ₃ ) ₂ —, —C (CH ₃ ) ₂ —, —O—, —CO—, —S— and —SO. ₂ - is a bivalent radical selected from the more preferred.

Formula (6)

Specific examples of R ¹¹⁵ include a tetracarboxylic acid residue remaining after removal of the acid anhydride group from tetracarboxylic dianhydride.
Specific examples include tetracarboxylic acid residues remaining after the removal of the acid anhydride group from the following tetracarboxylic dianhydrides.
Pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl sulfide tetracarboxylic dianhydride, 3,3 ', 4,4'-Diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylmethanetetracarboxylic dianhydride 2,2 ′, 3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetra Carboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2 , 2-bis (3,4-dica Boxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3 -Diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalene tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic Acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Anhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarbo Ciphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and at least one selected from alkyls having 1 to 6 carbon atoms and / or alkoxy derivatives having 1 to 6 carbon atoms Seed tetracarboxylic dianhydride.

Examples of R ¹¹⁵ also include tetracarboxylic acid residues remaining after removal of the acid anhydride groups from tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below.

From the viewpoint of solubility in an alkali developer, it is preferable that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, as R ¹¹¹ , 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) sulfone, bis (4-amino) -3-Hydroxyphenyl) sulfone and the above (DA-1) to (DA-18) are mentioned as preferred examples, and as R ¹¹⁵ , the above (DAA-1) to (DAA-5) are mentioned as preferred examples. It is done.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is a polymerizable group. As a polymeric group, it is synonymous with the polymeric group mentioned above, and its preferable range is also the same. In the present ^invention, at least one of ^{R 113} and ^{R 114} is a polymerizable ^group, it is preferred that both ^{R 113} and ^{R 114} is a polymerizable group.
As the monovalent organic group represented by R ¹¹³ and R ^114, a substituent that improves the solubility in a developer is preferably used.

From the viewpoint of solubility in an aqueous developer, the monovalent organic group as R ¹¹³ or R ¹¹⁴ is one, two, or three, preferably one acidic group bonded to the carbon atom of the aryl group. An aryl group and an aralkyl group having Specific examples include an aryl group having 6 to 20 carbon atoms having an acidic group and an aralkyl group having 7 to 25 carbon atoms having an acidic group. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group.
R ¹¹³ or R ¹¹⁴ is preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl or 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aryl group, and more preferably an alkyl group substituted with an aryl group.
The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, Examples include octadecyl, isopropyl, isobutyl, sec-butyl, t-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 alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. Groups. Among these, a cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity. Moreover, as an alkyl group substituted by the aryl group, the linear alkyl group substituted by the aryl group mentioned later is preferable.
Specific examples of the aryl group include a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthylene ring, phenanthrene ring, anthracene ring. Naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, Indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring Phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and a phenazine ring. A benzene ring is most preferred.

In the formula (2), when R ¹¹³ is a hydrogen atom, or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor forms a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. Also good. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.

In the case of alkali development, the polyimide precursor preferably has a fluorine atom in the structural unit from the viewpoint of improving resolution. The fluorine atom imparts water repellency to the surface of the film during alkali development, and soaking in from the surface can be suppressed. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less from the viewpoint of solubility in an alkaline aqueous solution.

Further, an aliphatic group having a siloxane structure may be copolymerized for the purpose of improving the adhesion to the substrate. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

Further, in order to further improve the storage stability, the polyimide precursor may be sealed with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. preferable. Of these, it is more preferable to use a monoamine. Monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1- Hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-amino Naphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-amino Benzoic acid, 3-aminobenzoic acid, -Aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxy Examples include pyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

The repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (1-1). That is, it is preferable that at least one of the heterocyclic ring-containing polymer precursors used in the present invention is a precursor having a repeating unit represented by the formula (1-1). By adopting such a structure, it becomes possible to further widen the width of the exposure latitude.

In formula (1-1), A ¹ and A ² each represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent It represents a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is a polymerizable group.

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

The polyimide precursor may be one type of repeating structural unit represented by the formula (2), but may be two or more types. Moreover, the structural isomer of the repeating unit represented by Formula (2) may be included. Needless to say, the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (2).

As one embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all repeating units is a repeating unit represented by the formula (2). Is exemplified.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 30,000, and further preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 5,000 to 14,000, and more preferably 6,000 to 10,000.
The degree of dispersion of the polyimide precursor is preferably 1.0 to 10.0, more preferably 1.1 to 5.0, and still more preferably 1.2 to 4.0.

<<< Polybenzoxazole precursor >>>
The polybenzoxazole precursor used in the present invention is not particularly limited as long as it has a polymerizable group and can be converted into polybenzoxazole, but is not particularly limited, but is a compound represented by the following formula (3). Preferably there is.

Formula (3)

In Formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represents a hydrogen atom or a monovalent organic group. And at least one of R ¹²³ and R ¹²⁴ is a polymerizable group.

R ¹²¹ represents a divalent organic group. Examples of the divalent organic group include an aliphatic group and an aryl group.
The following are mentioned as an example of a bivalent aryl group.

In the formula, A represents —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and —C (CH ₃ ) ₂ —. Represents a divalent group selected from the group consisting of

As the divalent aliphatic group, a linear aliphatic group is preferable from the viewpoint of promoting cyclization at a low temperature. The linear aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms, still more preferably 3 to 20 carbon atoms, and still more preferably 4 to 15 carbon atoms. 5 to 10 is even more preferable. The linear aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3- Dimethyl glutaric acid, 3-ethyl-3-methyl glutaric acid, adipic acid, octafluoroadipic acid, 3-methyl adipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluoro Suberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, Lidecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosandioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid Acid, hexacosane diacid, heptacosane diacid, octacosane diacid, nonacosane diacid, triacontane diacid, hentriacontane diacid, dotriacontane diacid, diglycolic acid, and dicarboxylic acid represented by the following formula Can be mentioned.

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

R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the formula (2), and preferred ranges are also the same.
R ¹²² is preferably a residue of a bisaminophenol derivative represented by the following formula (A).
Ar (NH ₂ ) ₂ (OH) ₂ (A)
In the formula, Ar is an aryl group.

Examples of the bisaminophenol derivative of the above formula (A) include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, and 3,3′- Diamino-4,4′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, bis (3-amino-4-hydroxyphenyl) methane, 2,2-bis (3-amino- 4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, bis (4-amino) -3-hydroxyphenyl) methane, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 4,4 -Diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4, Examples thereof include 4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used alone or in combination of two or more.

Of the bisaminophenol derivatives represented by the formula (A), bisaminophenol derivatives having the following aryl groups are preferred.

In the formula, X ₁ represents —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, or —NHCO—. In the above structure, —OH and —NH ₂ contained in the structure of the formula (A) are bonded to each other at the ortho position (adjacent position).
The bisaminophenol derivative represented by the above formula (A) is a bisphenol represented by the following formula (As) because a polybenzoxazole precursor that is highly transparent to i-line and can be cured at a low temperature can be obtained. Preferably there is.

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

(In the formula, * indicates binding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As)).

In the above formula (As), it is considered that the ortho position of the phenolic hydroxyl group, that is, that R ₃ also has a substituent is considered to make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and cured at a low temperature. In particular, it is particularly preferable in that the effect of increasing the cyclization rate is further increased.

Further, in the above formula (As), R ₂ is an alkyl group and R ₃ is an alkyl group, which means that it has high transparency to i-line and a high cyclization rate when cured at low temperature. This is particularly preferable in that a polybenzoxazole precursor having sufficient solubility and excellent balance can be obtained when an alkaline aqueous solution is used as a developer while maintaining the effect.

In the formula (As), R ₁ is preferably alkylene or substituted alkylene. Specific examples of alkylene and substituted alkylene according to R ₁ include —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) (CH ₂ CH ₃ )-, -CH (CH ₂ CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) —, —CH (CH (CH ₃ ) ₂ ) —, —C (CH ₃ ) (CH (CH ₃ ) ₂ ) —, —CH (CH ₂ CH ₂ CH ₂ CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH (CH ₂ CH (CH ₃ ) ₂ )-, -C (CH ₃ ) (CH ₂ CH (CH ₃ ) ₂ )-, -CH _{_{_{_{(CH 2 CH 2 CH 2 CH}}}} 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 2 C _{_{_{_{2 CH 3) -, - CH}}}} (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) - but the like Among them, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — maintain the effect of high transparency to i-line and high cyclization rate when cured at low temperature. However, it is more preferable in that a polybenzoxazole precursor excellent in balance having sufficient solubility in not only an aqueous alkali solution but also a solvent can be obtained.

As a method for producing the bisaminophenol derivative represented by the above formula (As), for example, refer to paragraph numbers 0085 to 0094 and Example 1 (paragraph numbers 0189 to 0190) of JP2013-256506A. The contents of which are incorporated herein.

Specific examples of the structure of the bisaminophenol derivative represented by the formula (As) include those described in JP-A-2013-256506, paragraphs 0070 to 0080, and the contents thereof are described in the present specification. Incorporated into. Of course, it is needless to say that the present invention is not limited to these.

Among these, those shown below are preferable as the bisaminophenol derivative represented by the above formula (As).

R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹²³ and R ¹²⁴ is a polymerizable group. As a polymeric group, it is synonymous with the polymeric group mentioned above, and its preferable range is also the same. In the present ^invention, at least one of ^{R 123} and ^{R 124} is a polymerizable ^group, it is preferred that both ^{R 123} and ^{R 124} is a polymerizable group. When R ¹²³ or R ¹²⁴ represents a monovalent organic group, it has the same meaning as R ¹¹³ and R ¹¹⁴ in formula (2), and the preferred range is also the same.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3).
It is preferable that the diamine residue represented by the following formula (SL) is included as another type of repeating structural unit in that the occurrence of warpage accompanying ring closure can be suppressed.

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

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight within the above range, it is possible to reduce both the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor and to suppress the warp and to improve the solubility.

When the diamine residue represented by the formula (SL) is included as another type of repeating structural unit, the remaining tetra after the dianhydride group is removed from the tetracarboxylic dianhydride in terms of improving alkali solubility. It is preferable to include a carboxylic acid residue as a repeating structural unit. Examples of such tetracarboxylic acid residue, and examples of R ¹¹⁵ in formula (2).

In order to improve the storage stability of the composition, an acid anhydride containing an aliphatic group or a cyclic group having at least one alkenyl group or alkynyl group as the terminal amino group of the polybenzoxazole precursor is used. The amide is preferably capped.

As such a group derived from an acid anhydride containing a cyclic aliphatic group or cyclic group having at least one alkenyl group or alkynyl group after reacting with an amino group, that is, the end-capping group is: For example, the group shown below can be mentioned. These may be used alone or in combination of two or more.

In particular, the groups shown below are preferable because they can improve storage stability.

The polybenzoxazole precursor includes, for example, a bisaminophenol derivative represented by the formula (A), a dicarboxylic acid containing ^R121 , and a compound selected from dicarboxylic acid dichloride and dicarboxylic acid derivative of the above dicarboxylic acid Can be obtained by reacting.
When dicarboxylic acid is used, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 50,000, more preferably 25,000 to 45,000 when used in the composition described below. It is preferably 30,000 to 40,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further preferably 9,000 to 11,000.
The degree of dispersion of the polybenzoxazole precursor is preferably 1.0 to 10.0, more preferably 1.1 to 5.0, and still more preferably 1.2 to 4.0.

In the method for producing a heterocyclic ring-containing polymer precursor material of the present invention, only one heterocyclic ring-containing polymer precursor may be used, or two or more heterocyclic ring-containing polymer precursor materials may be used. Moreover, although you may use both a polyimide precursor and a polybenzoxazole precursor, the aspect using only 1 type, or 2 or more types of polyimide precursors, and 1 type, or 2 or more types of polybenzoxazole precursors only An embodiment using is more preferable.

<< Polymerization inhibitor >>
In the method for producing a heterocyclic-containing polymer precursor material of the present invention, the type of polymerization inhibitor to be blended is not particularly limited, and a known one can be used.
As the polymerization inhibitor, those having a phenolic hydroxyl group are preferred. Specifically, examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis ( (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), and N-nitroso-N-phenylhydroxyamine aluminum salt are preferred. Hydroquinone, p- Methoxyphenol, di-tert-butyl-p-cresol, benzoquinone and 2,6-di-tert-butyl-p-cresol are preferred, and 2,6-di-tert-butyl-p-cresol is more preferred.
The amount of the polymerization inhibitor to be blended is preferably 0.001 to 10% by mass of the heterocyclic-containing polymer precursor. The lower limit of the amount of the polymerization inhibitor to be blended is more preferably 0.1% by mass or more, and can also be 0.2% by mass or more. 9 mass% or less is more preferable, the upper limit of the quantity of the polymerization inhibitor to mix | blend may be 7 mass% or less, and can also be 5 mass% or less. In particular, in the present invention, the polymerization inhibitor is uniformly applied to the heterocyclic-containing polymer precursor material even when the content is 1.0% by mass or less, further 0.7% by mass or less, and particularly 0.4% by mass or less. It is preferable in that it can be incorporated.
Only one polymerization inhibitor may be included, or two or more polymerization inhibitors may be included. In the case of two or more types, the total amount is preferably within the above range.
Here, when the amount of the polymerization inhibitor is 10% by mass or less of the heterocyclic-containing polymer precursor, the sensitivity tends to be further improved, and when the amount is 0.001% by mass or more, the resulting heterocyclic ring is obtained. The storage stability of the containing polymer precursor tends to be further improved.

