JP6531178B2 - Method for producing heterocycle-containing polymer precursor material and application thereof - Google Patents

Description

  The present invention relates to a method of producing a heterocycle-containing polymer precursor material. The present invention also relates to a heterocycle-containing polymer precursor material, and a composition and a photosensitive resin composition containing the heterocycle-containing polymer. Furthermore, the present invention relates to a cured film using the photosensitive resin composition, a method for producing the cured film, and a semiconductor device.

A thermosetting resin such as a polyimide resin which is cyclized and cured is used for an insulating layer or the like of a semiconductor device because it is excellent in heat resistance and insulation.
In addition, since the 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 or the like, and then heated to cyclize the polyimide precursor. It is practiced to form a cured film.

  For example, Patent Document 1 discloses that a polyimide resin (a) obtained by the reaction of a tetracarboxylic acid dianhydride and a diamine compound is obtained by reacting an energy ray-curable aqueous alkali solution-soluble resin (b) A photosensitive alkaline aqueous solution soluble polyimide resin (A) is disclosed.

Further, in Patent Document 2, (a) aromatic tetracarboxylic acid dianhydrides whose main components are (a) biphenyltetracarboxylic acid dianhydrides or bisether tetracarboxylic acid dianhydrides; Soluble polyimide obtained from diamines mainly composed of diamines represented by the formula (1), (b) a compound having a carbon-carbon double bond, (c) photosensitivity comprising a photoreactive initiator as an essential component Resin composition. (Wherein, R ¹ represents a direct bond or a divalent organic group, R ² represents -COOH or -OH, an integer of s = 0 to 4, and an integer of t = 1 to 4.)
Formula (1) is disclosed.

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

Further, Patent Document 4 includes the following steps: (A) coating of a substrate with a photopolymerizable composition comprising a polymer (a) and a photoinitiator (b), (B) i-line region (about 360) Used consisting of imagewise exposure of the coated substrate to UV radiation within -370 nm), (C) removal of unexposed parts by solvent, and (D) conditioning of the exposed and developed material The polymer (a) has the following formula I:
[Wherein, the arrows indicate structural isomers, X represents a tetravalent group of aromatic tetracarboxylic acid, and Y is a divalent aliphatic group, a cyclic aliphatic group or a monocyclic or polycyclic aromatic group A represents a group, A represents -COO-, -CONH- or
Wherein R ₂ and R ₃ independently represent an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 1 to 6 carbon atoms, and R ₁ represents a photopolymerization group. Or a group containing an olefinic double bond, provided that at least 50% of all X groups represent oxydiphthalic acid groups, or at least 50% of all Y groups are all four to two amine nitrogen atoms And R 14 independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aromatic diamine group substituted by an aryl group having 6 to 14 carbon atoms independently of one another 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.

Furthermore, 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, And R ₁ and R ₂ each independently represent 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).
And 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 The ratio of the total of 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%. }
Polyimide precursor having a structure represented by: 100 parts by mass; and (B) a photopolymerization initiator: 0.1 parts by mass to 20 parts by mass;
A negative photosensitive resin composition is disclosed.

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

However, when the present inventor examined a conventional polyimide precursor, it was found that storage stability may be poor. That is, it has been found that among the heterocycle-containing polymer precursors such as the polyimide precursor, those having a polymerizable group may undergo polymerization progress with time and the viscosity may increase.
An object of the present invention is to solve such problems, and an object thereof is to provide a method for producing a heterocycle-containing polymer precursor material excellent in storage stability over time. Furthermore, another object of the present invention is to provide a heterocycle-containing polymer precursor material, a composition, a photosensitive resin composition, a cured film, a method for producing a cured film, and a semiconductor device.

Under these circumstances, as a result of intensive studies conducted by the present inventor, the present inventors have found that the above problems can be solved by blending a polymerization inhibitor with a heterocycle-containing polymer under predetermined conditions.
Specifically, the above problems are solved by the following means <1>, preferably <2> to <23>.
A composition containing a <1> heterocycle-containing polymer precursor and a first solvent is blended with a polymerization inhibitor, or a composition containing a heterocycle-containing polymer precursor is a first solvent and a polymerization inhibitor Blending, and
Incorporating a second solvent into the composition containing the polymerization inhibitor, and depositing the heterocycle-containing polymer precursor and the polymerization inhibitor in the second solvent;
The method for producing a heterocycle-containing polymer precursor material, wherein the heterocycle-containing polymer precursor is selected from a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group.
The manufacturing method of the heterocyclic containing polymer precursor material as described in <1> whose quantity of the polymerization inhibitor to <2> mix | blends is 0.001-10 mass% of the said heterocyclic containing polymer precursor.
The manufacturing method of the heterocyclic containing polymer precursor material as described in <1> or <2> which 5 mass% or more of said heterocyclic containing polymer precursors melt | dissolve at 25 degreeC with respect to a <3> said 1st solvent.
The manufacturing method of the heterocyclic containing polymer precursor material in any one of <1>-<3> in which 5 mass% or more of said polymerization inhibitors melt | dissolve at 25 degreeC with respect to a <4> said 1st solvent.
The manufacturing method of the heterocyclic containing polymer precursor material in any one of <1>-<4> whose <5> said 1st solvent is tetrahydrofuran.
<6> The complex according to any one of <1> to <5>, wherein the production method includes blending a first solvent and a polymerization inhibitor in a composition containing the heterocycle-containing polymer precursor. Method for producing ring-containing polymer precursor material.
<7> The above production method includes blending a polymerization inhibitor into a composition containing the above-mentioned heterocycle-containing polymer precursor and the first solvent, and the above-mentioned heterocycle-containing polymer precursor and the first solvent The manufacturing method of the heterocyclic containing polymer precursor material in any one of <1>-<5> which is a synthesis reaction liquid of a heterocyclic containing polymer precursor, the composition containing these.
The manufacturing method of the heterocyclic containing polymer precursor material in any one of <1>-<7> whose <8> above-mentioned 2nd solvent is water or alcohol.
The <9> above-mentioned heterocyclic containing polymer precursor is described in any one of <1>-<8> in which the repeating unit represented by following formula (2) or the repeating unit represented by following formula (3) is included A method of producing a heterocycle-containing polymer precursor material of
Formula (2)
Formula (3)
In formula (2), each of A ¹ and A ² independently represents 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 ^{114 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 represent a hydrogen atom or a monovalent organic group. And at least one of R ¹²³ and R ¹²⁴ is a polymerizable group.
<10> The heterocycle-containing polymer according to <9>, wherein both of R ¹¹³ and R ¹¹⁴ in the above formula (2) and both of R ¹²³ and R ¹²⁴ in the above formula (3) are polymerizable groups Method of manufacturing precursor material.
The manufacturing method of the heterocyclic containing polymer precursor material in any one of <1>-<10> in which the <11> above-mentioned polymerization inhibitor has phenolic hydroxyl group.
<12> A heterocycle-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 of the mass of the polymerization inhibitor in the heterocyclic ring-containing polymer precursor material obtained by dividing the above-mentioned heterocyclic ring-containing polymer precursor material into four and the mass of the polymerization inhibitor in the entire heterocyclic ring-containing polymer precursor material is 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.
The composition containing the heterocyclic containing polymer precursor material as described in <14><12> or <13>.
The photosensitive resin composition containing the heterocyclic containing polymer precursor material as described in <15><12> or <13>, and a photoinitiator.
The cured film which hardens | cures the photosensitive resin composition as described in <16><15>.
The cured film as described in <16> which is an interlayer insulation film for <17> rewiring layers.
The manufacturing method of a cured film including the process of applying the photosensitive resin composition as described in <18><15> to a board | substrate, and the process of hardening | curing the photosensitive resin composition applied to the board | substrate.
The semiconductor device which has a cured film as described in <19><16> or <17>.
The heterocyclic containing polymer precursor material obtained by the manufacturing method of the heterocyclic containing polymer precursor material in any one of <20><1>-<11>.
<21> A heterocycle-containing polymer precursor material selected from a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group, wherein any one of the heterocycle-containing polymer precursor materials described above The heterocycle-containing polymer having a rate of change of ± 10% or less between the mass of the polymerization inhibitor in the sample collected 1 g at a time from each place and the mass of the polymerization inhibitor in the entire heterocycle-containing polymer precursor material Precursor material.
<22><1> to <11> in a sample obtained by collecting 1 g each from any four places of the heterocycle-containing polymer precursor material obtained by the method for producing a heterocycle-containing polymer precursor material according to any one of <22> A heterocycle-containing polymer precursor material, wherein the rate of change of 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 heterocycle-containing polymer precursor according to any one of <20> to <22>, wherein the amount of the polymerization inhibitor is 0.001 to 10% by mass of the heterocycle-containing polymer precursor material Body material.

  According to the present invention, it has become possible to provide a heterocycle-containing polymer precursor material excellent in storage stability. In addition, it has become possible to provide a heterocycle-containing polymer precursor material, a composition, a photosensitive resin composition, a cured film, a method for producing a cured film, and a semiconductor device.

FIG. 1 is a schematic view showing the configuration of an embodiment of a semiconductor device.

The description of components in the present invention described below may be made based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the notation of groups (atomic groups) in the present specification, the notations not describing substitution and non-substitution include those having no substituent and those having 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 the present specification, "active light" means, for example, a bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV light), X-rays, electron beams and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, the "exposure" in the present specification means not only exposure using far ultraviolet rays represented by a mercury lamp or excimer laser, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams. Include drawing in using in the exposure.
In the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
In the present specification, “(meth) acrylate” represents both “acrylate” and “methacrylate” or any of “acrylate” and “(meth) allyl” represents both “allyl” and “methallyl” or "(Meth) acrylic" represents either or both of "acrylic" and "methacrylic", and "(meth) acryloyl" represents both "acryloyl" and "methacryloyl" or Represents one.
As used herein, the term "step" does not only mean an independent step, but if the intended function of that step is achieved even if it can not be clearly distinguished from other steps, this term include.
In the present specification, the solid content concentration is a mass percentage of the mass of the other components excluding the solvent with respect to the total mass of the composition. Moreover, solid content concentration means the density | concentration in 25 degreeC unless it mentions specially.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene equivalent values by gel permeation chromatography (GPC) measurement, unless otherwise stated. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corp.), guard column HZ-L as a column, TSKgel Super HZM-M, TSKgel It can obtain | require by using Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (made by Tosoh Corp.). Eluents are to be determined using THF (tetrahydrofuran) unless otherwise stated. Moreover, a detection shall use the wavelength 254 nm detector of a UV ray (ultraviolet light), unless it mentions specially.

In the method for producing a heterocycle-containing polymer precursor material of the present invention, a polymerization inhibitor is added to a composition containing a heterocycle-containing polymer precursor and a first solvent, or a heterocycle-containing polymer precursor is used. Blending the first solvent and the polymerization inhibitor into the composition comprising
Incorporating a second solvent into the composition containing the polymerization inhibitor, and depositing the heterocycle-containing polymer precursor and the polymerization inhibitor in the second solvent;
The heterocycle-containing polymer precursor is characterized in that it is selected from a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group.
With such a configuration, a heterocycle-containing polymer precursor material excellent in storage stability can be obtained.

The polymerization may proceed during storage of the heterocycle-containing polymer having a polymerizable group. Here, in order to suppress the progress of polymerization, it is conceivable to blend a polymerization inhibitor. However, when the present inventors examined, as shown in the examples described later, the storage stability of the resulting heterocycle-containing polymer precursor, even if a polymerization inhibitor is added during the synthesis process of the heterocycle-containing polymer Was found to be inferior. Furthermore, it is also assumed that when the polymerization inhibitor is blended, an unexpected reaction proceeds. On the other hand, it was also found that the storage stability is similarly poor even when a polymerization inhibitor is added to the dried solid heterocycle-containing polymer precursor. When this reason was examined, even if it mixed a polymerization inhibitor with a dried solid heterocycle-containing polymer, it was found that the reason is that the polymerization inhibitor is not uniformly present in the heterocycle-containing polymer precursor. .
In the present invention, the polymerization inhibitor is added to the heterocycle-containing polymer precursor in addition to the polymerization inhibitor, and then the heterocycle-containing polymer precursor is precipitated, whereby the polymerization inhibitor is substantially uniform in the heterocycle-containing polymer precursor material. It has been found that a heterocycle-containing polymer precursor material excellent in storage stability can be obtained, and the present invention has been completed.
That is, in the heterocycle-containing polymer precursor material obtained by the production method of the present invention, the polymerization inhibitor is almost uniformly present 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 although it contains a polymerization inhibitor. Therefore, the photosensitive resin composition using the heterocycle-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 of Producing Heterocycle-Containing Polymer Precursor Material>
<< polymerization inhibitor combination process >>
The method for producing a heterocycle-containing polymer precursor material of the present invention comprises blending a polymerization inhibitor into a composition comprising a heterocycle-containing polymer precursor and a first solvent, or comprising a heterocycle-containing polymer precursor The composition comprises blending a first solvent and a polymerization inhibitor.
Thus, by the presence of the heterocycle-containing polymer precursor which has already been synthesized, the first solvent, and the polymerization inhibitor, these components are well mixed, and the polymerization inhibitor is A heterocycle-containing polymer precursor material uniformly incorporated into the heterocycle-containing polymer precursor and excellent in storage stability can be obtained.
Therefore, in the present invention, it is preferable to well stir in the state of the composition in which the heterocycle-containing polymer precursor, the first solvent, and the polymerization inhibitor are present. The stirring speed can be appropriately determined depending on the production scale and the stirring form, but can be, for example, about 10 rpm to about 6,000 rpm. The stirring time can also be about 5 minutes to 1 hour.

As a first embodiment of the polymerization inhibitor blending step, blending of a first solvent and a polymerization inhibitor into a composition containing a heterocycle-containing polymer precursor may be mentioned. Examples of the heterocycle-containing polymer precursor in this case include a solid heterocycle-containing polymer precursor and a precipitate obtained by depositing the heterocycle-containing polymer precursor from a reaction solution for synthesis of the heterocycle-containing polymer precursor.
As a second embodiment of the polymerization inhibitor blending step, blending of a polymerization inhibitor into a composition containing a heterocycle-containing polymer precursor and a first solvent can be mentioned. In this case, as a composition containing the heterocycle-containing polymer precursor and the first solvent, a synthesis reaction liquid of the heterocycle-containing polymer precursor and the like can be mentioned.
As a third embodiment of the polymerization inhibitor blending step, blending a first solvent and a polymerization inhibitor into a composition containing a heterocycle-containing polymer precursor and a first solvent can be 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, in a reaction solution for synthesis of a heterocycle-containing polymer precursor (corresponding to a composition containing a heterocycle-containing polymer precursor and a first solvent), a polymerization inhibitor (a first solvent and a polymerization inhibitor) dissolved in a solvent 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 usually functions 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 value of the solubility is not particularly limited, and may be 100% by mass. With such a configuration, the polymerization inhibitor can be more easily incorporated into the heterocycle-containing polymer precursor more uniformly.
In the present invention, it is preferable that the polymerization inhibitor be dissolved in an amount of 5% by mass or more at 25 ° C. in the first solvent. With such a configuration, the polymerization inhibitor can be more easily incorporated into the heterocycle-containing polymer precursor more uniformly. The upper limit value of the solubility is not particularly limited, and may be 100% by mass.

  As the first solvent, as esters, for example, 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 alkyl oxyacetate (eg methyl alkyl oxyacetate, ethyl alkyl oxy acetate, butyl alkyl oxy acetate (eg methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, ethoxy) Methyl acetate, ethyl ethoxyacetate etc.), 3-alkyloxypropionic acid alkyl esters (eg methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate etc. (eg methyl 3-methoxypropionate, 3- Me Ethyl xylopropionate, 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 (eg, 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 etc.), pyruvate Methyl, pi Ethyl vinylate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate Tate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-pyrrolidone and the like, and as aromatic hydrocarbons, for example, toluene, xylene, Anisole, limonene and the like, and as the sulfoxides, for example, dimethyl sulfoxide is preferably mentioned.

  Among the above, ethers and ketones are preferable, tetrahydrofuran and N-methyl-pyrrolidone are more preferable, and tetrahydrofuran is more preferable.

The amount of the first solvent to be used is preferably 1 to 100 times, and more preferably 4 to 20 times, the mass ratio of the heterocycle-containing polymer precursor.
The first solvent 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 said range.

<< precipitation process >>
In the method for producing a heterocycle-containing polymer precursor material of the present invention, a second solvent is blended in a composition in which the polymerization inhibitor is blended, and the heterocycle-containing polymer precursor is incorporated in the second solvent. And depositing the above-mentioned polymerization inhibitor. With such a configuration, a heterocycle-containing polymer precursor material in which the polymerization inhibitor is uniformly incorporated into the heterocycle-containing polymer precursor can be obtained.
Here, precipitation means that at least a part of the heterocycle-containing polymer precursor and at least a part of the polymerization inhibitor, which are present in the first solvent, separate from the first solvent as a solid. It usually precipitates in the second solvent. Preferably, 80% by mass or more of the total of the heterocycle-containing polymer precursor and the polymerization inhibitor present in the first solvent is separated from the first solvent and precipitated in the second solvent. .
It is not essential for the precipitation to precipitate all of the heterocycle-containing polymer precursor and the polymerization inhibitor present in the first solvent into the second solvent, and the heterocycle-containing polymer precursor It is needless to say that precipitation of part of the above-mentioned polymerization inhibitor is also included in the scope of the present invention. In the present invention, preferably 60 to 100% by mass, more preferably 80 to 100% by mass, of the total of the heterocyclic ring-containing polymer precursor and the polymerization inhibitor contained in the above composition is contained in the second solvent. It is preferable to precipitate.
The precipitation step is usually performed at 15 to 40 ° C.

<< Second solvent >>
The second solvent used in the present invention is generally one that acts 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 lower solubility in the heterocycle-containing polymer precursor at 25 ° C. than the first solvent, and the heterocycle-containing polymer precursor is more preferred than the first solvent. It is more preferable that the solubility at 25 ° C. with respect to is lower by 10% by mass or more. With such a configuration, precipitation of the heterocycle-containing polymer precursor can be more effectively progressed, and a heterocycle-containing polymer precursor material in which a polymerization inhibitor is incorporated more uniformly can be obtained. The solubility of the second solvent in the heterocycle-containing polymer precursor at 25 ° C. is preferably 5% by mass or less or does not dissolve 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, and more preferably 10 to 500 times that of the heterocycle-containing polymer. The amount of the second solvent used is preferably 1 to 1,000 times, more preferably 4 to 100 times the amount used of the first solvent.
The second solvent 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 said range.

<< Heterocycle-Containing Polymer Precursor >>
The heterocycle-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 capable of undergoing a crosslinking reaction by the action of an actinic ray, radiation, a radical, an acid or a base, and as a preferred example, a group having an ethylenically unsaturated bond, an alkoxymethyl group Examples thereof include hydroxymethyl group, acyloxymethyl group, epoxy group, oxetanyl group, benzoxazolyl group, blocked isocyanate group, methylol group and amino group. As a polymeric group which a heterocyclic containing polymer precursor has, the group which has an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a group represented by the following formula (III).

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, with a methyl group being more preferred.
In Formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH (OH) CH ₂ — or a 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 the like, ethylene, propylene, _{trimethylene, -CH 2 CH (OH) CH} 2 - is preferred.
Particularly preferably, R ²⁰⁰ is methyl and R ²⁰¹ is ethylene.
Hereinafter, the polyimide precursor having a polymerizable group and the 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 its structure etc. as long as it contains a polymerizable group and can be polyimidated, and it is intended to include also 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, and 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 the formula (2) each independently represent an oxygen atom or NH, and an oxygen atom is preferable.

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 The group which consists of a C6-C20 cyclic aliphatic group, a C6-C20 aryl group, or these combination is preferable, and the group which consists of a C6-C20 aryl group is more preferable. The following is mentioned as an example of an aryl group.

In the formula, A represents 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 combination thereof are preferable, and a single bond, a C1-C3 alkylene group which may be substituted with a fluorine atom, -O-,- It is more preferable that it is a group selected from C (= O)-, -S- and -SO _2- , and -CH _2- , -O-, -S-, -SO ₂ -and -C (CF _{3 ) 2 -, - C (CH} 3) 2 - and more preferably a divalent group selected from.

More specifically, R ¹¹¹ includes a diamine residue remaining after removal of the amino group of the diamine. As the diamine, linear or branched aliphatic, cyclic aliphatic or aromatic diamines and the like can be mentioned.
Specifically, the diamine residue etc. which remain after removal of the amino group of the following diamine are mentioned.
1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2 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 isophorone diamine; m- and p-phenylene diamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4, 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′-diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenyl 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'-Tetraaminodiphenylether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) Fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 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, 1 5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-amino) 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) C) 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 ′, 5,5 At least one diamine selected from 5 ', 6,6'-hexafluorotolidine and 4,4'''-diamino quaterphenyl.

Further, the diamine residues remaining after removal of the amino groups of the diamine shown below (DA-1) ~ (DA -18) may also be mentioned as examples of ^{R 111.}

Further, the diamine residues remaining at least two alkylene glycol units after the removal of the amino groups of the diamine having the main chain may also be mentioned as examples of R ^111. Preferably, it is a diamine residue containing two or more of ethylene glycol chain and / or propylene glycol chain together in one molecule, and more preferably a diamine residue not containing an aromatic ring. As an example, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 ( As described above, trade names, manufactured by HUNTSMAN Ltd., 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, 1- (2- (2- (2) (2) -Aminopropoxy) ethoxy) propoxy) propan-2-amine and the like, but it is not limited thereto. 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 a tetravalent organic group, the tetravalent organic group containing an aromatic ring is preferable, and the group represented by 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 is a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO _2- , and -NHCO-, and It is preferable that it is a group selected from a combination. R ¹¹² is a single bond or a divalent selected from an alkylene group of 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- and -SO _2- It is more preferable that the group be a single bond, or a single bond, or -CH _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _2- , -O-, -CO-, -S- and -SO _The divalent group selected from 2- is more preferable.

Formula (6)

Specific examples of R ¹¹⁵ include tetracarboxylic acid residues remaining after removal of the acid anhydride group from tetracarboxylic acid dianhydride.
Specifically, the tetracarboxylic acid residue etc. which remain after removal of an acid anhydride group from the following tetracarboxylic acid dianhydride are mentioned.
Pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl sulfide tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylmethane tetracarboxylic acid dianhydride , 2,2 ', 3,3'-Diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetra Carboxylic acid dianhydride, 4,4′-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid dianhydride, 2 , 2-bis (3,4-dika Voxyphenyl) 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 acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic acid Acid dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, 1,2,4,5-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid Anhydride, 1,8,9,10-phenanthrene tetracarboxylic acid dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxylic acid) Ciphenyl) ethane dianhydride, 1,2,3,4-benzene tetracarboxylic acid dianhydride, and at least one selected from these C 1 to C 6 alkyl and / or C 1 to C 6 alkoxy derivatives Seed of tetracarboxylic acid dianhydride.

Also, tetracarboxylic acid residue remaining tetracarboxylic dianhydride represented by the following from (DAA-1) ~ (DAA -5) after removal of the anhydride groups mentioned as examples of R ^115.

From the viewpoint of solubility in an alkaline developer, at least one of R ¹¹¹ and R ¹¹⁵ preferably 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, the above (DA-1) to (DA-18) is mentioned as a preferred example, and as R ¹¹⁵ , the above (DAA-1) to (DAA-5) is mentioned as a preferred example Be

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. And aryl groups and aralkyl groups having the Specifically, a C6-C20 aryl group which has an acidic group, and a C7-C25 aralkyl group which has an acidic group are mentioned. 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.
It is preferable that R ¹¹³ or R ¹¹⁴ be a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aryl group, and more preferably an alkyl group substituted with an aryl group.
The carbon number of the alkyl group is preferably 1 to 30. The alkyl group may be linear, branched or cyclic. As a linear or branched alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, Examples include octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. 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. As a polycyclic cyclic alkyl group, for example, 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 are mentioned. Among them, a cyclohexyl group is most preferable in terms of coexistence with 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 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, quinolizine 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. The benzene ring is most preferred.

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

  Moreover, in the case of alkaline development, it is preferable that a polyimide precursor has a fluorine atom in a structural unit from the point which improves resolution. The fluorine atom imparts water repellency to the surface of the film during alkali development, and it is possible to suppress the penetration from the surface. 10 mass% or more is preferable, and, as for the fluorine atom content in a polyimide precursor, 20 mass% or less is preferable from the soluble point with respect to aqueous alkali solution.

  In addition, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized. Specifically, as the diamine component, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane and the like can be mentioned.