In the present invention, a polymerization inhibitor containing 2,6-di-tert-butyl-p-cresol is added to the composition containing a heterocyclic ring-containing polymer precursor and tetrahydrofuran, and 0.1 to 0.5% of the heterocyclic ring-containing polymer precursor. Mixing in a proportion of 5% by mass, or in a composition containing a heterocyclic ring-containing polymer precursor, tetrahydrofuran and 2,6-di-ethylene in a proportion of 0.1 to 5% by mass of the heterocyclic ring-containing polymer precursor blending a polymerization inhibitor containing tert-butyl-p-cresol, and blending water into the composition blended with the polymerization inhibitor, into the water, the heterocyclic-containing polymer precursor and the above. Precipitation of 2,6-di-tert-butyl-p-cresol, wherein the heterocycle-containing polymer precursor includes a polyimide precursor having a polymerizable group and a polymer having a polymerizable group. Is selected from Zookisazoru precursors, it is a manufacturing method of a heterocyclic ring-containing polymer precursor materials are particularly preferred.

<Heterocycle-containing polymer precursor material>
The present invention also discloses a heterocycle-containing polymer precursor material obtained by a method for producing the heterocycle-containing polymer precursor material.
A first embodiment of the heterocyclic-containing polymer precursor material of the present invention is a heterocyclic-containing polymer precursor material selected from a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group. The rate of change between the mass of the polymerization inhibitor in the heterocycle-containing polymer precursor material obtained by dividing the heterocycle-containing polymer precursor material into four parts and the mass of the polymerization inhibitor in the entire heterocycle-containing polymer precursor material is Are heterocycle-containing polymer precursor materials that are each ± 10% or less.
A second embodiment of the heterocyclic-containing polymer precursor material of the present invention is a heterocyclic-containing polymer precursor material selected from a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group. The rate of change between the mass of the polymerization inhibitor in the sample collected from 1 g each of the four heterocycle-containing polymer precursor materials and the mass of the polymerization inhibitor in the entire heterocycle-containing polymer precursor material. Are heterocycle-containing polymer precursor materials that are each ± 10% or less.
The third embodiment of the heterocyclic ring-containing polymer precursor material of the present invention is obtained by adding 1 g from any four positions of the heterocyclic ring-containing polymer precursor material obtained by the method for producing the heterocyclic ring-containing polymer precursor material of the present invention. The rate of change between the mass of the polymerization inhibitor in each sample collected and the mass of the polymerization inhibitor in the entire heterocyclic ring-containing polymer precursor material is ± 10% or less, respectively. .
In the first to third embodiments, the rate of change from the mass of the polymerization inhibitor in the entire heterocyclic ring-containing polymer precursor material is preferably 8% or less, more preferably ± 6% or less, and ± 4 % Or less is more preferable.
In the present invention, in the first to third embodiments, the heterocyclic ring-containing polymer precursor material further contains a polymerization inhibitor in a proportion of 0.001 to 10% by mass of the heterocyclic ring-containing polymer precursor material. Is preferred.
The lower limit of the amount of the polymerization inhibitor in the heterocyclic ring-containing polymer precursor material is more preferably 0.1% by mass or more, and can also be 0.2% by mass or more. The upper limit of the amount of the polymerization inhibitor in the heterocyclic-containing polymer precursor material is more preferably 9% by mass or less, may be 7% by mass or less, may be 5% by mass or less, The amount may be 1.0% by mass or less, particularly 0.7% by mass or less, and more particularly 0.4% by mass or less.
The heterocyclic ring-containing polymer precursor material of the present invention may be in a dry solid state or may contain a solvent such as a second solvent. As a preferred embodiment, 95% by mass or more of the heterocyclic ring-containing polymer precursor material is exemplified by a heterocyclic ring-containing polymer precursor.

<Composition>
As long as the composition containing the heterocyclic ring-containing polymer precursor material of the present invention contains the heterocyclic ring-containing polymer precursor material, the other components are not particularly defined. Ingredients can be blended. The composition containing the heterocyclic-containing polymer precursor material of the present invention is preferably a photosensitive resin composition.
The photosensitive resin composition of the present invention contains a heterocyclic-containing polymer precursor material and a photopolymerization initiator. The photosensitive resin composition of the present invention is preferably used as a negative photosensitive resin composition. When used as a negative photosensitive resin composition, a polymerizable compound may be included. The polymerizable compound preferably includes a compound having an ethylenically unsaturated bond. Furthermore, a thermal polymerization initiator, a corrosion inhibitor, a thermal base generator, a polymerization inhibitor, and the like may be included.
The photosensitive resin composition in the present invention may be a positive photosensitive resin composition. In particular, in the case of a positive photosensitive resin composition, it is preferable that the heterocyclic ring-containing polymer precursor material contains a polybenzoxazole precursor. When used as a positive photosensitive resin composition, it may contain a polymerizable compound.
The photosensitive resin composition used in the present invention may further contain a ring-closed structure polyimide, polybenzoxazole, or the like without departing from the spirit of the present invention.

The content of the heterocyclic-containing polymer precursor material in the photosensitive resin composition of the present invention is preferably 20 to 100% by mass, and preferably 50 to 99% by mass, based on the total solid content of the photosensitive resin composition. More preferred is 70 to 98% by mass, and particularly preferred is 80 to 95% by mass.
Hereinafter, the component which the photosensitive resin composition of this invention may contain is demonstrated. It goes without saying that the present invention may contain components other than these, and these components are not essential.

<< photopolymerization initiator >>
The photosensitive resin composition of the present invention may contain a photopolymerization initiator. In particular, when the photosensitive resin composition contains a photo radical polymerization initiator, the photosensitive resin composition is applied to a semiconductor wafer or the like to form a photosensitive resin composition layer, and then irradiated with light to generate radicals. Curing takes place and the solubility in the light irradiation part can be reduced. For this reason, for example, by exposing the photosensitive resin composition layer through a photomask having a pattern in which only the electrode portion is masked, it is possible to easily produce regions having different solubility according to the electrode pattern. There is.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light in the ultraviolet region to the visible region are preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

As the photopolymerization initiator, known compounds can be used without limitation. For example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group), Acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo series Examples thereof include compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, and the like.

Examples of halogenated hydrocarbon derivatives having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in GB 1388492, a compound described in JP-A-53-133428, a compound described in DE 3337024, F . C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, Examples include the compounds described in Japanese Patent No. 4221976.

Examples of the compounds described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloro Methyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl)- 1,3,4-oxadiazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) 1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl)- 1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.).

Further, as photopolymerization initiators other than those described above, compounds described in paragraph No. 0086 of JP-A-2015-087611, JP-A-53-133428, JP-B-57-1819, JP-A-57-6096 And the compounds described in US Pat. No. 3,615,455, and the like, the contents of which are incorporated herein.

Examples of the ketone compound include compounds described in paragraph No. 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
Kayacure DETX (manufactured by Nippon Kayaku) is also suitably used as a commercial product.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a light source of 365 nm or 405 nm can also be used.
As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

More preferred examples of the photopolymerization initiator include oxime compounds. Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Preferred oxime compounds include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy And imino-1-phenylpropan-1-one.

Examples of the oxime compounds include JCSPerkin II (1979) p.1653-1660, JCSPerkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP 2000 -66385, JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166, and the like.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), and N-1919 (manufactured by ADEKA) are also preferably used. Also, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (made by ADEKA) can be used.

Further, a compound described in JP-A-2009-519904, in which an oxime is linked to the N-position of the carbazole ring, a compound described in US Pat. A compound described in JP2010-15025A and US Patent Publication No. 2009-292039, a ketoxime compound described in WO2009 / 131189, a triazine skeleton and an oxime skeleton in the same molecule. In addition, a compound described in US Pat. No. 7,556,910, a compound described in JP-A-2009-221114, which has an absorption maximum at 405 nm, and good sensitivity to a g-ray light source may be used.
In addition, the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can also be suitably used. Among the cyclic oxime compounds, in particular, the cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorption and high sensitivity. It is preferable from the viewpoint.
In addition, a compound described in JP-A-2009-242469, which is a compound having an unsaturated bond at a specific site of the oxime compound, can also be suitably used.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in paragraph No. 0345 of JP-T-2014-500852, JP Examples thereof include compound (C-3) described in paragraph No. 0101 of 2013-164471. Specific examples include the following compounds.

As the most preferred oxime compounds, there are oxime compounds having a specific substituent as disclosed in JP-A-2007-267979, oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, and the like.

Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryls from the viewpoint of exposure sensitivity. Selected from the group consisting of imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. Compounds are preferred.
More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, and acetophenone compounds, and more preferred are trihalomethyltriazine compounds. , Α-aminoketone compounds, oxime compounds, triarylimidazole dimers and benzophenone compounds, and oxime compounds are most preferred.

When the photosensitive resin composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1% by mass with respect to the total solid content of the photosensitive resin composition. -20% by mass, more preferably 0.1-10% by mass.
Only one type of photopolymerization initiator may be used, or two or more types may be used. When there are two or more photopolymerization initiators, the total is preferably in the above range.

<< polymerizable compound >>
The photosensitive resin composition of the present invention preferably contains a polymerizable compound. By containing a polymerizable compound, a cured film having more excellent heat resistance can be formed.
The polymerizable compound is a compound having a polymerizable group, and a known compound that can be crosslinked by a radical, an acid, a base, or the like can be used. Examples of the polymerizable group include the polymerizable group described in the above-mentioned heterocyclic ring-containing polymer precursor.
The compound having an ethylenically unsaturated bond used in the present invention is more preferably a compound containing two or more ethylenically unsaturated groups.
The polymerizable compound may be in any chemical form such as a monomer, a prepolymer, an oligomer or a mixture thereof, and a multimer thereof.

In the present invention, a monomer type polymerizable compound (hereinafter also referred to as a polymerizable monomer) is a compound different from a polymer compound. The polymerizable monomer is typically a low molecular compound, preferably a low molecular compound having a molecular weight of 2,000 or less, more preferably a low molecular compound having a molecular weight of 1,500 or less, and a molecular weight of 900 or less. More preferably, it is a low molecular weight compound. The molecular weight of the polymerizable monomer is usually 100 or more.
The oligomer type polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 polymerizable monomers are bonded. As the molecular weight, the polystyrene-reduced weight average molecular weight by gel permeation chromatography (GPC) method is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and more preferably 2,000 to 2,000. Most preferred is 10,000.

In the present invention, the number of functional groups of the polymerizable compound means the number of polymerizable groups in one molecule.
From the viewpoint of resolution, the polymerizable compound preferably contains at least one bifunctional or higher functional polymerizable compound containing two or more polymerizable groups, and preferably contains at least one trifunctional or higher functional polymerizable compound. More preferred.
Moreover, it is preferable that the polymeric compound in this invention contains at least 1 sort (s) of trifunctional or more polymeric compounds also from the point that a three-dimensional crosslinked structure can be formed and heat resistance can be improved. Also, a mixture of a bifunctional or lower polymerizable compound and a trifunctional or higher functional polymerizable compound may be used.

<<< Compound having an ethylenically unsaturated bond >>>
As a group having an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth) acryloyl group and a (meth) allyl group are preferable, and a (meth) acryloyl group is more preferable.

Specific examples of the compound having an ethylenically unsaturated bond include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters, amides thereof, and these Preferred are an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, an amide of an unsaturated carboxylic acid and a polyvalent amine compound, and a multimer thereof. In addition, an addition reaction product of an ester or amide of an unsaturated carboxylic acid having a nucleophilic substituent such as a hydroxy group, an amino group, or a mercapto group, and a monofunctional or polyfunctional isocyanate or epoxy, A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used. In addition, an addition reaction product of an ester or amide of an unsaturated carboxylic acid having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol; A substitution reaction product of an ester or amide of an unsaturated carboxylic acid having a leaving substituent such as a group or a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.