  In addition, in order to further improve storage stability, the polyimide precursor may be sealed at the main chain terminal with an end capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, etc. preferable. Among these, it is more preferable to use a monoamine. Examples of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, and 1-hydroxy-6-aminonaphthalene. 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 Pyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like can be mentioned. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end capping 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 1 sort (s) of the heterocyclic containing polymer precursor used by this invention is a precursor which has a repeating unit represented by Formula (1-1). Such a structure makes it possible to further widen the exposure latitude.
In Formula (1-1), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently. 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.

  In the polyimide precursor, the repeating structural unit represented by the formula (2) may be one type, or two or more types. Moreover, the structural isomer of the repeating unit represented by Formula (2) may be included. Moreover, it goes without saying that the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above-mentioned 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 the repeating units are the repeating units represented by the formula (2) Is illustrated.

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 still more preferably 22,000 to 28,000. Also, the number average molecular weight (Mn) is preferably 5,000 to 14,000, and more preferably 6,000 to 10,000.
The dispersion degree 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 is a compound having a polymerizable group and capable of forming a polybenzoxazole, but the compound represented by the following formula (3) is not particularly limited. Is preferred.

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 represent 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. An aliphatic group or an aryl group is mentioned as a bivalent organic group.
Examples of the divalent aryl group include the following.

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

  As the divalent aliphatic group, a linear aliphatic group is preferable in terms of promoting cyclization at a low temperature. The carbon number of the linear aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, and still more preferably 4 to 15. And 5 to 10 are more preferable. The linear aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethyl malonic acid, ethyl malonic acid, isopropyl malonic acid, di-n-butyl malonic acid, succinic acid, tetrafluorosuccinic acid, methyl succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methyl glutaric acid, 3-methyl glutaric acid, 2, 2-dimethyl glutaric acid, 3, 3- Dimethyl glutaric acid, 3-ethyl-3-methyl glutaric acid, adipic acid, octafluoro adipic acid, 3-methyl adipic acid, pimelic acid, 2,2,6,6-tetramethyl pimelic acid, suberic acid, dodecafluoro Suberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, Lydecane diacid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosan diacid, henicosane diacid, docosane diacid, trichosan diacid, tetracosane diacid, pentacosan di Acid, hexacosan diacid, heptacosan diacid, octacosan diacid, nonacosane diacid, triacontan diacid, hentriacontan diacid, dotriacontan diacid, diglycolic acid, and dicarboxylic acids represented by the following formulas It 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.
Further, 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, 3,3′- Diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, 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-4,4 '-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.

  Among the bisaminophenol derivatives represented by the formula (A), bisaminophenol derivatives having the following aryl group are preferable.

In the formula, X ₁ represents -O-, -S-, -C (CF ₃ ) _2- , -CH _2- , -SO _2- or -NHCO-. Further, in the above structure, -OH and -NH ₂ contained in the structure of the formula (A) bind to each other at the ortho position (adjacent position).
The bisaminophenol derivative of the above formula (A) is a bisphenol represented by the following formula (A-s) from the viewpoint of being able to obtain a polybenzoxazole precursor which is highly transparent to i-ray and can be cured at low temperature. Is preferred.

In the formula, R ₁ is a single bond or selected from the group of alkylene, substituted alkylene, -O-, -S-, -SO _2- , -CO-, -NHCO-, and the following formula (A-sc) Organic group. R ₂ is any 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 a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group or a cyclic alkyl group, and may be the same or different.

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

In the above formula (As), having a substituent at the ortho position of the phenolic hydroxyl group, that is, R ₃ is considered to make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer and cure at low temperature It is particularly preferable in that the effect of achieving a high degree of cyclization is further enhanced.

Further, in the above formula (A-s), that R ₂ is an alkyl group and R ₃ is an alkyl group is said to have a high degree of transparency to i-line and a high degree of cyclization when cured at low temperature It is particularly preferable in that a polybenzoxazole precursor having sufficient solubility and excellent balance can be obtained when using an aqueous alkaline solution as a developer while maintaining the effect.

Moreover, it is preferable that R < ₁ > is alkylene or substituted alkylene in said Formula (A-s). Specific examples of the alkylene and substituted alkylene for 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 )-and -C (CH ₃ ) _2- maintain high transparency to i-line and high cyclization ratio when cured at low temperature. However, it is more preferable at the point which can obtain the polybenzoxazole precursor which has sufficient solubility with respect to not only aqueous alkali solution but solvent, and is excellent in balance.

  As a manufacturing method of the bisamino phenol derivative shown by said Formula (As), paragraph number 0085-0094 of Unexamined-Japanese-Patent No. 2013-256506 and Example 1 (Paragraph number 0189-0190) are referred to, for example The contents of which are incorporated herein.

  Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs [0070] to [0080] of JP-A-2013-256506, the contents of which are incorporated herein by reference. Incorporated into Of course, it is needless to say that it is not limited to these.

  Among them, those shown below are preferable as the bisaminophenol derivative represented by the above formula (A-s).

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. The case where R ¹²³ or ^{R 124} represents a monovalent organic group is ^the same meanings as those of ^{R 113} and ^{R 114} in formula (2), and preferred ranges are also the same.

The polybenzoxazole precursor may also contain other types of repeating structural units in addition to the repeating unit of the above-mentioned formula (3).
It is preferable that the diamine residue represented by following formula (SL) is included as another kind of repeating structural unit by the point which can suppress generation | occurrence | production of the curvature accompanying ring closing.

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 And at least one of R ^3s , R ^4s , R ^5s and R ^6s is an aryl group, and the rest 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 mole percentage of the Z moiety is 5 to 95 mole% for the a structure, 95 to 5 mole% for the b structure, and a + b is 100 mole%.

In the formula (SL), preferable Z includes those in which R ^5s and R ^6s in the b structure are a phenyl group. Moreover, it is preferable that it is 400-4,000, and, as for the molecular weight of the structure shown by Formula (SL), 500-3,000 are more preferable. Molecular weight can be determined by commonly used gel permeation chromatography. By making the said molecular weight into the said range, the elastic modulus after dehydration ring-closing of a polybenzoxazole precursor can be reduced, and the effect which can control curvature, and the effect of improving solubility can be compatible.

When a diamine residue represented by the formula (SL) is contained as another type of repeating structural unit, the tetracarboxylic acid residue remaining after removal of the dianhydride group from the tetracarboxylic acid 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 residues include the examples of R ¹¹⁵ in the formula (2).

  Also, 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 at least one alkynyl group is used for the terminal amino group of the polybenzoxazole precursor. It is preferable to make it into an amide and cap.

  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 reaction with an amino group, that is, the end capping group is For example, the groups 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 in that they can improve the storability.

The polybenzoxazole precursor includes, for example, a compound selected from a bisaminophenol derivative represented by the formula (A), a dicarboxylic acid containing R ¹²¹ , and a dicarboxylic acid dichloride and a dicarboxylic acid derivative of the dicarboxylic acid. Can be obtained by reacting
In addition, when using dicarboxylic acid, in order to raise reaction yield etc., you may use the dicarboxylic acid derivative of the active ester type which made 1-hydroxy 1,2,3- benzotriazole etc. react beforehand.

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 later. Preferably, it is 30,000 to 40,000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,000 to 11,000.
The dispersion degree 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 heterocycle-containing polymer precursor material of the present invention, only one heterocycle-containing polymer precursor may be used, or two or more heterocycle-containing polymer precursors may be used. In addition, although both a polyimide precursor and a polybenzoxazole precursor may be used, an embodiment using only one or two or more polyimide precursors, and only one or more polybenzoxazole precursors The aspect which uses is more preferable.

<< polymerization inhibitor >>
In the method for producing a heterocycle-containing polymer precursor material of the present invention, the kind of polymerization inhibitor to be blended is not particularly limited, and a known one may be used.
As a polymerization inhibitor, what has a phenolic hydroxyl group is preferable. Specifically, as a polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-thiobis ( Preferred examples include 3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, hydroquinone, p- Methoxyphenol, di-tert-butyl-p-cresol, benzoquinone and 2,6-di-tert-butyl-p-cresol are preferable, and 2,6-di-tert-butyl-p-cresol is more preferable.
The amount of the polymerization inhibitor blended is preferably 0.001 to 10% by mass of the heterocycle-containing polymer precursor. The lower limit value of the amount of the polymerization inhibitor to be blended is more preferably 0.1% by mass or more, and can be 0.2% by mass or more. 9 mass% or less is more preferable, 7 mass% or less may be sufficient, and the upper limit of the quantity of the polymerization inhibitor to mix | blended can also be 5 mass% or less. In particular, in the present invention, the polymerization inhibitor is uniformly applied to the heterocycle-containing polymer precursor material even if 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.
The polymerization inhibitor may contain only one type, or two or more types. In the case of two or more types, the total amount is preferably in the above range.
Here, the sensitivity tends to be further improved by setting the amount of the polymerization inhibitor to 10% by mass or less of the heterocycle-containing polymer precursor, and the heterocycle obtained by setting the amount to 0.001% by mass or more The storage stability of the contained polymer precursor tends to be further improved.

  In the present invention, in the composition containing the heterocycle-containing polymer precursor and tetrahydrofuran, a polymerization inhibitor containing 2,6-di-tert-butyl-p-cresol is added to 0.1 to 0.1 of the heterocycle-containing polymer precursor. In the composition containing 5% by mass of the heterocyclic-containing polymer precursor, it is possible to use tetrahydrofuran and 2,6-di- in the proportion of 0.1 to 5% by mass of the heterocyclic-containing polymer precursor. blending a polymerization inhibitor containing tert-butyl-p-cresol; and blending the composition containing the polymerization inhibitor with water to obtain the above-mentioned heterocycle-containing polymer precursor and the above-mentioned water in the water The heterocyclic-containing polymer precursor includes precipitation of 2,6-di-tert-butyl-p-cresol, and the above-mentioned heterocycle-containing polymer precursor is a polyimide precursor having a polymerizable group and a polyben having a polymerizable group Is selected from oxazole precursor, 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 the method for producing a heterocycle-containing polymer precursor material or the like.
The first embodiment of the heterocycle-containing polymer precursor material of the present invention is a heterocycle-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 and the mass of the polymerization inhibitor in the entire heterocycle-containing polymer precursor material is These are heterocycle-containing polymer precursor materials each having ± 10% or less.
The second embodiment of the heterocycle-containing polymer precursor material of the present invention is a heterocycle-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 1 g each from any four parts of the above-mentioned heterocycle-containing polymer precursor material and the mass of the polymerization inhibitor in the whole of the above-mentioned heterocycle-containing polymer precursor material Are each not more than ± 10%.
The third embodiment of the heterocycle-containing polymer precursor material of the present invention is 1 g from any four points of the heterocycle-containing polymer precursor material obtained by the method for producing a heterocycle-containing polymer precursor material of the present invention The ratio of change in the mass of the polymerization inhibitor in the samples collected separately and the mass of the polymerization inhibitor in the entire heterocycle-containing polymer precursor material is ± 10% or less of the heterocycle-containing polymer precursor material. .
In the first to third embodiments, the rate of change with the mass of the polymerization inhibitor in the entire heterocycle-containing polymer precursor material is preferably 8% or less, more preferably ± 6% or less, ± 4 % Or less is more preferable.
Furthermore, in the present invention, in the first to third embodiments, the heterocycle-containing polymer precursor material contains a polymerization inhibitor in a proportion of 0.001 to 10% by mass of the heterocycle-containing polymer precursor material. Is preferred.
The lower limit value of the amount of the polymerization inhibitor in the heterocycle-containing polymer precursor material is more preferably 0.1% by mass or more, and can be 0.2% by mass or more. The upper limit of the amount of the polymerization inhibitor in the heterocycle-containing polymer precursor material is preferably 9% by mass or less, may be 7% by mass or less, and may be 5% by mass or less. It can be 1.0 mass% or less, in particular, 0.7 mass% or less, more particularly, 0.4 mass% or less.
The heterocycle-containing polymer precursor material of the present invention may be in a dried solid state or may contain a solvent such as a second solvent. As a preferred embodiment, one in which 95% by mass or more of the heterocycle-containing polymer precursor material is a heterocycle-containing polymer precursor is exemplified.