Specific examples of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate. , Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetra Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Pentaerythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, isocyanuric acid ethylene oxide modified triacrylate, polyester acrylate There are oligomers and the like.

Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxyp Epoxy) phenyl] dimethyl methane, there are bis [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.

Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. The compounds having an aromatic skeleton described in JP-A No. 59-5241, JP-A-2-226149, compounds containing an amino group described in JP-A 1-165613, and the like are also preferably used. It is done.

Specific examples of amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic. Examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

Examples of other preferable amide monomers include monomers having a cyclohexylene structure described in JP-B No. 54-21726.

In addition, urethane-based addition-polymerizable monomers produced using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. Examples thereof include a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula to a polyisocyanate compound having two or more isocyanate groups.
_{^{_{CH 2 = C (R 4)}}} COOCH 2 CH (R 5) OH
(Wherein, ^{R 4} and ^{R 5} represents H or CH _3.)
Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in JP 17654, JP-B 62-39417, and JP-B 62-39418 are also suitable.

As the compound having an ethylenically unsaturated bond, the compounds described in paragraph numbers 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

Moreover, as a compound which has an ethylenically unsaturated bond, the compound which has a boiling point of 100 degreeC or more under a normal pressure is also preferable. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) A polyfunctional alcohol such as sosocyanurate, glycerin or trimethylolethane is added with ethylene oxide or propylene oxide and then converted to (meth) acrylate. JP-B-48-41708, JP-B-50-6034, JP-A-51 Urethane (meth) acrylates described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof. Further, the compounds described in paragraph numbers 0254 to 0257 of JP-A-2008-292970 are also suitable. Moreover, the polyfunctional (meth) acrylate obtained by making the compound which has cyclic ether groups, such as glycidyl (meth) acrylate, and an ethylenically unsaturated group, react with polyfunctional carboxylic acid etc. can be mentioned.
Further, as other preferable compounds having an ethylenically unsaturated bond, those having a fluorene ring described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc. A compound having two or more groups having an unsaturated bond, a cardo resin can also be used.
Other examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. The vinyl phosphonic acid-type compound of these can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photopolymerizable monomers and oligomers, can also be used.

In addition to the above, compounds having an ethylenically unsaturated bond represented by the following formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. A plurality of R and T present in one molecule may be the same or different.
In each of the polymerizable compounds represented by the above formulas (MO-1) to (MO-5), at least one of a plurality of R is —OC (═O) CH═CH ₂ or —OC (= O) represents a group represented by C (CH ₃ ) ═CH ₂ .
Specific examples of the compound having an ethylenically unsaturated bond represented by the above formulas (MO-1) to (MO-5) are described in paragraph numbers 0248 to 0251 of JP-A No. 2007-267979. The compound can also be suitably used in the present invention.

In addition, in JP-A-10-62986, compounds (meth) acrylates obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol described in the formulas (1) and (2) together with specific examples thereof are also provided. It can be used as a polymerizable compound.

Examples of the compound having an ethylenically unsaturated bond include dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320). Manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues are preferred. These oligomer types can also be used.

The compound having an ethylenically unsaturated bond may be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. More preferably, the ester is a polyfunctional monomer in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
As the polyfunctional monomer having an acid group, one kind may be used alone, or two or more kinds may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the polyfunctional monomer is in the above range, the production and handling properties are excellent, and further, the developability is excellent. Also, the polymerizability is good.

As the compound having an ethylenically unsaturated bond, a compound having a caprolactone structure can also be used.
The compound having a caprolactone structure and an ethylenically unsaturated bond is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, Polyfunctional alcohol such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylol melamine, ε-caprolactone modified polyfunctionality obtained by esterifying (meth) acrylic acid and ε-caprolactone Mention may be made of (meth) acrylates. Among these, a polymerizable compound having a caprolactone structure represented by the following formula (C) is preferable.

Formula (C)

(In the formula, all 6 Rs are groups represented by the following formula (D), or 1 to 5 of 6 Rs are groups represented by the following formula (D), The remainder is a group represented by the following formula (E).)

Formula (D)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents 1 or 2, and “*” represents a bond.)

Formula (E)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)

Such a polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, for example, DPCA-20 (m = 1 in the above formulas (C) to (E), The number of groups represented by D) = 2, a compound in which R ¹ is all hydrogen atoms), DPCA-30 (formula, m = 1, the number of groups represented by formula (D) = 3, R ¹ In which all are hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (D) = 6, R ¹ is all hydrogen atoms), DPCA-120 (same as above) In the formula, m = 2, the number of groups represented by formula (D) = 6, and compounds in which R ¹ is all a hydrogen atom).
In the present invention, the compounds having a caprolactone structure and an ethylenically unsaturated bond can be used alone or in admixture of two or more.

The compound having an ethylenically unsaturated bond is also preferably at least one selected from the group of compounds represented by the following formula (i) or (ii).

In the formulas (i) and (ii), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) —, y Each independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In the formula (i), the total number of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40 . However, when the total of each m is 0, any one of X is a carboxyl group.
In formula (ii), the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60 is there. However, when the total of each n is 0, any one of X is a carboxyl group.

In the formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In formula (i) or formula (ii), — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) — is bonded to X at the end on the oxygen atom side. The form is preferred. In particular, in the formula (ii), a form in which all six Xs are acryloyl groups is preferable.

The compound represented by the formula (i) or (ii) is a conventionally known step, which is a step of bonding a ring-opening skeleton by subjecting pentaerythritol or dipentaerythritol to a ring-opening addition reaction of ethylene oxide or propylene oxide. The compound can be synthesized from the step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opened skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by formula (i) or (ii).

Among the compounds represented by formulas (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”). Among them, exemplary compounds (a), (f) b), (e) and (f) are preferred.

Examples of commercially available polymerizable compounds represented by formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and pliers manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six lenoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the compound having an ethylenically unsaturated bond include those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane acrylates and urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. It is. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are described as polymerizable compounds. Monomers can also be used.
Commercially available compounds having an ethylenically unsaturated bond include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp 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), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Manufactured by Kyoeisha Chemical Co., Ltd.), Bremer PME400 (manufactured by NOF Corporation) and the like.

The compound having an ethylenically unsaturated bond preferably has a partial structure represented by the following formula from the viewpoint of heat resistance. However, * in the formula is a connecting hand.

Specific examples of the compound having an ethylenically unsaturated bond having the above partial structure include, for example, trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, and isocyanuric acid ethylene oxide-modified tri (meth). Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylol methane tetra ( (Meth) acrylate etc. are mentioned, and these polymerizable compounds can be particularly preferably used in the present invention.

In the photosensitive resin composition, the content of the compound having an ethylenically unsaturated bond is 1 to 50% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of good polymerizability and heat resistance. preferable. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. As the compound having an ethylenically unsaturated bond, one kind may be used alone, or two or more kinds may be mixed and used.
The mass ratio of the heterocyclic ring-containing polymer precursor material to the compound having an ethylenically unsaturated bond (heterocyclic ring-containing polymer precursor material / polymerizable compound) is preferably 98/2 to 10/90, and 95/5. ~ 30/70 is more preferable, and 90/10 to 50/50 is most preferable. When the mass ratio of the heterocyclic ring-containing polymer precursor material and the compound having an ethylenically unsaturated bond is in the above range, a cured film having excellent polymerizability and heat resistance can be formed.

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

(AM1)

(In the formula, t represents an integer of 1 to 20, R ⁴ represents a t-valent organic group having 1 to 200 carbon atoms, R ⁵ represents a hydroxyl group, or the following formula (AM2) or the following formula (AM3 ) Represents a group represented by

(AM2), (AM3)

(Wherein R ⁶ represents an organic group having 1 to 10 carbon atoms)

The content of the compound represented by the formula (AM1) with respect to 100 parts by mass of the heterocyclic-containing polymer precursor material is preferably 5 parts by mass or more and 40 parts by mass or less. More preferably, it is 10 to 35 mass parts. Further, in the total polymerizable compound, the compound represented by the following formula (AM4) is contained in an amount of 10% by mass or more and 90% by mass or less, and the compound represented by the following formula (AM5) in the total polymerizable compound is 10% by mass or more. It is also preferable to contain 90 mass% or less.

(AM4)

(Wherein R ⁴ represents a divalent organic group having 1 to 200 carbon atoms, and R ⁵ represents a hydroxyl group or a group represented by the following formula (AM2) or the following formula (AM3)).

(AM5)

(Wherein u represents an integer of 3 to 8, R ⁴ represents a u-valent organic group having 1 to 200 carbon atoms, and R ⁵ represents a hydroxyl group, the following formula (AM2) or the following formula ( A group represented by AM3).)

(AM2), (AM3)

(Wherein R ⁶ represents an organic group having 1 to 10 carbon atoms)

By setting it as this range, when a photosensitive resin composition layer is formed on an uneven substrate, cracks are less likely to occur. Furthermore, it is excellent in pattern processability, and can have high heat resistance such that the 5% weight loss temperature is preferably 350 ° C. or higher, more preferably 380 ° C. or higher.
Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML. -PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKACALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl- Examples thereof include p-cresol.

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

<<< Epoxy Compound (Compound Having Epoxy Group) >>>
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy compound undergoes a cross-linking reaction at 200 ° C. or lower and does not cause a dehydration reaction in the cross-linking reaction, so that film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective for low-temperature curing and low warpage of the photosensitive resin composition.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and the warpage can be further reduced. Moreover, since the flexibility is high, a cured film having excellent elongation and the like can be obtained. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of the epoxy compound include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl Examples include, but are not limited to, epoxy group-containing silicones such as (roxypropyl) siloxane. Specifically, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-150, Epicron (registered trademark) EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Rikaresin (registered trademark) BEO-60E , New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (trade name, (Ltd.) and the like Adeka). Among these, an epoxy resin containing a polyethylene oxide group is preferable in terms of excellent low warpage and heat resistance. For example, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Licaredin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.

The content of the epoxy compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the heterocyclic-containing polymer precursor material. If the blending amount is 5 parts by mass or more, warpage of the cured film can be further suppressed, and if it is 50 parts by mass or less, pattern filling associated with reflow during sampling heating (curing) can be further suppressed.

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

The content of the oxetane compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the heterocyclic-containing polymer precursor material.

<<< benzoxazine compound (compound having a benzoxazolyl group) >>>
Since a benzoxazine compound undergoes a crosslinking reaction by a ring-opening addition reaction, no degassing due to curing occurs and shrinkage due to heat is small. For this reason, generation | occurrence | production of curvature can be made well.

Preferred examples of the benzoxazine compound include Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzoxazine. Compounds. These may be used alone or in combination of two or more.

The content of the benzoxazine compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the heterocyclic-containing polymer precursor material.

<< Resin containing phenolic OH group >>
When the photosensitive resin composition of the present invention is an alkali-developable positive-type photosensitive resin composition, the inclusion of a resin containing a phenolic OH group adjusts the solubility in an alkaline developer and is good. This is preferable in that sensitivity can be obtained.
Preferred examples of the resin containing a phenolic OH group include novolak resins and polyhydroxystyrene resins.

<<< Novolac resin >>>
The novolak resin can be obtained by polycondensing phenols and aldehydes by a known method. Two or more novolac resins may be combined.
Preferred examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3 , 5-trimethylphenol, 3,4,5-trimethylphenol and the like. Particularly preferred are phenol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol and 2,3,5-trimethylphenol. Two or more of these phenols may be used in combination. From the viewpoint of solubility in an alkali developer, m-cresol is preferable, and a combination of m-cresol and p-cresol is also preferable. That is, the novolak resin preferably includes an m-cresol residue or a cresol novolak resin containing an m-cresol residue and a p-cresol residue. At this time, the molar ratio of m-cresol residue to p-cresol residue (m-cresol residue / p-cresol residue, m / p) in the cresol novolak resin is preferably 1.8 or more. If it is this range, the moderate solubility to an alkali developing solution will be shown, and favorable sensitivity will be obtained. More preferably, it is 4 or more.
Preferred examples of the aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like. Two or more of these aldehydes may be used.

Further, a wholly aromatic novolak resin obtained by polycondensation with an acidic catalyst using a compound represented by the following formula (Phe) as phenols and a compound represented by the following formula (Ald) as aldehydes, It is preferable at the point which can provide high heat resistance to the cured film of the photosensitive resin composition of this invention.

Formula (Phe)

In the formula (Phe), R ₁ represents an organic group selected from an alkyl group having 1 to 20 carbon atoms and an alkoxy group, and p is an integer of 1 to 3, preferably 2 to 3 It is.

Formula (Ald)

In the formula (Ald), R ₂ represents a group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and a hydroxy group, and q is an integer of 0 to 3 inclusive.

As the phenol compound represented by the above formula (Phe), a phenol compound having 1 to 3 and preferably 2 to 3 substituents is used, and the substituent has 1 to 20 carbon atoms. It is an organic group selected from the following alkyl groups and alkoxy groups. Specific examples of the alkyl group and alkoxy group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a methoxy group, and an ethoxy group. Preferred examples of such a phenol compound include o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, and 3,4-dimethylphenol. 3,5-dimethylphenol, 2-methyl-3-ethylphenol, 2-methyl-3-methoxyphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,3,6- Trimethylphenol or the like can be used. Among these, although not particularly limited, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,6-dimethylphenol Those selected from among these are preferred. Furthermore, these phenols can be used alone or in combination of two or more.
By using a phenol compound having 1 or more and 3 or less, preferably 2 or more and 3 or less substituents as the phenol compound, the phenol resin has sufficient heat resistance necessary for the composition by suppressing intramolecular rotation. Can be obtained.

As the aromatic aldehyde compound represented by the above formula (Ald), an aromatic aldehyde compound which is unsubstituted or has 3 or less substituents is used, and the substituent has 1 to 20 carbon atoms. An organic group selected from an alkyl group, an alkoxy group and a hydroxy group. Specific examples of the alkyl group and alkoxy group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a methoxy group, and an ethoxy group. Examples of such aromatic aldehyde compounds include benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehuman, 2,3-dimethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 2,6-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, 2,3,4-trimethylbenzaldehyde, 2,3,5-trimethylbenzaldehyde, 2,3,6-trimethylbenzaldehyde, 2, 4,5-trimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde, 3,4,5-trimethylbenzaldehyde, 4-ethylbenzaldehyde, 4-tert-butylbenzaldehyde, 4-i Butylbenzaldehyde, 4-methoxybenzaldehyde, salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 3-methylsalicylaldehyde, 4-methylsalicylaldehyde, 2-hydroxy-5-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2 , 5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, and the like can be used, but are not limited to these. Among them, R ₂ in the formula (Ald) is hydrogen, a methyl group, or a hydroxy group. Certain aromatic aldehyde compounds are preferred, and those selected from the aromatic aldehyde compounds shown below are more preferred. Furthermore, these aldehydes can be used alone or in combination of two or more.

In the synthesis reaction for obtaining a novolak resin from phenols and aldehydes, it is preferable to react 0.5 mol or more and 2 mol or less of an aldehyde compound with respect to 1 mol of phenol compound, and 0.6 mol or more and 1.2 mol or less. It is more preferable to make it react by 0.7 mol or more, and it is especially preferable to make it react by 0.7 mol or more and 1.0 mol or less. By setting it as the said molar ratio, the molecular weight which can exhibit a characteristic sufficient as a composition can be obtained.

In the polycondensation reaction between phenols and aldehydes, an acidic catalyst is usually used. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, p-toluenesulfonic acid, and the like. The amount of these acidic catalysts used is usually 1 × 10 ⁻⁵ to 5 × 10 ⁻¹ mol per 1 mol of phenols. In the polycondensation reaction, water is usually used as a reaction medium. However, when a heterogeneous system is formed from the beginning of the reaction, a hydrophilic solvent or a lipophilic solvent is used as the reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol, butanol and propylene glycol monomethyl ether; and cyclic ethers such as tetrahydrofuran and dioxane. Examples of the lipophilic solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. The amount of these reaction media used is usually 20 to 1,000 parts by mass per 100 parts by mass of the reaction raw material.

The reaction temperature of the polycondensation can be appropriately adjusted according to the reactivity of the raw material, but is usually 10 to 200 ° C. As a polycondensation reaction method, phenols, aldehydes, acidic catalysts, etc. are charged all at once and reacted, or phenols, aldehydes, etc. are added as the reaction proceeds in the presence of acidic catalysts, etc. Can be adopted as appropriate. After completion of the polycondensation reaction, in order to remove unreacted raw materials, acidic catalyst, reaction medium, etc. existing in the system, the reaction temperature is generally increased to 130 to 230 ° C., and volatile components are reduced under reduced pressure. Remove and recover novolac resin.

The polystyrene equivalent weight average molecular weight (Mw) of the novolak resin is preferably 1,000 or more, more preferably 2,000 or more. Moreover, 5,000 or less is preferable. Within this range, good sensitivity can be obtained.

The content of the novolak resin is preferably 1 part by mass or more and 70 parts by mass or less, and more preferably 10 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the heterocyclic-containing polymer precursor material. Within this range, a pattern that is highly sensitive and does not flow after heat treatment at a high temperature can be obtained. Only one type of novolac resin may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<<< Polyhydroxystyrene resin >>>
The hydroxystyrene resin is a polymer containing hydroxystyrene and / or a derivative thereof, and is not particularly limited, but may be a copolymer containing hydroxystyrene and / or a derivative thereof and a monomer other than these. Examples of the monomer used here include ethylene, propylene, 1-butene, 2-methylpropene, styrene and derivatives thereof. Among these, from the viewpoint of easily adjusting the solubility in an aqueous alkali solution, a copolymer composed of hydroxystyrene and / or a derivative thereof and styrene and / or a derivative thereof is preferable. The above derivatives are those in which an alkyl group, an alkoxy group, a hydroxy group or the like is substituted at the ortho, meta, and para positions of hydroxystyrene and the aromatic ring of styrene. The hydroxystyrene of the hydroxystyrene resin may be any of orthohydroxystyrene, metahydroxystyrene, and parahydroxystyrene. A plurality of the above hydroxystyrenes may be mixed.

The constituent ratio of the hydroxystyrene and its derivative in the hydroxystyrene resin is preferably 50% or more, and more preferably 60% or more. The upper limit is preferably 90% or less, and more preferably 80% or less. By setting it as the said range, it has the effect excellent in coexistence of reduction of the post-exposure residue of an exposure part, and high sensitivity.

Among these, a hydroxystyrene resin having a repeating structural unit represented by the following formula (PHS-1) is preferable.

Formula (PHS-1)

In the formula (PHS-1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a represents 1 to 4, b represents 1 to 3, and a + b is in the range of 1 to 5. . R ₂ represents an atom or one group selected from a hydrogen atom, a methyl group, an ethyl group, and a propyl group.

Examples of the structural unit represented by the above formula (PHS-1) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol and the like. Among these aromatic vinyl compounds having a phenolic hydroxyl group and aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene, one or two or more of them are polymerized by known methods. It is obtained by subjecting a part of the obtained polymer or copolymer to an addition reaction of an alkoxy group by a known method.
As the aromatic vinyl compound having a phenolic hydroxyl group, p-hydroxystyrene and / or m-hydroxystyrene is preferably used, and styrene is preferably used as the aromatic vinyl compound.

Among the hydroxystyrene resins having a repeating structural unit represented by the above formula (PHS-1), the following formula (PHS-2) is used from the viewpoint of convenience in which sensitivity can be further improved and solubility in an alkali developer can be adjusted. ), A copolymer containing a structural unit represented by the formula (PHS-3) and the formula (PHS-4) is preferable. Furthermore, from the viewpoint of solubility in an alkali developer, the structural unit of the formula (PHS-4) is preferably 50 mol% or less.

Formula (PHS-2)

In the formula (PHS-2), R ₄ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, c represents 1 to 4, d represents 1 to 3, and c + d is in the range of 2 to 5. . R ₃ represents an atom or one group selected from a hydrogen atom, a methyl group, an ethyl group, and a propyl group.

Formula (PHS-3)

In the formula (PHS-3), R ₅ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e represents 1 to 5.

Formula (PHS-4)

In the formula (PHS-4), R ₆ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

The weight average molecular weight (Mw) of the hydroxystyrene resin is preferably 1,000 or more, more preferably 2,000 or more, particularly preferably 2,500 or more, and preferably 10,000 or less, more preferably 8, 000 or less, and particularly preferably 7,000 or less. By setting it as the said range, it has the effect which is excellent in coexistence of high-sensitivity and the normal temperature storage stability of a varnish.
The content of the hydroxystyrene resin is preferably 1 part by mass or more and 70 parts by mass or less, and more preferably 10 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the heterocyclic ring-containing polymer precursor material. Within this range, a pattern that is highly sensitive and does not flow after heat treatment at a high temperature can be obtained. Only one kind of hydroxystyrene resin may be used or two or more kinds thereof may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< thermal base generator >>
The photosensitive resin composition of the present invention may contain a thermal base generator.
The type of the thermal base generator is not particularly defined, but is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having an pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one kind. Here, pKa1 represents a logarithmic representation (−Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the polyvalent acid.
By mix | blending such a compound, the cyclization reaction of a polyimide precursor can be performed at low temperature, and it can be set as the photosensitive resin composition excellent in stability more. Moreover, since the base is not generated unless heated, the thermal base generator can suppress cyclization of the polyimide precursor during storage even if it coexists with the polyimide precursor, and is excellent in storage stability.

The thermal base generator in the present invention is at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation. including.
Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can accelerate the cyclization reaction of the polyimide precursor, thereby cyclizing the polyimide precursor. Can be performed at low temperatures. In addition, even if these compounds coexist with a polyimide precursor that is cured by cyclization with a base, since the cyclization of the polyimide precursor hardly proceeds unless heated, a polyimide precursor composition having excellent stability can be obtained. Can be prepared.
In the present specification, an acidic compound means that 1 g of a compound is collected in a container, and 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added to the mixture at room temperature for 1 hour. The value obtained by stirring and measuring the obtained solution at 20 ° C. using a pH meter is less than 7.

In the present invention, the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C. The upper limit of the base generation temperature is more preferably 190 ° C. or lower, still more preferably 180 ° C. or lower, and even more preferably 165 ° C. or lower. The lower limit of the base generation temperature is more preferably 130 ° C or higher, and still more preferably 135 ° C or higher.
If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, a base is unlikely to be generated during storage, so that a polyimide precursor composition having excellent stability can be prepared. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C. or lower, the cyclization temperature of the polyimide precursor can be lowered. The base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.

In the present invention, the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amine has high basicity, the cyclization temperature of a polyimide precursor can be made lower. The base generated by the thermal base generator preferably has a boiling point of 80 ° C. or higher, preferably 100 ° C. or higher, and most preferably 140 ° C. or higher. The molecular weight of the generated base is preferably 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The molecular weight value is a theoretical value obtained from the structural formula.

In the present invention, the acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the formula (1) described later.

In the present invention, the ammonium salt (A2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.), or 40 ° C. or higher (preferably 120 to 200 ° C.). ) May be a compound other than an acidic compound that generates a base when heated.

<<< Ammonium salt >>>
In the present invention, the ammonium salt means a salt of an ammonium cation represented by the following formula (1) or formula (2) and an anion. The anion may be bonded to any part of the ammonium cation via a covalent bond, and may be outside the molecule of the ammonium cation, but is preferably outside the molecule of the ammonium cation. In addition, that an anion exists outside the molecule | numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple | bonded through a covalent bond. Hereinafter, the anion outside the molecule of the cation moiety is also referred to as a counter anion.

In the formula, R ¹ to R ⁶ each independently represents a hydrogen atom or a hydrocarbon group, and R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ⁷ may be bonded to each other to form a ring.

In the present invention, the ammonium salt preferably has an anion having an pKa1 of 0 to 4 and an ammonium cation. The upper limit of the anion pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is more preferably 0.5 or more, and further preferably 1.0 or more. If the pKa1 of the anion is in the above range, the polyimide precursor can be cyclized at a low temperature, and further, the stability of the polyimide precursor composition can be improved. If pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base without heating can be suppressed, and the stability of the polyimide precursor composition is good. If pKa1 is 0 or more, the generated base is hardly neutralized, and the cyclization efficiency of the polyimide precursor is good.
The kind of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it can be set as the thermal base generator which can improve more stability, sclerosis | hardenability, and developability of a polyimide precursor composition. In particular, the stability, curability and developability of the polyimide precursor composition can be further improved by using an anion of a divalent carboxylic acid.
In the present invention, the carboxylic acid anion is preferably a carboxylic acid anion having a pKa1 of 4 or less. pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. According to this aspect, the stability of the polyimide precursor composition can be further improved.
Here, pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid. Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Compilation: Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) are used.

In the present invention, the carboxylate anion is preferably represented by the following formula (X1).

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

In the present invention, the electron-withdrawing group means a group having a positive Hammett's substituent constant σm. Here, σm is a review by Yugo Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) P.I. 631-642. The electron-withdrawing group of the present invention is not limited to the substituents described in the above documents.
Examples of substituents in which σm has a positive value include, for example, CF ₃ group (σm = 0.43), CF ₃ CO group (σm = 0.63), HC≡C group (σm = 0.21), CH ₂ ═CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH═CH group (σm = 0.21), PhCO group (σm = 0.34), H ₂ NCOCH ₂ group (σm = 0.06), and the like. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

In the present invention, EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).