<Composition>
The composition containing the heterocycle-containing polymer precursor material of the present invention is not particularly limited as long as the other components are specified, as long as the composition contains the heterocycle-containing polymer precursor material. The ingredients can be blended. The composition containing the heterocycle-containing polymer precursor material of the present invention is preferably a photosensitive resin composition.
The photosensitive resin composition of the present invention comprises a heterocycle-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, it may contain a polymerizable compound. 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 contained.
The photosensitive resin composition in the present invention may also be a positive photosensitive resin composition. In particular, in the case of a positive photosensitive resin composition, the heterocycle-containing polymer precursor material preferably 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-closing polyimide, polybenzoxazole or the like within the scope of the present invention.

The content of the heterocycle-containing polymer precursor material in the photosensitive resin composition of the present invention is preferably 20 to 100% by mass, and 50 to 99% by mass, with respect to the total solid content of the photosensitive resin composition. Is more preferably 70 to 98% by mass, and particularly preferably 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 other components than these, and these components are not essential.

<< photoinitiator >>
The photosensitive resin composition of the present invention may contain a photopolymerization initiator. In particular, when the photosensitive resin composition contains a radical photopolymerization initiator, the photosensitive resin composition is applied to a semiconductor wafer or the like to form a photosensitive resin composition layer, and then light is irradiated to form a radical. Hardening occurs by this, and the solubility in a light irradiation part can be reduced. Therefore, 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 pattern of the electrodes. There is.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the 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. In addition, it may be an activator which produces an active radical by causing an action with a photoexcited sensitizer.
The photopolymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

  As the photopolymerization initiator, known compounds can be used without limitation, and for example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group, etc.), Acyl phosphine compounds such as acyl phosphine oxides, oxime compounds such as hexaaryl biimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ether, aminoacetophenone compounds, hydroxyacetophenone, azo system Compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes and the like can be mentioned.

  As a halogenated hydrocarbon derivative having a triazine skeleton, for example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F . C. Schaefer et al. Org. Chem. Compounds described in JP-A-62-58241; compounds described in JP-A-5-281728; compounds described in JP-A-5-34920; Examples thereof include the compounds described in Japanese Patent No. 4212976.

  Examples of the compounds described in US Pat. No. 4,129,976 include compounds having an oxadiazole skeleton (eg, 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)- , 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 and the like) and the like.

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

As a ketone compound, the compound as described in Paragraph No. 0087 of Unexamined-Japanese-Patent No. 2015-087611 is illustrated, for example, These content is integrated in this specification.
Among commercial products, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acyl phosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
As a hydroxy acetophenone type initiator, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (brand name: all are BASF Corporation make) can be used.
As aminoacetophenone initiators, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corporation) can be used.
As the aminoacetophenone initiator, a compound described in JP 2009-191179 A, in which the absorption wavelength is matched to a light source such as 365 nm or 405 nm, can also be used.
As an acyl phosphine type initiator, IRGACURE-819 and DAROCUR-TPO (brand name: all made by BASF Corporation) which are commercial items can be used.

As a photoinitiator, More preferably, an oxime compound is mentioned. As specific examples of the oxime compound, the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, and the compounds described in JP-A-2006-342166 can be used.
As preferable oxime compounds, 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 Examples include imino-1-phenylpropan-1-one and the like.

As oxime compounds, JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000 The compound etc. which are described in each gazette of -66385, Unexamined-Japanese-Patent No. 2000-80068, Japanese Patent Publication No. 2004-534797, and Unexamined-Japanese-Patent No. 2006-342166 are mentioned.
Among commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), and N-1919 (manufactured by ADEKA) are also suitably used. In addition, TR-PBG-304 (made by Changzhou Strong Electronic New Material Co., Ltd.), Adeka Akuls NCI-831 and Adeka Ark's NCI-930 (made by ADEKA Corporation) can also be used.

Further, a compound described in JP-A-2009-519904, in which an oxime is linked to the N-position of a carbazole ring, a compound described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into a benzophenone moiety, a nitro Compounds described in JP-A-2010-15025 and US Patent Publication 2009-292039, ketoxime compounds described in WO2009 / 131189, triazine skeleton and oxime skeleton in the same molecule The compound described in US Pat. No. 7,556,910, the compound described in JP 2009-221114 A having an absorption maximum at 405 nm and having good sensitivity to a g-line light source may be used.
Moreover, the cyclic oxime compound described in Unexamined-Japanese-Patent No. 2007-231000 and Unexamined-Japanese-Patent No. 2007-322744 can also be used suitably. Among cyclic oxime compounds, cyclic oxime compounds fused to a carbazole dye described in, for example, JP-A-2010-32985 and JP-A-2010-185072 have high light absorption and high sensitivity. It is preferable from the viewpoint.
Moreover, the compound of Unexamined-Japanese-Patent No. 2009-242469 which is a compound which has an unsaturated bond in the specific part of an oxime compound can also be used suitably.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. As a specific example of such an oxime compound, a compound described in JP-A-2010-262028, a compound 24 described in JP-A-2014-500852, paragraph No. 0345, 36 to 40, JP-A The compound (C-3) etc. which are described in stage number 0101 of the 2013-164471 gazette etc. are mentioned. Specific examples include the following compounds.
As a most preferable oxime compound, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-269779, the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061, etc. are mentioned.

The photopolymerization initiator is a trihalomethyl triazine compound, a benzyldimethyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl from the viewpoint of exposure sensitivity. Imidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivative thereof, cyclopentadiene-benzene-iron complex and salt thereof, halomethyl oxadiazole compound, 3-aryl substituted coumarin compound Compounds are preferred.
More preferable are trihalomethyl triazine compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and more preferably trihalomethyl triazine compounds Α-amino ketone compounds, oxime compounds, triarylimidazole dimers, benzophenone compounds, and the use of oxime compounds is 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 with respect to the total solid content of the photosensitive resin composition, and more preferably 0.1 It is -20 mass%, More preferably, it is 0.1-10 mass%.
The photopolymerization initiator may be used alone or in combination of two or more. When two or more photopolymerization initiators are used, the total is preferably in the above range.

<< polymeric compound >>
The photosensitive resin composition of the present invention preferably contains a polymerizable compound. By containing the polymerizable compound, a cured film more excellent in heat resistance can be formed.
The polymerizable compound is a compound having a polymerizable group, and a known compound which can be crosslinked by a radical, an acid, a base or the like can be used. Examples of the polymerizable group include the polymerizable groups described above for the heterocycle-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, for example, monomers, prepolymers, oligomers or mixtures thereof and multimers 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 weight compound, preferably a low molecular weight compound having a molecular weight of 2,000 or less, more preferably a low molecular weight compound having a molecular weight of 1,500 or less, and a molecular weight of 900 or less It is more preferable that it is a low molecular weight compound of The molecular weight of the polymerizable monomer is usually 100 or more.
Also, the polymerizable compound of the oligomer type is typically a polymer of relatively low molecular weight, and is preferably a polymer in which 10 to 100 polymerizable monomers are bonded. As a molecular weight, it is preferable that the weight average molecular weights of polystyrene conversion by gel permeation chromatography (GPC) method are 2,000-20,000, 2,000-15,000 are more preferable, and 2,000- Most preferably, it is 10,000.

In the present invention, the functional group number of the polymerizable compound means the number of polymerizable groups in one molecule.
The polymerizable compound preferably contains at least one bifunctional or more polymerizable compound containing two or more polymerizable groups, and preferably contains at least one trifunctional or more polymerizable compound from the viewpoint of resolution. More preferable.
In addition, the polymerizable compound in the present invention preferably contains at least one trifunctional or higher polymerizable compound also from the viewpoint that the heat resistance can be improved by forming a three-dimensional crosslinked structure. In addition, a mixture of a bifunctional or less polymerizable compound and a trifunctional or more polymerizable compound may be used.

<<< compound having an ethylenically unsaturated bond >>>
As a group which has 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 (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.) and esters thereof, amides thereof, and these And the esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and the amides of unsaturated carboxylic acids and polyhydric amine compounds, and multimers thereof. Also, an addition reaction product of an ester or amide of unsaturated carboxylic acid having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, a monofunctional or monofunctional Dehydration condensation products with polyfunctional carboxylic acids and the like are also suitably used. Also, addition reaction products of esters or amides of unsaturated carboxylic acids having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, thiols, and halogens Substitution products of esters or amides of unsaturated carboxylic acids having leaving substituents such as groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines and thiols are also suitable. As another example, instead of the above unsaturated carboxylic acid, it is also possible to use unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether or the like, and a group of compounds replaced.

  Specific examples of monomers of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include, as acrylic acid esters, 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, tetramer Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, di Interaerythritol 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.

  As methacrylic acid esters, 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-hydroxypro ) Phenyl] dimethyl methane, there are bis [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  As itaconic acid esters, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetraitaconate.

  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 esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  As examples of other esters, for example, aliphatic alcohol-based esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. Compounds having an aromatic skeleton described in JP-A-59-5241 and JP-A-2-226149, compounds containing an amino group described in JP-A-1-165613, and the like are also suitably used. Be

  Moreover, as a specific example of the monomer of the amide of a polyvalent amine compound and unsaturated carboxylic acid, methylene bis- acrylamide, methylene bis- methacrylamide, 1, 6- hexamethylene bis- acrylamide, 1, 6- hexamethylene bis- methacryl Amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bis methacrylamide and the like.

  As an example of another preferable amide-type monomer, the monomer which has the cyclohexylene structure of Japanese Patent Publication No.54-21726 can be mentioned.

In addition, a urethane addition polymerization monomer produced by using an addition reaction of an isocyanate and a hydroxyl group is also preferable, and as such a specific example, for example, one molecule described in JP-B-48-41708 Examples thereof include a vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule, in which a vinyl monomer containing a hydroxyl group represented by the following formula is added to a polyisocyanate compound having two or more isocyanate groups.
CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH
(However, R ⁴ and R ⁵ represent H or CH _3. )
Also, 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-based skeleton described in JP-A-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.

  Moreover, as a compound which has an ethylenically unsaturated bond, the compound described in Paragraph No. 0095-0108 of Unexamined-Japanese-Patent No. 2009-288705 can be used suitably also in this invention.

Moreover, as a compound which has an ethylenically unsaturated bond, the compound which has a boiling point of 100 degreeC or more under normal pressure is also preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( Meta) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) Those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as socyanurate, glycerin or trimethylolethane and then converting it to (meth) acrylate, JP-B-48-41708, JP-B-50-6034, JP-A-51. Urethane (meth) acrylates described in each publication of JP-37193, and polyester acrylates described in JP-A-48-64183, JP-B-49-43191, and JP-B-52-30490 Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates, which are the reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof. Moreover, the compound as described in Paragraph No. 0254-0257 of Unexamined-Japanese-Patent No. 2008-292970 is also suitable. In addition, polyfunctional (meth) acrylates obtained by reacting a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group with a polyfunctional carboxylic acid can also be mentioned.
Moreover, as a compound having another preferable ethylenically unsaturated bond, it has a fluorene ring described in JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. Compounds having two or more groups having unsaturated bonds, cardo resins can also be used.
Further, as other examples, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493 are disclosed. And the like. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Japan Adhesiveness Association magazine vol. 20, no. Also those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can be used.

  Besides 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 the plurality of R is —OC (OCO) CH = CH ₂ or —OC (= O) represents a group represented by C (CH ₃ ) = CH ₂ .
As a specific example of a compound which has an ethylenically unsaturated bond represented by said Formula (MO-1)-(MO-5), it describes in stage number 0248-0251 of Unexamined-Japanese-Patent No. 2007-269779. The compounds can also be suitably used in the present invention.

  Further, in JP-A No. 10-62986, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then converting it into (meth) acrylate as described in the formulas (1) and (2) together with specific examples thereof are also available. It can be used as a polymerizable compound.

  Examples of compounds having an ethylenically unsaturated bond include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320). Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; 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 linked via ethylene glycol and propylene glycol residues are preferable. 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 the unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a nonaromatic carboxylic acid anhydride to obtain an acid group. More preferred are polyfunctional monomers having an alkyl group, particularly preferably in this ester, where 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.
The polyfunctional monomer having an acid group may be used singly or in combination of two or more. Moreover, you may use together the polyfunctional monomer which does not have an acidic radical, and the polyfunctional monomer which has an acidic radical as needed.
As a preferable acid value of the polyfunctional monomer which has an acidic radical, it is 0.1-40 mgKOH / g, Especially preferably, it is 5-30 mgKOH / g. When the acid value of the polyfunctional monomer is in the above-mentioned range, it is excellent in production and handling, and further, excellent in developability. Moreover, 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, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, and the like. An ε-caprolactone modified multifunctional obtained by esterifying (meth) acrylic acid and ε-caprolactone with a polyhydric alcohol such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine etc. Mention may be made of (meth) acrylates. Among them, a polymerizable compound having a caprolactone structure represented by the following formula (C) is preferable.