In the formula, R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group, or a carboxyl group, and Ar represents an aromatic group.

In the present invention, the carboxylate anion is also preferably represented by the following formula (X).

In the formula (X), L ¹⁰ represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, —NR ^X —, and a combination thereof, and R ^X represents a hydrogen atom Represents an alkyl group, an alkenyl group or an aryl group.

Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion. These can be preferably used.

The ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-6).

In the above formula, R ¹⁰¹ represents an n-valent organic group,
R ¹⁰² to R ¹¹¹ each independently represents a hydrogen atom or a hydrocarbon group,
R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group,
R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring,
Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group,
n represents an integer of 1 or more,
m represents an integer of 0 to 5.

<<< Compound represented by Formula (1) >>>
In the present invention, the acidic compound is also preferably a compound represented by the following formula (1). This compound is acidic at room temperature, but by heating, the carboxyl group is lost by decarboxylation or dehydration cyclization, and the amine site that has been neutralized and inactivated becomes active. It becomes sex. Hereinafter, Formula (1) is demonstrated.

In Formula (1), A ¹ represents a p-valent organic group, R ¹ represents a monovalent organic group, L ¹ represents an (m + 1) -valent organic group, m represents an integer of 1 or more, p represents an integer of 1 or more.

In the present invention, the compound represented by the formula (1) is preferably a compound represented by the following formula (1a).

In formula (1a), A ¹ represents a p-valent organic group, L ¹ represents an (m + 1) -valent linking group, L ² represents an (n + 1) -valent linking group, and m represents an integer of 1 or more. N represents an integer of 1 or more, and p represents an integer of 1 or more.
A ¹ , L ¹ , L ² , m, n, and p in the formula (1a) have the same meaning as the range described in the formula (1).

Specific examples of the thermal base generator in the present invention are described below, but the present invention is not limited to these. These can be used alone or in admixture of two or more. Me in the following formulas represents a methyl group.

As the thermal base generator used in the present invention, those described in Paragraph Nos. 0015 to 0055 of Japanese Patent Application No. 2015-034388 are also preferably used, the contents of which are incorporated herein.

When a thermal base generator is used, the content of the thermal base generator in the photosensitive resin composition is preferably 0.1 to 50% by mass with respect to the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
1 type (s) or 2 or more types can be used for a thermal base generator. When using 2 or more types, it is preferable that a total amount is the said range.

<< Photoacid generator >>
The photosensitive resin composition of the present invention may contain a photoacid generator. By containing the photoacid generator, an acid is generated in the exposed area, and the solubility of the exposed area in the alkaline aqueous solution is increased. Therefore, it can be used as a positive photosensitive resin composition.

Examples of photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Among these, a quinonediazide compound is preferably used from the viewpoint that a positive photosensitive resin composition exhibiting an excellent dissolution inhibiting effect and having high sensitivity and little film loss can be obtained. Moreover, you may contain 2 or more types of photo-acid generators. Thereby, the ratio of the dissolution rate of an exposed part and an unexposed part can be enlarged more, and a highly sensitive positive type photosensitive resin composition can be obtained.

As quinonediazide compounds, quinonediazide sulfonic acid is ester-bonded to a polyhydroxy compound, quinonediazide sulfonic acid is sulfonamide-bonded to a polyamino compound, and quinonediazide sulfonic acid is ester-bonded and / or sulfonamide to a polyhydroxypolyamino compound. Examples include those that are combined. By using such a quinonediazide compound, a positive photosensitive resin composition sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp which is a general ultraviolet ray is obtained. be able to. In addition, all the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may not be substituted with quinonediazide, but it is preferable that two or more functional groups per molecule are substituted with quinonediazide. .
As an example, the following compounds are exemplified.

In the above compound, 1 to 10% of the whole Q may be a hydrogen atom, and 4 to 6% may be a hydrogen atom.

Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC , DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TM -HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Honshu Chemical Industry), BIR-OC, BIP-PC, BIR-PC, BIR- PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, manufactured by Asahi Organic Materials Industries), 2,6-dimethoxy Methyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol , BisP-AP (above, trade name, Honshu Chemical Ltd.), but such a novolak resin include, but are not limited to.

Examples of polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diamino. Examples thereof include, but are not limited to, diphenyl sulfide.

In addition, examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3′-dihydroxybenzidine, and the like, but are not limited thereto.

As the quinonediazide compound, both a compound having a 5-naphthoquinonediazidesulfonyl group and a compound having a 4-naphthoquinonediazidesulfonyl group are preferably used. A compound having both of these groups in the same molecule may be used, or a compound using different groups may be used in combination.

Examples of the method for producing a quinonediazide compound include a method in which 5-naphthoquinonediazidesulfonyl chloride and a phenol compound are reacted in the presence of triethylamine. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acidic catalyst.

The content of the photoacid generator is preferably 3 to 40 parts by mass with respect to 100 parts by mass of the heterocyclic ring-containing polymer precursor material. By setting the content of the photoacid generator within this range, higher sensitivity can be achieved. Furthermore, you may contain a sensitizer etc. as needed.
Only one type of photoacid generator may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< thermal acid generator >>
The photosensitive resin composition of the present invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating, promotes cyclization of the heterocyclic ring-containing polymer precursor material and further improves the mechanical properties of the cured film, and has a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group. There is an effect of accelerating the crosslinking reaction of at least one compound selected from a compound, an epoxy compound, an oxetane compound and a benzoxazine compound.

The thermal decomposition starting temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 250 ° C. or less. In addition, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the photosensitive resin composition is applied to the substrate, and final heating (curing: about 100 to 400 after patterning by subsequent exposure and development). It is preferable to select one that generates an acid at the time of (° C.) because it can suppress a decrease in sensitivity during development.

The acid generated from the thermal acid generator is preferably a strong acid. For example, arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid, and trifluoromethane Haloalkyl sulfonic acids such as sulfonic acid are preferred. Examples of such a thermal acid generator include those described in paragraph No. 0055 of JP2013-072935A.

Among these, those that generate alkyl sulfonic acid having 1 to 4 carbon atoms or haloalkyl sulfonic acid having 1 to 4 carbon atoms are more preferable from the viewpoint that there is little residue in the cured film and physical properties of the cured film are not deteriorated.
As the thermal acid generator, methanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonic acid benzyl (4-hydroxyphenyl) methylsulfonium, Benzyl (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium methanesulfonate, (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium methanesulfonate, trifluoromethanesulfonic acid (4-hydroxyphenyl) Dimethylsulfonium, trifluoromethanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl trifluoromethanesulfonic acid (4-hydroxyphenyl) methyl Sulfonium, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium trifluoromethanesulfonate, 3- (5- ( ((Propylsulfonyl) oxy) imino) thiophene-2 (5H) -ylidene) -2- (o-tolyl) propanenitrile, 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoro Propane is preferred.

Further, the compound described in paragraph No. 0059 of JP2013-167742A is also preferable as the thermal acid generator.

When using a thermal acid generator, 0.01 mass part or more is preferable with respect to 100 mass parts of heterocyclic containing polymer precursor materials, and 0.1 mass part or more is more preferable. By containing 0.01 part by mass or more, the crosslinking reaction and the cyclization of the heterocyclic ring-containing polymer precursor material are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. Moreover, from a viewpoint of the electrical insulation of a cured film, 20 mass parts or less are preferable, 15 mass parts or less are more preferable, and 10 mass parts or less are more preferable.
One type of thermal acid generator may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Thermal polymerization initiator >>
The photosensitive resin composition of the present invention may contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator). As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used.
The thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be advanced when the cyclization reaction of the heterocyclic ring-containing polymer precursor material is advanced. In addition, when the heterocyclic ring-containing polymer precursor material contains an ethylenically unsaturated bond, the polymerization reaction of the heterocyclic ring-containing polymer precursor material can proceed together with the cyclization of the heterocyclic ring-containing polymer precursor material. Higher heat resistance can be achieved.
Thermal radical polymerization initiators include aromatic ketones, onium salt compounds, peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens. Examples thereof include a compound having a bond and an azo compound. Among these, a peroxide or an azo compound is more preferable, and a peroxide is particularly preferable.
The thermal radical polymerization initiator used in the present invention preferably has a 10-hour half-life temperature of 90 to 130 ° C, more preferably 100 to 120 ° C.
Specific examples include compounds described in paragraph numbers 0074 to 0118 of JP-A-2008-63554.
In a commercial item, perbutyl Z and park mill D (made by NOF Corporation) can be used conveniently.

When the photosensitive resin composition contains a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably 0.1 to 50% by mass with respect to the total solid content of the photosensitive resin composition, Is more preferably from 30 to 30% by weight, particularly preferably from 0.1 to 20% by weight. Further, the thermal radical polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by mass, and more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the polymerizable compound. According to this aspect, it is easy to form a cured film having more excellent heat resistance.
Only one type of thermal radical polymerization initiator may be used, or two or more types may be used. When there are two or more thermal radical polymerization initiators, the total is preferably in the above range.

<< Corrosion inhibitor >>
It is preferable to add a corrosion inhibitor to the photosensitive resin composition of the present invention. The corrosion inhibitor is added for the purpose of preventing the outflow of ions from the metal wiring. Examples of the compound include a rust inhibitor described in paragraph No. 0094 of JP2013-15701A, and JP2009-283711A. The compounds described in Paragraph Nos. 0073 to 0076, the compound described in Paragraph No. 0052 of JP 2011-59656 A, the compounds described in Paragraph Nos. 0114, 0116, and 0118 of JP 2012-194520 A are used. be able to. Among them, a compound having a triazole ring or a compound having a tetrazole ring can be preferably used. 1,2,4-triazole, 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole, 1H-tetrazole 5-methyl-1H-tetrazole is more preferred, and 1H-tetrazole is most preferred.
When a corrosion inhibitor is used, the content of the corrosion inhibitor is preferably in the range of 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the heterocyclic-containing polymer precursor material. It is the range of mass parts.
The corrosion inhibitor may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Metal adhesion improver >>
The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving the adhesion with a metal material used for electrodes and wirings. Examples of the metal adhesion improver include sulfide compounds described in paragraph numbers 0046 to 0049 of JP-A-2014-186186 and paragraph numbers 0032 to 0043 of JP-A-2013-072935. Examples of the metal adhesion improver also include the following compounds.

When a metal adhesion improver is used, the content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably 0 with respect to 100 parts by mass of the heterocyclic-containing polymer precursor material. The range is from 5 to 15 parts by mass. By setting it as 0.1 mass part or more, the adhesiveness of the film | membrane and metal after thermosetting becomes favorable, and the heat resistance of the film | membrane after hardening and mechanical characteristics become favorable by setting it as 30 mass parts or less.
Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.

<< Silane coupling agent >>
The photosensitive resin composition of the present invention preferably contains a silane coupling agent from the viewpoint of improving the adhesion to the substrate. Examples of the silane coupling agent include compounds described in paragraph numbers 0062 to 0073 of JP2014-191002, compounds described in paragraph numbers 0063 to 0071 of international publication WO2011 / 080992A1, and JP2014-191252. And compounds described in paragraph Nos. 0060 to 0061 of JP, No. 2014-41264, compounds described in paragraph Nos. 0045 to 0052 of JP-A-2014-41264, and compounds described in paragraph No. 0055 of International Publication No. WO2014 / 097594. It is also preferable to use two or more different silane coupling agents as described in paragraph numbers 0050 to 0058 of JP2011-128358A.
When a silane coupling agent is used, the content of the silane coupling agent is preferably in the range of 0.1 to 20 parts by mass, more preferably 1 to 10 parts per 100 parts by mass of the heterocyclic-containing polymer precursor material. It is the range of mass parts. When it is 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed.
Only one type of silane coupling agent may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Solution Accelerator >>
When the photosensitive resin composition of the present invention is a positive type using an alkaline developer, it is preferable to add a dissolution accelerator (a compound that promotes solubility) from the viewpoint of improving sensitivity. Examples of the solubility promoter include low molecular weight phenols (for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P (trade name, manufactured by Honshu Chemical Industry), BIR- PC, BIR-PTBP, BIR-BIPC-F (trade name, manufactured by Asahi Organic Materials Co., Ltd.), phenols described in paragraph numbers 0056 to 0062 of JP2013-152381A) and arylsulfonamide derivatives (for example, And compounds described in paragraph No. 0058 of JP2011-164454A).
When a dissolution accelerator is used, the content of the dissolution accelerator is preferably in the range of 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the heterocyclic-containing polymer precursor material. Part range.
Only one type of dissolution promoter may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Dissolution inhibitor >>
When the photosensitive resin composition of the present invention is a positive type using an alkaline developer, it contains a dissolution inhibitor (a compound that inhibits solubility) in order to adjust the solubility in the alkaline developer. Can do. As such compounds, onium salts, diaryl compounds and tetraalkylammonium salts are preferred.
Examples of the onium salt include iodonium salts such as diaryliodonium salts, sulfonium salts such as triarylsulfonium salts, diazonium salts such as phosphonium salts, aryldiazonium salts, and the like.
Examples of the diaryl compound include those in which two aryl groups such as diaryl urea, diaryl sulfone, diaryl ketone, diaryl ether, diaryl propane, and diaryl hexafluoropropane are bonded via a linking group. Groups are preferred.
Examples of the tetraalkylammonium salt include tetraalkylammonium halides in which the alkyl group is a methyl group or an ethyl group.

Among them, those showing a good dissolution inhibiting effect include diaryl iodonium salts, diaryl ureas, diaryl sulfones, tetramethyl ammonium halides, etc., and diaryl ureas include diphenyl urea, dimethyl diphenyl urea, etc. Examples of the tetramethylammonium halide include tetramethylammonium chloride, tetramethylammonium bromide, and tetramethylammonium iodide.

Among these, a diaryl iodonium salt represented by the formula (Inh) is preferable.

(Wherein, X ^- represents a counteranion, ^{R 7} and ^{R 8} each independently represents a monovalent organic group, a and b are each independently an integer of 0 to 5)

Examples of the counter anion X ⁻ include nitrate ion, boron tetrafluoride ion, perchlorate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, thiocyanate ion, chlorine ion, bromine ion, iodine ion and the like. It is done.

Examples of the diaryliodonium salt include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, and diphenyliodonium. Bromide, diphenyliodonium chloride, diphenyliodonium iodide, diphenyliodonium-8-anilinonanaphthalene-1-sulfonate and the like can be used.
Among these, diphenyliodonium nitrate, diphenyliodonium trifluoromethanesulfonate, and diphenyliodonium-8-anilinonanaphthalene-1-sulfonate are preferable because of their high effects.

In the case of containing a dissolution inhibitor, the content of the dissolution inhibitor is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the heterocyclic-containing polymer precursor material from the viewpoints of sensitivity and allowable width of development time. 0.1 to 15 parts by mass is more preferable, and 0.5 to 10 parts by mass is further preferable.
Only one type of dissolution inhibitor may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Sensitizing dye >>
The photosensitive resin composition of the present invention may contain a sensitizing dye. A sensitizing dye absorbs specific actinic radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with an amine generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like, and causes actions such as electron transfer, energy transfer, and heat generation. As a result, the amine generator, the thermal radical polymerization initiator, and the photopolymerization initiator are decomposed by causing a chemical change to generate radicals, acids, or bases.

Examples of preferable sensitizing dyes include those belonging to the following compounds and having a maximum absorption wavelength in the range of 300 nm to 450 nm. For example, polynuclear aromatics (eg, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (eg, 2,4-diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines ( For example, acridine orange, chloroflavin, acriflavine), anthraquinones (eg anthraquinone), squaryliums (eg squarylium), coumarins (eg 7-di Chiruamino 4-methylcoumarin), styryl benzenes, distyryl benzenes, carbazoles, and the like.

Among them, in the present invention, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene), thioxanthones, distyrylbenzenes, and styrylbenzenes are preferably used from the viewpoint of starting efficiency, and the anthracene skeleton is used. It is more preferable to use the compound which has. Particularly preferred specific compounds include 9,10-diethoxyanthracene and 9,10-dibutoxyanthracene.

When the photosensitive resin composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, and preferably 0.1 to 15% by mass with respect to the total solid content of the photosensitive resin composition. Is more preferable, and 0.5 to 10% by mass is even more preferable. A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

<< Chain transfer agent >>
The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in Polymer Dictionary 3rd Edition (edited by the Society of Polymer Science, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) can be preferably used.

When the photosensitive resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 100 parts by mass of the total solid content of the photosensitive resin composition. 1 to 10 parts by mass, more preferably 1 to 5 parts by mass.
Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably in the above range.

<< Polymerization inhibitor >>
In addition to the polymerization inhibitor incorporated in the heterocyclic ring-containing polymer precursor material, the photosensitive resin composition of the present invention may further contain a polymerization inhibitor.
Further polymerization inhibitors include, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2- Nitro -1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4-hydroxy-3,5 A preferred example is (tert-butyl) phenylmethane.
When the photosensitive resin composition contains a further polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the photosensitive resin composition.
The further polymerization inhibitor may be only one kind or two or more kinds. When two or more further polymerization inhibitors are used, the total is preferably within the above range.
Moreover, the photosensitive resin composition of this invention can also be set as the structure which does not mix | blend further polymerization inhibitors other than the polymerization inhibitor taken in into the heterocyclic containing polymer precursor material. When substantially not blended, the content of the further polymerization inhibitor is less than 0.01% by mass of the solid content contained in the photosensitive resin composition of the present invention, more preferably less than 0.001% by mass, in particular , Less than 0.0001% by mass.

<< Surfactant >>
Various surfactants may be added to the photosensitive resin composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
In particular, by including a fluorosurfactant, liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the uniformity of coating thickness and liquid-saving properties can be further improved. .
In the case of forming a film using a coating liquid containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid, and the coated surface The coating property of is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

The fluorine content of the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility.
Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
As the fluorosurfactant, a block polymer can also be used. Specific examples thereof include compounds described in JP-A-2011-89090.
The following compounds are also exemplified as the fluorosurfactant used in the present invention.

The weight average molecular weight of the above compound is, for example, 14,000.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, poly Oxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61 from BASF, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 15 R1), Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like. Alternatively, Pionein D-6112-W manufactured by Takemoto Yushi Co., Ltd., NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. may be used.

Specific examples of cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based surfactants. (Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.

When the photosensitive resin composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably based on the total solid content of the photosensitive resin composition. 0.005 to 1.0% by mass.
Only one type of surfactant may be used, or two or more types may be used. When there are two or more surfactants, the total is preferably in the above range.

<< Higher fatty acid derivatives, etc. >>
In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide or the like is added to the photosensitive resin composition of the present invention, and the photosensitive resin composition is dried during the coating process. It may be unevenly distributed on the surface of the object.
When the photosensitive resin composition contains a higher fatty acid derivative or the like, the content of the higher fatty acid derivative or the like is preferably 0.1 to 10% by mass with respect to the total solid content of the photosensitive resin composition.
Only one type of higher fatty acid derivative or the like may be used. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.

<< solvent >>
When making the photosensitive resin composition of this invention into a layer form by application | coating, it is preferable to mix | blend a solvent. Any known solvent can be used without limitation as long as the photosensitive resin composition can be formed into a layer.
Examples of the solvent used in the photosensitive resin composition of the present invention include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid. Butyl, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetate alkyl (eg alkyl oxyacetate, alkyl oxyacetate ethyl, alkyl oxyacetate butyl (eg methyl methoxyacetate, methoxy Ethyl acetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 2-alkyloxypropionate, Ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropyl) Ethyl pionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as diethylene glycol dimethyl ether , Tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, and As propylene glycol monopropyl ether acetate and the like, and ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and aromatic hydrocarbons Suitable examples of the sulfoxides include toluene, xylene, anisole and limonene, and sulfoxides.

The solvent is preferably in the form of a mixture of two or more from the viewpoint of improving the coated surface. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone A mixed solution composed of two or more selected from dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. In particular, the combined use of dimethyl sulfoxide and γ-butyrolactone is preferable.

When the photosensitive resin composition contains a solvent, the content of the solvent is preferably such that the total solid concentration of the photosensitive resin composition is 5 to 80% by mass from the viewpoint of applicability. More preferred is ˜70% by mass, and further more preferred is 10˜60% by mass.
One type of solvent may be sufficient and 2 or more types may be sufficient as it. When there are two or more solvents, the total is preferably in the above range.
The contents of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide are determined based on the total mass of the photosensitive resin composition from the viewpoint of film strength. Is less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.5% by weight, and still more preferably less than 0.1% by weight.

<< Other additives >>
The photosensitive resin composition of the present invention has various additives, for example, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, as necessary, as long as the effects of the present invention are not impaired. Further, an aggregation inhibitor and the like can be blended. When mix | blending these additives, it is preferable that the total compounding quantity shall be 3 mass% or less of solid content of the photosensitive resin composition.

The water content of the photosensitive resin composition of the present invention is preferably less than 5% by weight, more preferably less than 1% by weight, and even more preferably less than 0.6% by weight from the viewpoint of the coated surface.

From the viewpoint of insulation, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
In addition, as a method for reducing metal impurities that are unintentionally contained in the photosensitive resin composition, a raw material having a low metal content is selected as a raw material constituting the photosensitive resin composition. For example, the raw material to be filtered may be filtered, or the inside of the apparatus may be lined with polytetrafluoroethylene or the like, and distillation may be performed under a condition in which contamination is suppressed as much as possible.

In the photosensitive resin composition of the present invention, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass from the viewpoint of wiring corrosiveness. Especially, what exists in the state of a halogen ion is less than 5 mass ppm, More preferably, it is less than 1 mass ppm, More preferably, it is less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chloride ions and bromide ions is preferably in the above range.

<< Preparation of photosensitive resin composition >>
The photosensitive resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the composition. The pore size 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 filter material is preferably a polytetrafluoroethylene, polyethylene, or nylon filter. A filter that has been previously washed with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step. Moreover, you may pressurize and filter and the pressure to pressurize is 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Further, filtration using a filter and removal of impurities using an adsorbent may be combined. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

<Application>
The photosensitive resin composition of the present invention can be cured and used as a cured film. The method for producing a cured film of the present invention can be preferably used in the fields of insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and the like. That is, this invention also discloses the manufacturing method of a semiconductor device containing the manufacturing method of the cured film of this invention. In particular, since the resolution is good, it can be preferably used for manufacturing an interlayer insulating film for a rewiring layer in a three-dimensional mounting device. That is, this invention also discloses the manufacturing method of the interlayer insulation film for rewiring layers including the manufacturing method of the cured film of this invention. Furthermore, the cured film obtained by the manufacturing method of the cured film of this invention and the semiconductor device obtained by the manufacturing method of the cured film of this invention are disclosed.
Further, the cured film produced according to the present invention can also be used for a photoresist for electronics (galvanic resist, galvanic resist, etching resist, solder top resist).
The cured film produced according to the present invention can also be used for the production of printing plates such as offset printing plates or screen printing plates, the use for etching molded parts, the production of protective lacquers and dielectric layers in electronics, in particular microelectronics, etc. .

Next, an embodiment of a semiconductor device using the composition as an interlayer insulating film for a rewiring layer will be described.
A semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a stacked body 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are stacked is arranged on a wiring board 120.
In this embodiment, the case where the number of stacked semiconductor elements (semiconductor chips) is four will be mainly described. However, the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. It may be a layer, 8 layers, 16 layers, 32 layers, or the like. Moreover, one layer may be sufficient.

Each of the plurality of semiconductor elements 101a to 101d is made of a semiconductor wafer such as a silicon substrate.
The uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof.
The semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) provided integrally with the through electrodes are provided on both surfaces of each semiconductor element.

The stacked body 101 has a structure in which a semiconductor element 101a having no through electrode and semiconductor elements 101b to 101d having through electrodes 102b to 102d are flip-chip connected.
That is, the electrode pad of the semiconductor element 101a having no through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the adjacent through electrode 102b are connected by the metal bump 103a such as a solder bump, The connection pad on the other side of the semiconductor element 101b having the electrode 102b is connected to the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the penetrating electrode 102c adjacent thereto by a metal bump 103b such as a solder bump. Similarly, the connection pad on the other side of the semiconductor element 101c having the through electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the adjacent through electrode 102d by the metal bump 103c such as a solder bump. ing.

An underfill layer 110 is formed in the gaps between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked via the underfill layer 110.

The stacked body 101 is stacked on the wiring board 120.
As the wiring substrate 120, for example, a multilayer wiring substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used. Examples of the wiring board 120 to which the resin board is applied include a multilayer copper-clad laminate (multilayer printed wiring board).

A surface electrode 120 a is provided on one surface of the wiring board 120.
An insulating layer 115 in which a rewiring layer 105 is formed is disposed between the wiring substrate 120 and the stacked body 101, and the wiring substrate 120 and the stacked body 101 are electrically connected via the rewiring layer 105. It is connected. The insulating layer 115 is formed using the photosensitive resin composition in the present invention.
That is, one end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the rewiring layer 105 side through a metal bump 103d such as a solder bump. The other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
An underfill layer 110 a is formed between the insulating layer 115 and the stacked body 101. In addition, an underfill layer 110 b is formed between the insulating layer 115 and the wiring substrate 120.