Formula (C)

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

Formula (D)

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

Formula (E)

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

A polymerizable compound having such a caprolactone structure is, for example, commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (in the above formulas (C) to (E), m = 1, D) the number of groups represented by D = 2, a compound wherein all R ^{1 s} are hydrogen atoms, DPCA-30 (in the formula, m = 1, the number of groups represented by the formula (D) = 3, R ¹ Compounds in which all are hydrogen atoms, DPCA-60 (same formula, m = 1, number of groups represented by formula (D) = 6, compounds in which R ¹ is all hydrogen atoms), DPCA-120 (same formula In the formula, m = 2, the number of groups represented by the formula (D) = 6, and compounds wherein all R ¹ are hydrogen atoms can be mentioned.
In the present invention, the compounds having a caprolactone structure and an ethylenically unsaturated bond can be used alone or in combination 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 formulas (i) and (ii), E each independently represents-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-; 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 formula (i), the total of (meth) acryloyl groups is three or four, m independently represents an integer of 0 to 10, and the sum of each m is an integer of 0 to 40 . However, when the sum of each m is 0, any one of X is a carboxyl group.
In formula (ii), the total of (meth) acryloyl groups is 5 or 6, n independently represents an integer of 0 to 10, and the sum of each n is an integer of 0 to 60 is there. However, when the sum of each n is 0, any one of X is a carboxyl group.

In formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and, as for the sum of each m, the integer of 4-8 is especially preferable.
In formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 3-60 is preferable, the integer of 3-24 is more preferable, and, as for the sum of each n, the integer of 6-12 is especially preferable.
In the formula (i) or the formula (ii),-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-has a terminal at the oxygen atom side bonded to The preferred form is In particular, in the formula (ii), a form in which all six X's are an acryloyl group is preferable.

  In the compound represented by the formula (i) or (ii), a ring-opened skeleton is linked by ring-opening addition reaction of ethylene oxide or propylene oxide with pentaerythritol or dipentaerythritol, which is a conventionally known step; For example, (meth) acryloyl chloride is reacted with the terminal hydroxyl group of the ring-opened skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, and those skilled in the art can easily synthesize a compound represented by formula (i) or (ii).

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

  As commercially available products of the polymerizable compounds represented by the formulas (i) and (ii), for example, SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmar, a pench manufactured by Nippon Kayaku Co., Ltd. Examples include DPCA-60 which is a hexafunctional acrylate having 6 lenoxy chains, and TPA-330 which is a trifunctional acrylate having 3 isobutylene oxy chains.

Examples of compounds 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 as 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, JP-A-1-105238 as a polymerizable compound Monomers can also be used.
As a commercial item of the compound which has an ethylenically unsaturated bond, Urethane oligomer UAS-10, UAB-140 (made 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 Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer PME 400 (manufactured by NOF Corporation), and the like.

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

  Specific examples of the compound having an ethylenically unsaturated bond having the above partial structure include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide modified with isocyanuric acid ethylene oxide, di (meth) acrylate, ethylene oxide oxide modified tri (meth) isocyanuric acid. Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra ( Examples thereof include meta) acrylates, and in the present invention, these polymerizable compounds can be particularly preferably used.

The content of the compound having an ethylenically unsaturated bond in the photosensitive resin composition is 1 to 50% by mass based on 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. Although the compound which has an ethylenically unsaturated bond may be used individually by 1 type, you may mix and use 2 or more types.
In addition, the mass ratio of the heterocycle-containing polymer precursor material and the compound having an ethylenically unsaturated bond (heterocycle-containing polymer precursor material / polymerizable compound) is preferably 98/2 to 10/90, 95/5. -30/70 is more preferable, and 90 / 10-50 / 50 is the most preferable. If the mass ratio of the heterocycle-containing polymer precursor material and the compound having an ethylenically unsaturated bond is in the above-mentioned range, a cured film which is more excellent in the polymerizability and heat resistance can be formed.

<<< compound having a hydroxymethyl group, an alkoxymethyl group or an 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)
(Wherein 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) Shows 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 Formula (AM1) is preferably 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the heterocycle-containing polymer precursor material. More preferably, it is 10 parts by mass or more and 35 parts by mass or less. In addition, the compound represented by the following formula (AM4) is contained in an amount of 10% by mass to 90% by mass and the compound represented by the following formula (AM5) is contained in an amount of 10% by mass or more in all the polymerizable compounds. 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 (AM 2) or the following formula (AM 3)).

(AM5)
(Wherein u represents an integer of 3 to 8, R ⁴ represents a u-valent organic group having 1 to 200 carbon atoms, R ⁵ represents a hydroxyl group, or the following formula (AM2) or the following formula (AM2) It shows the group shown by AM 3).

(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 the board | substrate with an unevenness | corrugation, it is less and a crack arises. Furthermore, it is excellent in pattern processability, and 5% weight loss temperature can have high heat resistance which becomes 350 degreeC or more preferably, more preferably 380 degreeC or more.
Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (all trade names, 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, dimethyol BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (all trade names, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl- p-cresol etc. are mentioned.

  In addition, 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-TPHAP (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 an epoxy group)>>>
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy compound crosslinks at a temperature of 200 ° C. or less, and a dehydration reaction does not occur in the crosslinking reaction, so that film contraction 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. In addition, since the flexibility is high, a cured film excellent in 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 epoxy compounds are: 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; Examples include epoxy group-containing silicones such as (oxypropyl) siloxane and the like, but are not limited thereto. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (R) EXA-4710, Epiclon (R) HP-4770, Epiclon (R) EXA-859 CRP, Epiclon (R) EXA-1514, Epiclon (R) EXA-4880, Epiclon (R) EXA-4850-150, Epiclon (registered trademark) EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822 (trade names, manufactured by Dainippon Ink and Chemicals, Inc.), Rika Resin (registered trademark) BEO-60E (Products above , New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (trade name, (Ltd.) and the like Adeka). Among these, the epoxy resin containing a polyethylene oxide group is preferable at the point which is excellent in low curvature and heat resistance. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and Rikaresin (registered trademark) BEO-60E are preferable because they contain polyethylene oxide groups.

  The content of the epoxy 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 heterocycle-containing polymer precursor material. If the compounding amount is 5 parts by mass or more, warpage of the cured film can be further suppressed, and if 50 parts by mass or less, pattern filling accompanying reflow at the time of collection heating (cure) can be further suppressed.

<<< Oxetane Compound (Compound Having Oxetanyl Group) >>>
Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyl oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, Examples include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like. As a specific example, Aon oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be suitably used, and these can be used alone or in combination. You may mix species or more.

  The content of the oxetane 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 heterocycle-containing polymer precursor material.

<<< benzoxazine compound (compound having a benzoxazolyl group) >>>
Since a benzoxazine compound causes a crosslinking reaction by a ring opening addition reaction, no degassing due to curing occurs, and furthermore, the shrinkage due to heat is small. For this reason, the occurrence of warpage can be well attributed.

  Preferred examples of the benzoxazine compound include B-a type benzoxazine, B-m type benzoxazine (all trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzoxazine Compounds are mentioned. 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 heterocycle-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, including a resin containing a phenolic OH group adjusts the solubility in an alkali developer and is good It is preferable in that the sensitivity can be obtained.
As resins containing phenolic OH groups, novolak resins and polyhydroxystyrene resins are mentioned as preferred examples.

<<< Novolak resin >>>
The novolak resin is obtained by polycondensation of phenols and aldehydes by a known method. The novolak resin may be used in combination of two or more.
Preferred examples of the above-mentioned phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3 There can be mentioned 5-trimethylphenol, 3,4,5-trimethylphenol and the like. In particular, phenol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol and 2,3,5-trimethylphenol are preferred. Two or more of these phenols may be used in combination. From the viewpoint of solubility in an alkaline developer, m-cresol is preferable, and a combination of m-cresol and p-cresol is also preferable. That is, it is preferable to include, as a novolac resin, a cresol novolac resin containing m-cresol residue or m-cresol residue and p-cresol residue. At this time, the molar ratio (m-cresol residue / p-cresol residue, m / p) of m-cresol residue to p-cresol residue in cresol novolac resin is preferably 1.8 or more. If it is in this range, it exhibits appropriate solubility in an alkali developer and good sensitivity can be obtained. More preferably, it is 4 or more.
Further, as preferable examples of the above-mentioned aldehydes, formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like can be mentioned. 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 the phenol and a compound represented by the following formula (Ald) as the aldehyde is 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 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 and preferably 2 or more and 3 or less It is.

Formula (Ald)
In 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.

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 above-mentioned 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 etc. 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 the above are preferable. Furthermore, these phenols can be used 1 type or in mixture of 2 or more types.
By using a phenol compound having a number of substituents of 1 or more and 3 or less, preferably 2 or more and 3 or less as the above-mentioned phenol compound, the intramolecular rotation is suppressed, and a phenol resin having sufficient heat resistance necessary for the composition You can get

As the aromatic aldehyde compound represented by the above formula (Ald), an unsubstituted or aromatic aldehyde compound in which the number of substituents is 3 or less is used, and the substituent has 1 to 20 carbon atoms. And 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. As such aromatic aldehyde compounds, for example, benzaldehyde, 2-methyl benzaldehyde, 3-methyl benzaldehyde, 4-methyl benzaldehyde, 2,3-dimethyl benzaldehyde, 2,4-dimethyl benzaldehyde, 2,5-dimethyl benzaldehyde, 2,6-dimethyl benzaldehyde, 3,4-dimethyl benzaldehyde, 3,5-dimethyl benzaldehyde, 2,3,4-trimethyl benzaldehyde, 2,3,5-trimethyl benzaldehyde, 2,3,6-trimethyl benzaldehyde, 2, 4,5-trimethyl benzaldehyde, 2,4,6-trimethyl benzaldehyde, 3,4,5-trimethyl benzaldehyde, 4-ethyl benzaldehyde, 4-tert-butyl benzaldehyde, 4-i Butyl benzaldehyde, 4-methoxy benzaldehyde, salicylaldehyde, 3-hydroxy benzaldehyde, 4-hydroxy benzaldehyde, 3-methyl salicylaldehyde, 4-methyl salicyl aldehyde, 2-hydroxy-5-methoxy benzaldehyde, 2,4-dihydroxy benzaldehyde, 2 It is possible to use 5-dihydroxy benzaldehyde, 2,3,4- trihydroxy benzaldehyde and the like, without being limited thereto, among these, R ₂ in the formula (Ald) is hydrogen, methyl group, 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 1 type or in mixture of 2 or more types.

  In a synthesis reaction for obtaining a novolak resin from phenols and aldehydes, it is preferable to react the aldehyde compound at 0.5 mol or more and 2 mol or less, preferably 0.6 mol or more and 1.2 mol or less, with 1 mol of the phenol compound. It is more preferable to make it react by these, 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.

An acidic catalyst is usually used for the polycondensation reaction of phenols and aldehydes. 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 to be 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 the reaction medium, but when it becomes heterogeneous from the initial stage 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; cyclic ethers such as tetrahydrofuran and dioxane. Examples of lipophilic solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and 2-heptanone. The amount of the reaction medium 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 depending on the reactivity of the raw material, but is usually 10 to 200 ° C. As a reaction method for polycondensation, a method in which phenols, aldehydes, acidic catalysts, etc. are charged at one time and reacted, or a method in which phenols, aldehydes, etc. are added with the progress of reaction in the presence of acidic catalysts, etc. Can be adopted as appropriate. After completion of the polycondensation reaction, the reaction temperature is generally raised to 130 to 230 ° C. in order to remove unreacted raw materials, acidic catalysts, reaction media, etc. present in the system, and volatile components are removed under reduced pressure. Remove and recover the novolak resin.

  1,000 or more are preferable and, as for polystyrene conversion weight average molecular weight (Mw) of novolak resin, 2,000 or more are more preferable. Moreover, 5,000 or less is preferable. Within this range, good sensitivity can be obtained.

  The content of the novolac resin is preferably 1 part by mass to 70 parts by mass and more preferably 10 parts by mass to 70 parts by mass with respect to 100 parts by mass of the heterocycle-containing polymer precursor material. Within this range, a pattern with high sensitivity and which does not flow after heat treatment at high temperature can be obtained. The novolak resin 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 said range.