In addition to the above, the cured film produced according to the present invention can be widely used in various applications using polyimide or polybenzoxazole.
In addition, since polyimide and polybenzoxazole are resistant to heat, cured films and the like produced by the present invention are used for transparent plastic substrates for liquid crystal displays, display devices such as electronic paper, automotive parts, heat resistant paints, coating agents, and films. Can also be suitably used.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, 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. “Parts” and “%” are based on mass unless otherwise specified.

Example 1
[Synthesis of polyimide precursor A-1 from 4,4′-oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
21.2 g of 4,4′-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme (Diglyme, diethylene glycol dimethyl ether) were mixed. Stirring at temperature for 4 hours produced a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes. The mixture was stirred for 2 hours.
Subsequently, 6 liters of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred at a speed of 200 rpm for 15 minutes. The precipitate (polyimide precursor solid) after stirring was collected by filtration and 2,6-di-tert-butyl-p was used as a polymerization inhibitor G-1 in tetrahydrofuran (good solvent, manufactured by Wako Pure Chemical Industries, Ltd.). -Cresol (BHT) was dissolved in 500 g). 6 L of water (poor solvent) was added to the resulting solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred at a speed of 200 rpm for 15 minutes. The stirred precipitate (polyimide precursor solid) was filtered again and dried under reduced pressure at 45 ° C. for 3 days.
This polyimide precursor had a weight average molecular weight of 24,800 and a number average molecular weight of 7,900.

The following evaluation was performed about the obtained polyimide precursor (heterocycle containing polymer precursor material).
<Uniformity of polymerization inhibitor content>
1 g was arbitrarily sampled 4 times from 50 g of the obtained heterocyclic-containing polymer precursor material, and each was transferred to a 20 mL light-shielding glass container. To each light-shielding glass container, 5 g of N-methylpyrrolidone was added to dissolve the heterocyclic ring-containing polymer precursor material to prepare a sample solution. The obtained sample solution was subjected to gas chromatography measurement (apparatus: Agilent 7890A, column: HP-55, column temperature: 300 ° C.), and the content of the polymerization inhibitor contained in each heterocyclic ring-containing polymer precursor material (unit: : Mass ppm), and the difference between each of the measured values and the four average values was taken as an absolute value and divided by the average value. Among the obtained values, the largest value was shown as the rate of change (unit:%). The smaller the change rate, the more uniformly the polymerization inhibitor is present. The results are shown in Table 5.

<Storage stability>
10 g of the obtained heterocyclic-containing polymer precursor material was dissolved in 200 mL of N-methylpyrrolidone, and the viscosity of the solution at 25 ° C. was measured using an Ubbelohde tube (C = about 0.005 mm ² / s ² diameter). Next, 10 g of the same heterocycle-containing polymer precursor material was sealed in a 200 mL light-shielding glass container and allowed to stand in an environment of 25 ° C. and humidity 65% for 1 week. The viscosity of the heterocyclic-containing polymer precursor material after one week was measured again as described above, and the amount of increase or decrease in viscosity was calculated by (viscosity after standing / initial viscosity) × 100 (unit:%). The results are shown in Table 5.
A: The amount of increase / decrease in viscosity is 90% or more and less than 110%.
B: The increase / decrease amount of the viscosity is 110% or more and less than 130%.
C: The increase / decrease amount of the viscosity is 130% or more and less than 150%.
D: The amount of increase / decrease in viscosity is 130% or more.

(Example 2)
[Synthesis of polyimide precursor A-2 from 4,4′-oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
21.2 g of 4,4′-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed and stirred at a temperature of 60 ° C. for 4 hours. Thus, a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes. The mixture was stirred for 2 hours.
Next, 250 g of tetrahydrofuran (containing 0.03% by mass of 2,6-di-tert-butyl-p-cresol, manufactured by Wako Pure Chemical Industries, Ltd.) 250 g was added to the obtained reaction mixture, and 6 L of water was further added. In addition, the polyimide precursor was precipitated and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The stirred precipitate was filtered again and dried at 45 ° C. for 3 days under reduced pressure.
This polyimide precursor had a weight average molecular weight of 25,200 and a number average molecular weight of 8,000.
In the same manner as in Example 1, the uniformity of the polymerization inhibitor content and the storage stability were evaluated. The results are shown in Table 5.

(Example 3)
[Synthesis of polyimide precursor A-3 from 4,4'-oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]
21.2 g of 4,4′-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed and stirred at a temperature of 60 ° C. for 4 hours. Thus, a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes. And the mixture was stirred for 2 hours. Next, 6 L of water was added to the resulting solution to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The precipitate after stirring was collected by filtration, and 2,6-di-tert-butyl-p-cresol as a polymerization inhibitor G-1 manufactured by Wako Pure Chemical Industries, Ltd. was added to tetrahydrofuran under reduced pressure. 500 g dissolved so as to contain 0.03% by mass, and 0.15 g of p-methoxyphenol was added as a polymerization inhibitor G-2. 6 L of water was added to the resulting solution to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The stirred precipitate was filtered again and dried at 45 ° C. for 3 days under reduced pressure.
This polyimide precursor had a weight average molecular weight of 22,500 and a number average molecular weight of 7,400.
In the same manner as in Example 1, the uniformity of the polymerization inhibitor content and the storage stability were evaluated. The results are shown in Table 5.

Example 4
[Synthesis of polyimide precursor A-4 from 4,4′-oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
21.2 g of 4,4′-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed and stirred at a temperature of 60 ° C. for 4 hours. Thus, a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes. And the mixture was stirred for 2 hours.
Then 6 L of water was added to precipitate the polyimide precursor and the precipitate was stirred for 15 minutes at a speed of 200 rpm. The stirred precipitate is filtered and dissolved in 500 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., without stabilizer), and 0.15 g of 2,6-di-tert-butyl-p-cresol is added. It was. 6 L of water was added to the resulting solution to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The stirred precipitate was filtered again and dried at 45 ° C. for 3 days under reduced pressure.
This polyimide precursor had a weight average molecular weight of 23,800 and a number average molecular weight of 7,700.
In the same manner as in Example 1, the uniformity of the polymerization inhibitor content and the storage stability were evaluated. The results are shown in Table 5.

(Example 5)
[Synthesis of polyimide precursor A-5 from 4,4′-oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
21.2 g of 4,4′-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, 34 mg of hydroquinone and 250 mL of diglyme were mixed at a temperature of 60 ° C. For 4 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes. The mixture was stirred for 2 hours.
Then 6 L of water was added to precipitate the polyimide precursor and the precipitate was stirred for 15 minutes at a speed of 200 rpm. The precipitate after stirring was filtered and dissolved in 300 g of N-methylpyrrolidone, and 1.2 g of hydroquinone was added as a polymerization inhibitor G-3. 6 L of water was added to the resulting solution to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The stirred precipitate was filtered again and dried under reduced pressure at 45 ° C. for 3 days.
This polyimide precursor had a weight average molecular weight of 26,800 and a number average molecular weight of 8,800.
In the same manner as in Example 1, the uniformity of the polymerization inhibitor content and the storage stability were evaluated. The results are shown in Table 5.

(Example 6)
[Synthesis of polyimide precursor A-6 from pyromellitic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
15.5 g of pyromellitic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of N-methylpyrrolidone are mixed and stirred at a temperature of 60 ° C. for 4 hours. Thus, a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes. The mixture was stirred for 2 hours. Next, 3.2 g of benzoquinone as a polymerization inhibitor G-4 was added to the resulting reaction mixture, and 6 L of water was further added to precipitate the polyimide precursor, and the precipitate was allowed to flow at a rate of 200 rpm for 15 minutes. Stir. The stirred precipitate was filtered again and dried at 45 ° C. for 3 days under reduced pressure. This polyimide precursor had a weight average molecular weight of 24,500 and a number average molecular weight of 8,200.
In the same manner as in Example 1, the uniformity of the polymerization inhibitor content and the storage stability were evaluated. The results are shown in Table 5.

(Example 7)
[Synthesis of polyimide precursor A-7 from 4,4′-oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
21.2 g of 4,4′-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed and stirred at a temperature of 60 ° C. for 4 hours. Thus, a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes. The mixture was stirred for 2 hours.
Subsequently, 6 L of methanol was added to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The precipitate after stirring is collected by filtration and dissolved in 500 g of tetrahydrofuran (containing 0.03 mass% of 2,6-di-tert-butyl-p-cresol, manufactured by Wako Pure Chemical Industries, Ltd.), and 1.0 g Of 2,6-di-tert-butyl-p-cresol was added. 6 L of methanol was added to the resulting solution to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The precipitate was filtered again and dried at 45 ° C. under reduced pressure for 3 days.
This polyimide precursor had a weight average molecular weight of 24,800 and a number average molecular weight of 7,900.
In the same manner as in Example 1, the uniformity of the polymerization inhibitor content and the storage stability were evaluated. The results are shown in Table 5.

(Example 8)
[Synthesis of polyimide precursor A-8 from 4,4′-oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
21.2 g of 4,4′-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed and stirred at a temperature of 60 ° C. for 4 hours. Thus, a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes. The mixture was stirred for 2 hours.
Then, 6 L of water was added to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The precipitate after stirring was filtered and dissolved in 500 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., without stabilizer), and 4.0 g of 2,6-di-tert-butyl-p-cresol was added. . 6 L of water was added to the resulting solution to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The stirred precipitate was filtered again and dried at 45 ° C. for 3 days under reduced pressure.
This polyimide precursor had a weight average molecular weight of 22,000 and a number average molecular weight of 7,200.
In the same manner as in Example 1, the uniformity of the polymerization inhibitor content and the storage stability were evaluated. The results are shown in Table 5.

Example 9
[Synthesis of polyimide precursor A-9 from 4,4′-oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
21.2 g of 4,4′-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed and stirred at a temperature of 60 ° C. for 4 hours. Thus, a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes. The mixture was stirred for 2 hours.
Then, 6 L of water was added to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The stirred precipitate was collected by filtration and dissolved in 500 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., without stabilizer), and 25 mg of 2,6-di-tert-butyl-p-cresol was added. 6 L of water was added to the resulting solution to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The stirred precipitate was filtered again and dried at 45 ° C. for 3 days under reduced pressure.
This polyimide precursor had a weight average molecular weight of 22,000 and a number average molecular weight of 7,100.
In the same manner as in Example 1, the uniformity of the polymerization inhibitor content and the storage stability were evaluated. The results are shown in Table 5.

(Example 10)
[Synthesis of polyimide precursor A-10 from 4,4′-oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
21.2 g of 4,4′-oxydiphthalic anhydride, 9.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed and stirred at a temperature of 60 ° C. for 4 hours. Thus, a monoester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes. The mixture was stirred for 2 hours.
Then, 6 L of water was added to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The precipitate after stirring was filtered and dissolved in 500 g of tetrahydrofuran (containing 0.03% by mass of 2,6-di-tert-butyl-p-cresol, manufactured by Wako Pure Chemical Industries, Ltd.). 6 L of water was added to the resulting solution to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The stirred precipitate was filtered again and dried under reduced pressure at 45 ° C. for 3 days.
This polyimide precursor had a weight average molecular weight of 26,200 and a number average molecular weight of 8,800.
In the same manner as in Example 1, the uniformity of the polymerization inhibitor content and the storage stability were evaluated. The results are shown in Table 5.

(Example 11)
[Synthesis of Polybenzoxazole Precursor A-11 from 4,4'-Oxydibenzoyl Chloride, 2,2'-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane and Methacrylic Acid Chloride]
28.0 g of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 200 mL of N-methylpyrrolidone with stirring. Subsequently, while maintaining the temperature at 0 to 5 ° C., 25.0 g of 4,4′-oxydibenzoyl chloride 8.00 g was added dropwise over 10 minutes, and stirring was continued for 60 minutes. Subsequently, 25.0 g of pyridine was added, 5.8 g of methacrylic acid chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5 ° C., and stirring was continued for 60 minutes.
Then, 0.15 g of 2,6-di-tert-butyl-p-cresol was added to the resulting reaction mixture. 6 L of water was added to precipitate the polybenzoxazole precursor, and the precipitate (water-polybenzoxazole precursor mixture) was stirred at a speed of 200 rpm for 15 minutes. The stirred precipitate was filtered and dried at 45 ° C. under reduced pressure for 3 days.
This polybenzoxazole precursor had a weight average molecular weight of 32,500 and a number average molecular weight of 9,800.
In the same manner as in Example 1, the uniformity of the polymerization inhibitor content and the storage stability were evaluated. The results are shown in Table 5.