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

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

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

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

The structural unit represented by the above formula (PHS-1) is, for example, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenyl phenol, m-isopropenyl phenol, o-isopropenyl phenol, etc. And vinyl aromatic compounds having a phenolic hydroxyl group, and aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and the like, alone or in combination by polymerization of two or more thereof. A part of the polymer or copolymer thus obtained is obtained by 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 are preferably used, and as the aromatic vinyl compound, styrene is preferably used.

  Among hydroxystyrene resins having a repeating structural unit represented by the above formula (PHS-1), from the viewpoint of convenience that sensitivity can be further improved and solubility in an alkali developer can be adjusted, the following formula (PHS-2 Copolymers containing structural units represented by formula (PHS-3) and formula (PHS-4) are preferred. Furthermore, as for the structural unit of a formula (PHS-4), it is preferable that it is 50 mol% or less from the soluble point to alkaline developing solution.

Formula (PHS-2)
In formula (PHS-2), R ₄ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, c represents 1 to 4 and 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 or a propyl group.

Formula (PHS-3)

In 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 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, preferably 10,000 or less, more preferably 8, or more. It is at most 000, particularly preferably at most 7,000. By setting it as the said range, it has an effect which is excellent in coexistence of high sensitivity-ization and normal temperature storage property of a varnish.
The content of the hydroxystyrene resin is preferably 1 part by mass to 70 parts by mass and more preferably 10 parts by mass to 70 parts by mass with respect to 100 parts by mass of the heterocycle-containing polymer precursor material. Within this range, a pattern with high sensitivity and which does not flow after heat treatment at high temperature can be obtained. The hydroxystyrene resin 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 said range.

<< Thermal base generator >>
The photosensitive resin composition of the present invention may contain a thermal base generator.
The type and the like of the thermal base generator is not particularly limited, but is selected from an acidic compound which generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion of pKa1 of 0 to 4 and an ammonium cation It is preferable to include a thermal base generator containing at least one. Here, pKa1 is a logarithmic expression (−Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of a polyvalent acid.
By blending such a compound, the cyclization reaction of the polyimide precursor can be performed at a low temperature, and a photosensitive resin composition more excellent in stability can be obtained. In addition, since the thermal base generator does not generate a base without heating, the cyclization of the polyimide precursor during storage can be suppressed even when coexisted with the polyimide precursor, and the storage stability is excellent.

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

In the present invention, the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, and more preferably 120 to 200 ° C. The upper limit of the base generation temperature is more preferably 190 ° C. or less, further preferably 180 ° C. or less, and still more preferably 165 ° C. or less. The lower limit of the base generation temperature is more preferably 130 ° C. or more, and still more preferably 135 ° C. or more.
If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or more, a base is unlikely to be generated during storage, so that a polyimide precursor composition having excellent stability can be prepared. If the base generation temperature of an acidic compound (A1) and ammonium salt (A2) is 200 degrees C or less, the cyclization temperature of a polyimide precursor can be made low. The base generation temperature is measured by, for example, using differential scanning calorimetry, heating the compound at 5 ° C./min to 250 ° C. in a pressure resistant capsule, reading the peak temperature of the exothermic peak with the lowest temperature, and setting 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 amines are highly basic, the cyclization temperature of the polyimide precursor can be lowered. The boiling point of the base generated by the thermal base generator is preferably 80 ° C. or higher, preferably 100 ° C. or higher, and most preferably 140 ° C. or higher. Moreover, as for the molecular weight of the base to generate | occur | produce, 80-2,000 are preferable. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. In addition, the value of molecular weight is a theoretical value calculated | required from 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 Formula (1) described later.

  In the present invention, the ammonium salt (A2) is preferably an acidic compound. The above ammonium salt (A2) may be a compound containing an acidic compound which 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.). Compounds other than acidic compounds that generate a base when heated to

<<< Ammonia 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 covalently bonded to any part of the ammonium cation, or may be outside the molecule of the ammonium cation, but is preferably outside the molecule of the ammonium cation. In addition, that the anion is outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the anion outside the molecule of the cation part is also referred to as a counter anion.
^Wherein, R 1 to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, ^{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 combined to form a ring.

In the present invention, the ammonium salt preferably has an anion having a pKa of 0 to 4 and an ammonium cation. As for the upper limit of pKa1 of the anion, 3.5 or less is more preferable, and 3.2 or less is more preferable. The lower limit is more preferably 0.5 or more, and still more preferably 1.0 or more. If pKa1 of the anion is in the above range, the polyimide precursor can be cyclized at a low temperature, and furthermore, 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, 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 difficult to be neutralized, and the cyclization efficiency of the polyimide precursor is good.
The type of the 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 preferred because the stability of the salt and the thermal decomposition are compatible. That is, the ammonium salt is more preferably a salt of ammonium cation and carboxylic acid anion.
The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, it is possible to provide a thermal base generator capable of further improving the stability, the curability, and the developability of the polyimide precursor composition. In particular, the stability, the curability and the developability of the polyimide precursor composition can be further improved by using a divalent carboxylic acid anion.
In the present invention, the carboxylate anion is preferably an anion of a carboxylic acid having a pKa 1 of 4 or less. As for pKa1, 3.5 or less is more preferable, and 3.2 or less is further more preferable. 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, and is determined by Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Editing: Braude, The values described in EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (Author: Dawson, RMC et al .; Oxford, Clarendon Press, 1959) can be referred to. 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 Formula (X1), EWG represents an electron withdrawing group.

In the present invention, the electron withdrawing group means one having a positive value of Hammett's substituent constant σm. Here, σ m is a review by Tono Yuya, Journal of Organic Synthetic 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-mentioned documents.
Examples of the substituent having a positive value of σ m include, for example, CF ₃ group (σ m = 0.43), CF ₃ CO group (σ m = 0.63), HC≡C group (σ m = 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 (.sigma.m = 0.34), H ₂ NCOCH ₂ group (σ m = 0.06), and the like. Here, 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 one represented by the following formula (X).
In Formula (X), L ¹⁰ represents a single bond, or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, an -NR ^X- , and a combination thereof, and R ^X represents a hydrogen atom , An alkyl group, an alkenyl group or an aryl group.

  Specific examples of carboxylic acid anions include maleic acid anion, phthalic acid anion, N-phenyliminodiacetic acid anion and oxalic acid anion. These can be preferably used.

The ammonium cation is preferably represented by any one 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 represent 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 combined with 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 the carboxyl group is decarboxylated or dehydrated and cyclized and lost by heating, whereby the amine site which has been neutralized and inactivated becomes active, thereby being used as a base. 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 a (m + 1) -valent organic group, and 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 a (m + 1) -valent linking group, L ² represents a (n + 1) -valent linking group, and m is 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) are the same as the range described in the formula (1).

  Although the specific example of the thermal base generator in this invention is described below, this invention is not limited to these. These can be used alone or in combination 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, and the contents thereof are incorporated herein.

When using a thermal base generator, as for content of the thermal base generator in the photosensitive resin composition, 0.1-50 mass% is preferable with respect to the total solid of the photosensitive resin composition. As for a minimum, 0.5 mass% or more is more preferable, and 1 mass% or more is further more preferable. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.
The thermal base generator can be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount is the said range.

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

  Examples of the photoacid generator include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Above all, a quinone diazide compound is preferably used from the viewpoint of exhibiting an excellent dissolution inhibiting effect and obtaining a positive photosensitive resin composition with high sensitivity and little film loss. Moreover, you may contain 2 or more types of photo-acid generators. Thereby, the ratio of the dissolution rates of the exposed area and the unexposed area can be further increased, and a highly sensitive positive photosensitive resin composition can be obtained.

As a quinone diazide compound, a polyhydroxy compound obtained by ester bond of sulfonic acid of quinone diazide, a polyamino compound obtained by sulfonamide bond of sulfonic acid of quinone diazide, a polyhydroxy polyamino compound obtained by sulfonic acid of quinone diazide ester bond and / or a sulfonamide And the like. 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 general ultraviolet lamp is obtained. be able to. Also, all functional groups of these polyhydroxy compounds, polyamino compounds and polyhydroxy polyamino compounds may not be substituted with quinonediazide, but it is preferable that two or more functional groups per molecule be substituted with quinonediazide. .
The following compounds are illustrated as an example.
In the above compounds, 1 to 10% of the entire Q may be a hydrogen atom, and 4 to 6% may be a hydrogen atom.

  Examples of 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, Methylene Tris-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-35 XL, TML-BP, TML HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 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 (all manufactured by Asahi Organic Materials Co., Ltd.), 2, 6-dimethoxymethyl -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 (as mentioned above, brand name, Honshu Chemical Industry ), Although such a novolak resin include, but are not limited to.

  As polyamino compounds, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, 4,4′-diamino Although diphenyl sulfide etc. are mentioned, it is not limited to these.

  Moreover, as a polyhydroxy polyamino compound, although 2, 2-bis (3-amino 4-hydroxyphenyl) hexafluoro propane, 3,3'- dihydroxy benzidine etc. are mentioned, it is not limited to these.

  As the quinone diazide compound, any of a compound having a 5-naphthoquinone diazide sulfonyl group and a compound having a 4-naphthoquinone diazide sulfonyl group is preferably used. A compound having both of these groups in the same molecule may be used, or compounds using different groups may be used in combination.

  Examples of the method for producing the quinone diazide compound include a method in which 5-naphthoquinone diazide sulfonyl chloride is reacted with a phenol compound in the presence of triethylamine. The synthesis method of a phenol compound includes a method of reacting an α- (hydroxyphenyl) styrene derivative 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 heterocycle-containing polymer precursor material. By setting the content of the photoacid generator in this range, higher sensitivity can be achieved. Furthermore, a sensitizer may be contained as required.
The photoacid generator 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 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 upon heating, promotes cyclization of the heterocycle-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. It has the effect of promoting the crosslinking reaction of at least one compound selected from a compound, an epoxy compound, an oxetane compound and a benzoxazine compound.

  50 degreeC-270 degreeC are preferable, and, as for the thermal decomposition start temperature of a thermal acid generator, 250 degrees C or less is more preferable. In addition, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after applying the photosensitive resin composition to a substrate, and final heating (curing: about 100 to 400) after patterning by exposure and development thereafter. It is preferable to select one that generates an acid at the time of 1 ° C., because it is possible to suppress a decrease in sensitivity during development.

  The acid generated from the thermal acid generator is preferably a strong acid, for example, p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, methanesulfonic acid, alkylsulfonic acid such as ethanesulfonic acid, butanesulfonic acid, and trifluoromethane. Preferred are haloalkyl sulfonic acids such as sulfonic acids. As an example of such a thermal acid generator, the thing as described in Paragraph No. 0055 of Unexamined-Japanese-Patent No. 2013-072935 is mentioned.

Among them, those which generate an alkylsulfonic acid having 1 to 4 carbon atoms or a haloalkylsulfonic acid having 1 to 4 carbon atoms are more preferable from the viewpoint of having less residual in the cured film and not deteriorating the physical properties of the cured film.
As a thermal acid generator, methanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl (4-hydroxyphenyl) methylsulfonium methanesulfonate, Benzyl methanesulfonate (4-((methoxycarbonyl) oxy) phenyl) methyl sulfonium, (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium methanesulfonate, trifluoromethane sulfonic acid (4-hydroxyphenyl) Dimethylsulfonium, trifluoromethanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl trifluoromethanesulfonate (4-hydroxyphenyl) methyl Sulfonium, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl) oxy) phenyl) methyl sulfonium, trifluoromethane sulfonate (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, 3- (5- (5- ( ((Propylsulfonyl) oxy) imino) thiophene-2 (5H) -ylidene) -2- (o-tolyl) propanenitrile, 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoro Propane is preferred.

  Moreover, the compound of Paragraph No. 0059 of Unexamined-Japanese-Patent No. 2013-167742 is also preferable as a thermal acid generator.

When a thermal acid generator is used, the content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the heterocycle-containing polymer precursor material. By containing 0.01 parts by mass or more, the crosslinking reaction and the cyclization of the heterocycle-containing polymer precursor material are promoted, so that the mechanical properties and the 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.
The thermal acid generator 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 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). A well-known thermal radical polymerization initiator can be used as a thermal radical polymerization initiator.
The thermal radical polymerization initiator is a compound which generates a radical by the energy of heat to initiate or accelerate the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, when advancing the cyclization reaction of the heterocycle-containing polymer precursor material, the polymerization reaction of the polymerizable compound can be advanced. In addition, when the heterocycle-containing polymer precursor material contains an ethylenically unsaturated bond, the polymerization reaction of the heterocycle-containing polymer precursor material can also proceed along with the cyclization of the heterocycle-containing polymer precursor material, Higher heat resistance can be achieved.
As a thermal radical polymerization initiator, aromatic ketones, onium salt compounds, peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogen Compounds having a bond, azo compounds and the like can be mentioned. Among them, peroxides or azo compounds are more preferable, and peroxides are 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., and more preferably 100 to 120 ° C.
Specifically, compounds described in Paragraph Nos. 0074 to 0118 of JP-A-2008-63554 can be mentioned.
As a commercial item, Perbutyl Z and Percumil D (manufactured by NOF Corporation) can be suitably used.