Example 12
[Synthesis of polybenzoxazole precursor A-12 from 4,4′-oxydibenzoyl chloride, hydroxy group-containing diamine (a) shown below and methacrylic acid chloride]
21.5 g of the hydroxy group-containing diamine (a) shown below was stirred and dissolved in 200 mL of N-methylpyrrolidone. Subsequently, while maintaining the temperature at 0 to 5 ° C., 25.0 g of 4,4′-oxydibenzoyl chloride 8.00 g was added dropwise over 10 minutes, and stirring was continued for 60 minutes. Subsequently, 25.0 g of pyridine was added, 5.8 g of methacrylic acid chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5 ° C., and stirring was continued for 60 minutes.
Then, 0.15 g of 2,6-di-tert-butyl-p-cresol was added to the resulting reaction mixture. 6 L of water was blended to precipitate the polybenzoxazole precursor and the precipitate was stirred for 15 minutes at a speed of 200 rpm. The stirred precipitate was filtered and dried at 45 ° C. under reduced pressure for 3 days.
This polybenzoxazole precursor had a weight average molecular weight of 34,500 and a number average molecular weight of 10,200.
In the same manner as in Example 1, the uniformity of the polymerization inhibitor content and the storage stability were evaluated. The results are shown in Table 5.

Hydroxyl group-containing diamine (a)

(Comparative Example 1)
[Synthesis of polyimide precursor A-13 from 4,4'-oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]
21.2 g of 4,4′-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed and stirred at a temperature of 60 ° C. for 4 hours. Thus, a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes. The mixture was stirred for 2 hours.
Then, 6 L of water was added to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The stirred precipitate was filtered and dried at 45 ° C. under reduced pressure for 3 days.
This polyimide precursor had a weight average molecular weight of 22,800 and a number average molecular weight of 7,400.
In the same manner as in Example 1, the uniformity of the polymerization inhibitor content and the storage stability were evaluated. The results are shown in Table 5.

(Comparative Example 2)
[Synthesis of polyimide precursor A-14 from 4,4′-oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
21.2 g of 4,4′-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 0.15 g of 2,6-di-tert- Butyl-p-cresol and 250 mL of diglyme were mixed and stirred at a temperature of 60 ° C. for 4 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes. The mixture was stirred for 2 hours.
Next, 6 L of water was blended to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The stirred precipitate was filtered and dried at 45 ° C. under reduced pressure for 3 days.
This polyimide precursor had a weight average molecular weight of 25,300 and a number average molecular weight of 8,000.
In the same manner as in Example 1, the uniformity of the polymerization inhibitor content and the storage stability were evaluated. The results are shown in Table 5.

(Comparative Example 3)
[Synthesis of polyimide precursor A-15 from 4,4′-oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
21.2 g of 4,4′-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed and stirred at a temperature of 60 ° C. for 4 hours. Thus, a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes. The mixture was stirred for 2 hours.
Then, 6 L of water was added to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The stirred precipitate was filtered and dried at 45 ° C. under reduced pressure for 3 days. To the precipitate after drying, 0.15 g of 2,6-di-tert-butyl-p-cresol was added as a polymerization inhibitor and stirred for 12 hours.
This polyimide precursor had a weight average molecular weight of 24,900 and a number average molecular weight of 7,700.
In the same manner as in Example 1, the uniformity of the polymerization inhibitor content and the storage stability were evaluated. The results are shown in Table 5.

From the above results, the heterocyclic ring-containing polymer precursor materials of Examples 1 to 12 contained a polymerization inhibitor uniformly and had good storage stability.
The heterocyclic ring-containing polymer precursor material of Comparative Example 1 in which no polymerization inhibitor was blended was inferior in storage stability.
In addition, the heterocyclic-containing polymer precursor material of Comparative Example 2 in which a polymerization inhibitor is blended in the process of synthesizing the heterocyclic-containing polymer precursor does not contain the polymerization inhibitor uniformly and has insufficient storage stability. there were.
Furthermore, the heterocyclic-containing polymer precursor material of Comparative Example 3 in which a polymerization inhibitor is blended with a dried solid heterocyclic-containing polymer precursor also does not contain a polymerization inhibitor uniformly, resulting in poor storage stability. It was enough.

All the heterocyclic ring-containing polymer precursors were dissolved in tetrahydrofuran and N-methylpyrrolidone (first solvent) at 25 ° C. in an amount of 5% by mass or more. In addition, any of the heterocyclic-containing polymer precursors dissolved in water and methanol (second solvent) at 5 ° C. or less at 25 ° C. or not at all.
In addition, 2,6-di-tert-butyl-p-cresol and p-methoxyphenol (polymerization inhibitor) were dissolved in tetrahydrofuran (first solvent) at 5% by mass or more at 25 ° C. Furthermore, hydroquinone and benzoquinone (polymerization inhibitor) were also dissolved in tetrahydrofuran (first solvent) at 25 ° C. by 5% by mass or more.

(Example 13)
<Adjustment of photosensitive resin composition>
The components described in Table 6 were mixed to prepare a coating solution for the photosensitive resin composition as a uniform solution.

<Measurement of exposure energy>
The photosensitive resin composition obtained above was pressure filtered through a filter having a pore width of 0.8 μm, and then applied to a silicon wafer by spinning (1,200 rpm, 30 seconds). The silicon wafer coated with the photosensitive resin composition was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform film having a thickness of 10 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed using an aligner (Karl-Suss MA150). The exposure was performed with a high-pressure mercury lamp, and the exposure energy required to form the above 10 μm uniform film at a wavelength of 365 nm was measured. The lower the exposure energy, the higher the sensitivity and the better result. The reason why the wavelength is set to 365 nm is that it is considered as one of suitable wavelengths for producing a good pattern.

(Examples 14 to 34, Comparative Examples 4 to 6)
In Example 13, as shown in Table 2, the type and blending amount of each component were changed, and the others were performed in the same manner.

(A) Heterocycle-containing polymer precursor material A-1 to A-15: Heterocycle-containing polymer precursor materials produced in Examples 1 to 12 and Comparative Examples 1 to 3

(B) Polymerizable compound B-1: NK ester M-40G (monofunctional methacrylate, following structure, manufactured by Shin-Nakamura Chemical Co., Ltd.)

B-2: NK Ester 4G (Shin Nakamura Chemical Co., Ltd., bifunctional methacrylate, following structure)

B-3: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional acrylate, following structure)

(C) Photopolymerization initiator C-1: IRGACURE OXE-01 (manufactured by BASF)

C-2: Compound 24 described in paragraph No. 0345 of JP-T-2014-500852
C-3: Compound 36 described in paragraph No. 0345 of JP-T-2014-500852
C-4: Compound 37 described in paragraph No. 0345 of JP-T-2014-500852
C-5: Compound 40 described in paragraph No. 0345 of JP-T-2014-500852

(D) Thermal polymerization initiator D-1: Perbutyl Z (manufactured by NOF Corporation, tert-butyl peroxybenzoate, decomposition temperature (10-hour half-life temperature = 104 ° C.))
D-2: Park mill D (manufactured by NOF Corporation, dicumyl peroxide, decomposition temperature (10-hour half-life temperature = 116.4 ° C))

(E) Additive E-1: 1H-tetrazole E-2: 1,2,4-triazole E-3: the following compound

E-4: 1,4-benzoquinone

(F) Solvent F-1: γ-butyrolactone F-2: Dimethyl sulfoxide

From the above results, the photosensitive resin compositions of Examples 13 to 34 had high exposure sensitivity and low exposure energy necessary for producing a good pattern.
The photosensitive resin composition of Comparative Example 4 could not form a pattern. Further, the photosensitive resin compositions of Comparative Examples 5 and 6 had high exposure energy necessary for producing a good pattern and low sensitivity.

<Example 100>
The photosensitive resin composition of Example 15 was spun onto a resin substrate on which a copper thin layer was formed (3500 rpm, 30 seconds). The photosensitive resin composition applied to the resin substrate was dried at 100 ° C. for 5 minutes, and then exposed using an aligner (Karl-Suss MA150). Exposure was performed with a high-pressure mercury lamp, and exposure energy at a wavelength of 365 nm was measured. After exposure, the image was developed with cyclopentanone for 75 seconds.
Subsequently, it heated at 180 degreeC for 20 minutes. In this way, an interlayer insulating film for a rewiring layer was formed.
This interlayer insulation film for rewiring layers was excellent in insulation.
Moreover, when a semiconductor device was manufactured using this interlayer insulating film for rewiring layer, it was confirmed that it operated without any problem.

100: Semiconductor devices 101a to 101d: Semiconductor elements 101: Stacked bodies 102b to 102d: Through electrodes 103a to 103e: Metal bumps 105: Rewiring layers 110, 110a, 110b: Underfill layers 115: Insulating layers 120: Wiring substrates 120a: Surface electrode

Claims

A polymerization inhibitor is added to the composition containing the heterocyclic ring-containing polymer precursor and the first solvent, or a first solvent and a polymerization inhibitor are added to the composition containing the heterocyclic ring-containing polymer precursor. And
Including blending a second solvent with the composition blended with the polymerization inhibitor and precipitating the heterocyclic-containing polymer precursor and the polymerization inhibitor in the second solvent;
The method for producing a heterocyclic-containing polymer precursor material, wherein the heterocyclic-containing polymer precursor is selected from a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group.
The method for producing a heterocyclic-containing polymer precursor material according to claim 1, wherein the amount of the polymerization inhibitor to be blended is 0.001 to 10% by mass of the heterocyclic-containing polymer precursor.
The manufacturing method of the heterocyclic containing polymer precursor material of Claim 1 or 2 with which the said heterocyclic containing polymer precursor melt | dissolves 5 mass% or more at 25 degreeC with respect to a said 1st solvent.
The method for producing a heterocyclic-containing polymer precursor material according to any one of claims 1 to 3, wherein the polymerization inhibitor is dissolved in the first solvent at 5% by mass or more at 25 ° C.
The method for producing a heterocyclic-containing polymer precursor material according to any one of claims 1 to 4, wherein the first solvent is tetrahydrofuran.
The heterocycle-containing polymer according to any one of claims 1 to 5, wherein the production method comprises blending a first solvent and a polymerization inhibitor into a composition containing the heterocycle-containing polymer precursor. A method for producing a precursor material.
The production method includes blending a polymerization inhibitor into the composition containing the heterocyclic ring-containing polymer precursor and the first solvent, and
The heterocycle-containing polymer precursor according to any one of claims 1 to 5, wherein the composition containing the heterocycle-containing polymer precursor and the first solvent is a synthesis reaction solution of the heterocycle-containing polymer precursor. Material manufacturing method.
The method for producing a heterocyclic-containing polymer precursor material according to any one of claims 1 to 7, wherein the second solvent is water or alcohol.
The heterocyclic ring according to any one of claims 1 to 8, wherein the heterocyclic-containing polymer precursor includes a repeating unit represented by the following formula (2) or a repeating unit represented by the following formula (3). A process for producing the containing polymer precursor material;
Formula (2)

Formula (3)

In formula (2), A 1 and A 2 each independently represent an oxygen atom or NH,
R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, R 113 and R At least one of 114 is a polymerizable group;
In Formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represents a hydrogen atom or a monovalent organic group. And at least one of R 123 and R 124 is a polymerizable group.
The heterocyclic-containing polymer precursor material according to claim 9, wherein both R 113 and R 114 in the formula (2) and both R 123 and R 124 in the formula (3) are polymerizable groups. Manufacturing method.
The method for producing a heterocyclic-containing polymer precursor material according to any one of claims 1 to 10, wherein the polymerization inhibitor has a phenolic hydroxyl group.
A heterocyclic-containing polymer precursor material selected from a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group,
The rate of change between the mass of the polymerization inhibitor in the heterocycle-containing polymer precursor material obtained by dividing the heterocycle-containing polymer precursor material into four parts and the mass of the polymerization inhibitor in the entire heterocycle-containing polymer precursor material, respectively, Heterocycle-containing polymer precursor material that is ± 10% or less.
The heterocycle-containing polymer precursor material according to claim 12, wherein the heterocycle-containing polymer precursor material contains a polymerization inhibitor in a proportion of 0.001 to 10% by mass.
A composition comprising the heterocyclic-containing polymer precursor material according to claim 12 or 13.
A photosensitive resin composition comprising the heterocyclic ring-containing polymer precursor material according to claim 12 and a photopolymerization initiator.
A cured film obtained by curing the photosensitive resin composition according to claim 15.
The cured film of Claim 16 which is an interlayer insulation film for rewiring layers.
The manufacturing method of a cured film including the process of applying the photosensitive resin composition of Claim 15 to a board | substrate, and the process of hardening the photosensitive resin composition applied to the board | substrate.
A semiconductor device comprising the cured film according to claim 16.