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, 0.1 -30 mass% is more preferable, and 0.1-20 mass% is especially preferable. Moreover, it is preferable to contain 0.1-50 mass parts of thermal radical polymerization initiators with respect to 100 mass parts of polymeric compounds, and it is more preferable to contain 0.5-30 mass parts. According to this aspect, it is easy to form a cured film more excellent in heat resistance.
The thermal radical polymerization initiator may be used alone or in combination of two or more. When two or more thermal radical polymerization initiators are used, 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, and as a compound, for example, a rust inhibitor described in paragraph No. 0094 of JP-A-2013-15701, JP-A-2009-283711 Using the compounds described in paragraphs 0073 to 0076, the compounds described in paragraph 0052 of JP-A-2011-59656, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, etc. be able to. Among them, compounds having a triazole ring or compounds having a tetrazole ring can be preferably used, and 1,2,4-triazole, 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole, 1H-tetrazole More preferred is 5-methyl-1H-tetrazole, and most preferred is 1H-tetrazole.
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 heterocycle-containing polymer precursor material. It is the range of the mass part.
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 said range.

<< Metal Adhesion Improver >>
The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving the adhesion to a metal material used for electrodes, wiring and the like. As an example of a metal adhesiveness improving agent, the sulfide type compound as described in stage number 0046-0049 of Unexamined-Japanese-Patent No. 2014-186186 and stage number 0032-0043 of Unexamined-Japanese-Patent No. 2013-072935 is mentioned. The following compounds may also be exemplified as metal adhesion improvers.
When a metal adhesion modifier is used, the content of the metal adhesion modifier is preferably in the range of 0.1 to 30 parts by mass, more preferably 0 based on 100 parts by mass of the heterocycle-containing polymer precursor material. It is the range of 0.5-15 mass parts. When the amount is 0.1 parts by mass or more, the adhesion between the film after heat curing and the metal becomes good, and when the amount is 30 parts by mass or less, the heat resistance and mechanical properties of the film after curing become good.
The metal adhesion improver may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the sum 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. As examples of silane coupling agents, compounds described in paragraphs 0062 to 0073 of JP-A 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication WO 2011/09092 A1, and JP-A 2014-191252 The compounds described in paragraphs 0060 to 0061 of the gazette, the compounds described in paragraphs 0045 to 0052 in JP-A 2014-41264, and the compounds described in paragraph 0055 of International Publication WO 2014/097594. Moreover, as described in Paragraph No. 0050-0058 of Unexamined-Japanese-Patent No. 2011-128358, it is also preferable to use 2 or more types of different silane coupling agents.
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 by mass with respect to 100 parts by mass of the heterocycle-containing polymer precursor material. It is the range of the mass part. When the amount is 0.1 parts by mass or more, sufficient adhesion to the substrate can be imparted, and when the amount is 20 parts by mass or less, problems such as viscosity increase can be further suppressed during storage at room temperature.
The silane coupling agent 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 said range.

<< Dissolution 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 sensitivity improvement. As the dissolution accelerator, low molecular weight phenols (for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR- PC, BIR-PTBP, BIR-BIPC-F (above, trade name, manufactured by Asahi Organic Materials Industry Co., Ltd., phenols described in paragraphs 0056 to 0062 of JP-A-2013-152381) and aryl sulfonamide derivatives (for example, And compounds described in Paragraph No. 0058 of JP-A-2011-164454).
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 heterocycle-containing polymer precursor material. The scope of the department.
The dissolution accelerator 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 said range.

<< Dissolution inhibitor >>
When the photosensitive resin composition of the present invention is a positive type using an alkali developing solution, a dissolution inhibitor (a compound which inhibits the solubility) should be contained in order to adjust the solubility in the alkali developing solution. Can. 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, and diazonium salts such as phosphonium salts and aryldiazonium salts.
Examples of the diaryl compound include compounds in which two aryl groups such as diaryl urea, diaryl sulfone, diaryl ketone, diaryl ether, diaryl propane, and diaryl hexafluoropropane are linked via a linking group, and examples of the aryl group include phenyl 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 these, those showing a good dissolution inhibiting effect include diaryliodonium salts, diarylureas, diarylsulfones, tetramethyl ammonium halides, etc., and diarylureas include diphenylurea, dimethyldiphenylurea, etc. Examples of tetramethyl ammonium halides include tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetramethyl ammonium iodide and the like.

Among them, diaryl iodonium salts represented by the formula (Inh) are preferable.
(Wherein, X ⁻ represents a counter anion, R ⁷ and R ⁸ each independently represent a monovalent organic group, and 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, chloride ion, bromide ion, iodide ion and the like. Be

Examples of diaryl iodonium salts include diphenyl iodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyl iodonium trifluoromethane sulfonate, bis (p-tert-butyl phenyl) iodonium trifluoromethane sulfonate, diphenyl iodonium Bromide, diphenyliodonium chloride, diphenyliodonium iodide, diphenyliodonium-8-anilinonaphthalene-1-sulfonate and the like can be used.
Among these, diphenyliodonium nitrate, diphenyliodonium trifluoromethanesulfonate and diphenyliodonium-8-anilinonaphthalene-1-sulfonate are mentioned as highly effective and preferable.

When the dissolution inhibitor is contained, the content of the dissolution inhibitor is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the heterocycle-containing polymer precursor material from the viewpoint of sensitivity and an allowable width of development time. 0.1 to 15 parts by mass is more preferable, and 0.5 to 10 parts by mass is more preferable.
The dissolution 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 said range.

<< sensitizing dye >>
The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific actinic radiation to be in an electronically excited state. The sensitizing dye in the electronically excited state comes into contact with an amine generator, a thermal radical polymerization initiator, a photopolymerization initiator and the like to cause 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 undergo a chemical change and decompose to form a radical, an acid or a base.

  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, erythrosin, 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 (eg, For example, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaliliums (eg, squalilium), 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 in view of initiation efficiency, and anthracene skeleton It is more preferable to use the compound which it has. Particularly preferable specific compounds include 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and the like.

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

<< chain transfer agent >>
The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in Polymer Dictionary Third Edition (edited by the Polymer Society of Japan, 2005) pages 683 to 684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. They can donate hydrogen to a low active radical species to form a radical or be oxidized and then deprotonated to form a radical. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazole, 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. The amount is 1 to 10 parts by mass, more preferably 1 to 5 parts by mass.
The chain transfer agent may be used alone or in combination of two or more. When two or more chain transfer agents are used, the total is preferably in the above range.

<< polymerization inhibitor >>
In the photosensitive resin composition of the present invention, in addition to the polymerization inhibitor incorporated into the heterocycle-containing polymer precursor material, a polymerization inhibitor may be further added.
Further polymerization inhibitors include, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butyl catechol, 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-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic 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) Preferred is -tert-butyl) phenylmethane.
When the photosensitive resin composition further contains a 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 additional polymerization inhibitor may be only one, or two or more. When two or more additional polymerization inhibitors are used, the total is preferably in the above range.
Moreover, the photosensitive resin composition of this invention can also be set as the structure which does not mix | blend substantially a further polymerization inhibitor other than the polymerization inhibitor taken in into the heterocyclic containing polymer precursor material. If the content of the additional polymerization inhibitor is not substantially blended, the content of the additional polymerization inhibitor is less than 0.01% by mass, further less than 0.001% by mass, and particularly less than the solid content in the photosensitive resin composition of the present invention. , 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 the coating properties. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a silicone surfactant and the like can be used.
In particular, by containing a fluorine-based surfactant, the liquid properties (in particular, the flowability) when prepared as a coating liquid are further improved, so that the uniformity of coating thickness and the liquid saving property can be further improved. .
In the case of film formation using a coating liquid containing a fluorine-based surfactant, the wettability to the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, and the coating surface is to be coated. Coating properties are improved. For this reason, even in the case where a thin film of about several μm is formed with a small amount of liquid, it is effective in that film formation with a uniform thickness with small thickness unevenness can be more suitably performed.

3-40 mass% is suitable for the fluorine content rate of a fluorine-type surfactant, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. The fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film and the liquid saving property, and the solubility is also good.
Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F44, R30, F437, F475, F479, and the like. The F482, the F554, the F780, the F781 (above, made by DIC Corporation), the Florard FC430, the same FC431, the same FC171 (above, Sumitomo 3M Co., Ltd.), Surfron S-382, the same SC-101, The same SC-103, the same SC-104, the same SC-105, the same SC 1068, the same SC-383, the same S393, the same KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 , PF6520, PF7002 (manufactured by OMNOVA), and the like.
A block polymer can also be used as a fluorine-type surfactant, and the compound described in Unexamined-Japanese-Patent No. 2011-89090 is mentioned as a specific example, for example.
Further, the following compounds are also exemplified as the fluorine-based surfactant 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 their ethoxylates and propoxylates (eg, 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 manufactured by BASF, L62, 10R5, 17R2, 25R2, Tetronics 304, 701, 704, 901, 904, 150 1), Solsperse 20000 (Lubrizol Japan Ltd.) and the like. In addition, Pionin D-6112-W manufactured by Takemoto Oil & Fat Co., Ltd., NCW-101, NCW-1001 and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

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

  As silicone type surfactant, for example, Toray Dow Corning Co., Ltd. product "Tore silicone DC3PA", "Tore silicone SH7PA", "Tore silicone DC11PA", "Tore silicone SH21PA", "Tore silicone SH28PA", "Tore silicone SH21PA" Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400, Momentive Performance Materials, Inc. "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF “4452”, “KP341”, “KF6001”, “KF6002” manufactured by Shin-Etsu Silicone Co., Ltd., “BYK307”, “BYK323”, “BYK330” manufactured by BIC Chemie, and the like.

When the photosensitive resin composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the photosensitive resin composition, and more preferably It is 0.005-1.0 mass%.
The surfactant may be used alone or in combination of two or more. When two or more surfactants are used, the total is preferably in the above range.

<< Higher fatty acid derivatives etc. >>
The photosensitive resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide to prevent polymerization inhibition by oxygen, and the photosensitive resin composition is dried in the process of drying after coating. It may be unevenly distributed on the surface of an 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.
The higher fatty acid derivatives may be used alone or in combination of two or more. When two or more kinds of higher fatty acid derivatives and the like are used, the total is preferably in the above range.

<< solvent >>
When making the photosensitive resin composition of this invention into a layer by application | coating, it is preferable to mix | blend a solvent. As the solvent, known solvents can be used without limitation as long as the photosensitive resin composition can be formed into a layer.
As a solvent used for the photosensitive resin composition of the present invention, as esters, for example, 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 alkyl oxyacetate (for example, methyl alkyl oxyacetate, ethyl alkyl oxy acetate, butyl alkyl oxy acetate (for example, methyl methoxy acetate, methoxy) Ethyl acetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.), 3-alkyloxypropionic acid alkyl esters (eg methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate etc. (eg Methyl methoxypropionate, ethyl 3-methoxypropionate, 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 (eg 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-methylpropionate) Ethyl pyonate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate etc. and as ethers, eg, 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 ester Ether acetate, and Lopylene glycol monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and N-methyl-2-pyrrolidone and the like, and as aromatic hydrocarbons For example, toluene, xylene, anisole, limonene and the like, and as the sulfoxides, for example, dimethyl sulfoxide is preferably mentioned.

  The solvent is also preferably in the form of a mixture of two or more from the viewpoint of improvement of the coated surface condition and the like. 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 preferred.

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 coatability. -70 mass% is more preferable, and 10-60 mass% is further more preferable.
The solvent may be used alone or in combination of two or more. When two or more solvents are used, the total is preferably in the above range.
In addition, the content of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide is the total mass of the photosensitive resin composition from the viewpoint of film strength. The amount is preferably less than 5% by mass, more preferably less than 1% by mass, still more preferably less than 0.5% by mass, and still more preferably less than 0.1% by mass.

<< Other Additives >>
The photosensitive resin composition of the present invention may contain various additives, for example, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, UV absorbers, as needed, as long as the effects of the present invention are not impaired. And anticoagulation agents can be blended. When mix | blending these additives, it is preferable that the sum total compounding quantity sets it as 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 mass, more preferably less than 1% by mass, and still more preferably less than 0.6% by mass from the viewpoint of coated surface state.

From the viewpoint of insulation, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. 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.
Moreover, as a method of reducing the metal impurities contained unintentionally in the photosensitive resin composition, a photosensitive resin composition is selected, in which a raw material having a small metal content is selected as a raw material constituting the photosensitive resin composition. For example, the raw material may be subjected to filter filtration, or the inside of the apparatus may be lined with polytetrafluoroethylene or the like to carry out distillation under conditions in which contamination is suppressed as much as possible.

  The photosensitive resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and still more preferably less than 200 mass ppm from the viewpoint of wiring corrosion. Among them, those less than 5 mass ppm are preferable, those less than 1 mass ppm are more preferable, and less than 0.5 mass ppm is more preferable. The halogen atom includes a chlorine atom and a bromine atom. It is preferable that the total of a chlorine atom and a bromine atom, or a chloride ion and a bromide ion is respectively in the above range.

<< Preparation of photosensitive resin composition >>
The photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be carried out by a conventionally known method.
Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and particles in the composition. The pore diameter of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be one previously washed with an organic solvent. In the filter filtration step, a plurality of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes and / or different materials may be used in combination. Also, the various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step. Moreover, you may pressurize and you may filter, and the pressure to pressurize has preferable 0.05-0.3 MPa.
Besides filtration using a filter, removal of impurities may be performed using an adsorbent. In addition, filtration using a filter and removal of impurities using an adsorbent may be performed in combination. 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.

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

Next, an embodiment of a semiconductor device using the above composition for an interlayer insulating film for redistribution layers will be described.
A semiconductor device 100 illustrated 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 disposed on a wiring substrate 120.
Although this embodiment will be described focusing on the case where the number of stacked semiconductor elements (semiconductor chips) is four, the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. It may be a layer, eight layers, sixteen layers, thirty two layers or the like. Also, it may be a single layer.

The plurality of semiconductor elements 101a to 101d are all 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) integrally provided on 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 a semiconductor element 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 through electrode 102b adjacent thereto 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 through 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 through electrode 102d adjacent thereto via the metal bump 103c such as a solder bump. ing.

  Underfill layers 110 are 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 substrate 120.
As the wiring substrate 120, for example, a multilayer wiring substrate using an insulating substrate such as a resin substrate, a ceramic substrate, a glass substrate or the like as a base material is used. Examples of the wiring substrate 120 to which a resin substrate is applied include a multilayer copper-clad laminate (multilayer printed wiring board) and the like.

A surface electrode 120 a is provided on one surface of the wiring substrate 120.
The insulating layer 115 on which the 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 to each other through the rewiring layer 105. It is connected. The insulating layer 115 is formed by using the photosensitive resin composition of the present invention.
That is, one end of the redistribution layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the redistribution layer 105 side via the metal bump 103d such as a solder bump. Further, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via the metal bump 103e such as a solder bump.
An underfill layer 110 a is formed between the insulating layer 115 and the stack 101. Also, 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 by the present invention can be widely adopted in various applications using polyimide and polybenzoxazole.
In addition, since polyimide and polybenzoxazole are resistant to heat, the cured film produced according to the present invention is used for transparent plastic substrates for display devices such as liquid crystal displays and electronic papers, automobile parts, heat resistant paints, coating agents and films Can also be suitably used.

  Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise stated, "parts" and "%" are on a mass basis.

Example 1
[Synthesis of polyimide precursor A-1 from 4,4′-oxydiphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
Mix 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) at 60 ° C. Stirring at temperature for 4 hours produced the 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, keeping 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 in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 5 ° C. The mixture was then stirred for 2 hours.
Then, 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 after stirring (the solid of the polyimide precursor) is collected by filtration, and tetrahydrofuran (good solvent, manufactured by Wako Pure Chemical Industries, Ltd., as a polymerization inhibitor G-1) is used as 2,6-di-tert-butyl-p. Cresol (BHT) was dissolved in 500 g of 0.03% by mass). To the obtained solution was added 6 L of water (poor solvent) to precipitate a polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred at a speed of 200 rpm for 15 minutes. The precipitate after stirring (solid of polyimide precursor) was filtered again and dried under reduced pressure at 45 ° C. for 3 days.
The 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>
Four 1 g aliquots were optionally taken from 50 g of the resulting heterocycle-containing polymer precursor material, and each was transferred to a 20 mL light-shielded glass container. 5 g of N-methylpyrrolidone was added to each light-shielding glass container to dissolve the heterocycle-containing polymer precursor material to prepare a sample solution. The sample solution thus obtained is subjected to gas chromatography measurement (apparatus: Agilent 7890A, column: HP-55, column temperature: 300 ° C.), and the content of polymerization inhibitor contained in each heterocycle-containing polymer precursor material (unit: : The difference between each of the measured and 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 is shown as a change rate (unit:%). The smaller the rate of change, the more uniformly the polymerization inhibitor is present. The results are shown in Table 5.

<Storage stability>
10 g of the obtained heterocycle-containing polymer precursor material was dissolved in 200 mL of N-methylpyrrolidone, and the viscosity of the solution at 25 ° C. was measured using a 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 for one week in an environment of 25 ° C. and a humidity of 65%. The viscosity of the heterocycle-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 increase or decrease in viscosity is 90% or more and less than 110%.
B: The increase or decrease in viscosity is 110% or more and less than 130%.
C: The change in viscosity is 130% or more and less than 150%.
D: The increase or 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]
Mix 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 and stir at a temperature of 60 ° C. for 4 hours The diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate was prepared. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes, keeping 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 in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 5 ° C. The mixture was then 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.) is added to the obtained reaction mixture, and 6 L of water is further added. In addition, the polyimide precursor was precipitated and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The precipitate after stirring was filtered again and dried under reduced pressure at 45 ° C. for 3 days.
The polyimide precursor had a weight average molecular weight of 25,200 and a number average molecular weight of 8,000.
As in Example 1, the uniformity and storage stability of the content of the polymerization inhibitor 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]
Mix 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 and stir at a temperature of 60 ° C. for 4 hours The diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate was prepared. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes, keeping 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 in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 5 ° C. The mixture was stirred for 2 hours. Next, 6 L of water was added to the obtained solution to precipitate a polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The precipitate after stirring is collected by filtration, to which is added 2,6-di-tert-butyl-p-cresol as a polymerization inhibitor G-1 manufactured by Wako Pure Chemical Industries, Ltd. as a polymerization inhibitor under reduced pressure. 500 g of a solution so dissolved as to contain 0.03% by mass, and 0.15 g of p-methoxyphenol as a polymerization inhibitor G-2 were added. To the resulting solution was added 6 L of water 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 again and dried under reduced pressure at 45 ° C. for 3 days.
The polyimide precursor had a weight average molecular weight of 22,500 and a number average molecular weight of 7,400.
As in Example 1, the uniformity and storage stability of the content of the polymerization inhibitor 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]
Mix 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 and stir at a temperature of 60 ° C. for 4 hours The diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate was prepared. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes, keeping 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 in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 5 ° C. 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 is collected by filtration and dissolved in 500 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., stabilizer-free), and 0.15 g of 2,6-di-tert-butyl-p-cresol is added. The To the resulting solution was added 6 L of water 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 again and dried under reduced pressure at 45 ° C. for 3 days.
The polyimide precursor had a weight average molecular weight of 23,800 and a number average molecular weight of 7,700.
As in Example 1, the uniformity and storage stability of the content of the polymerization inhibitor 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]
Mix 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 at a temperature of 60 ° C. The mixture was stirred for 4 hours to produce diesters 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, keeping 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 in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 5 ° C. The mixture was then 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 300 g of N-methylpyrrolidone, and 1.2 g of hydroquinone was added as a polymerization inhibitor G-3. To the resulting solution was added 6 L of water 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 again and dried under reduced pressure at 45 ° C. for 3 days.
The polyimide precursor had a weight average molecular weight of 26,800 and a number average molecular weight of 8,800.
As in Example 1, the uniformity and storage stability of the content of the polymerization inhibitor 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]
Mix 15.5 g of pyromellitic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of N-methylpyrrolidone and stir at a temperature of 60 ° C. for 4 hours The diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate was prepared. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes, keeping 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 in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 5 ° C. The mixture was then stirred for 2 hours. Next, 3.2 g of benzoquinone as a polymerization inhibitor G-4 is added to the obtained reaction mixture, and 6 L of water is further added to precipitate a polyimide precursor, and the precipitate is subjected to 15 minutes at a speed of 200 rpm. It stirred. The precipitate after stirring was filtered again and dried under reduced pressure at 45 ° C. for 3 days. The polyimide precursor had a weight average molecular weight of 24,500 and a number average molecular weight of 8,200.
As in Example 1, the uniformity and storage stability of the content of the polymerization inhibitor 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]
Mix 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 and stir at a temperature of 60 ° C. for 4 hours The diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate was prepared. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes, keeping 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 in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 5 ° C. The mixture was then stirred for 2 hours.
Then, 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, dissolved in 500 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., containing 0.03% by mass of 2,6-di-tert-butyl-p-cresol), and 1.0 g Of 2,6-di-tert-butyl-p-cresol were added. To the resulting solution was added 6 L of methanol to precipitate the polyimide precursor, and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The precipitate was again filtered and dried under vacuum at 45 ° C. for 3 days.
The polyimide precursor had a weight average molecular weight of 24,800 and a number average molecular weight of 7,900.
As in Example 1, the uniformity and storage stability of the content of the polymerization inhibitor 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]
Mix 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 and stir at a temperature of 60 ° C. for 4 hours The diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate was prepared. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes, keeping 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 in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 5 ° C. The mixture was then 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., stabilizer-free), and 4.0 g of 2,6-di-tert-butyl-p-cresol was added. . To the resulting solution was added 6 L of water 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 again and dried under reduced pressure at 45 ° C. for 3 days.
The polyimide precursor had a weight average molecular weight of 22,000 and a number average molecular weight of 7,200.
As in Example 1, the uniformity and storage stability of the content of the polymerization inhibitor 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]
Mix 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 and stir at a temperature of 60 ° C. for 4 hours The diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate was prepared. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes, keeping 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 in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 5 ° C. The mixture was then 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 collected by filtration, dissolved in 500 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., stabilizer-free), and 25 mg of 2,6-di-tert-butyl-p-cresol was added. To the resulting solution was added 6 L of water 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 again and dried under reduced pressure at 45 ° C. for 3 days.
The polyimide precursor had a weight average molecular weight of 22,000 and a number average molecular weight of 7,100.
As in Example 1, the uniformity and storage stability of the content of the polymerization inhibitor 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]
Mix 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 and stir at a temperature of 60 ° C. for 4 hours The monoester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate was prepared. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes, keeping 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 in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 5 ° C. The mixture was then 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 Wako Pure Chemical Industries, Ltd., 0.03% by mass of 2,6-di-tert-butyl-p-cresol). To the resulting solution was added 6 L of water 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 again and dried under reduced pressure at 45 ° C. for 3 days.
The polyimide precursor had a weight average molecular weight of 26,200 and a number average molecular weight of 8,800.
As in Example 1, the uniformity and storage stability of the content of the polymerization inhibitor 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 stirred and dissolved in 200 mL of N-methylpyrrolidone. Subsequently, while maintaining the temperature at 0 to 5 ° C., 8.00 g of 25.0 g of 4,4′-oxydibenzoyl chloride was added dropwise over 10 minutes, and stirring was continued for 60 minutes. Subsequently, 25.0 g of pyridine was added, and 5.8 g of methacrylic acid chloride was dropped over 10 minutes while maintaining the temperature at 0 to 5 ° C., and then stirring was continued for 60 minutes.
Next, 0.15 g of 2,6-di-tert-butyl-p-cresol was added to the obtained 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 precipitate after stirring was filtered and dried under reduced pressure at 45 ° C. for 3 days.
The polybenzoxazole precursor had a weight average molecular weight of 32,500 and a number average molecular weight of 9,800.
As in Example 1, the uniformity and storage stability of the content of the polymerization inhibitor 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 dissolved in 200 mL of N-methylpyrrolidone with stirring. Subsequently, while maintaining the temperature at 0 to 5 ° C., 8.00 g of 25.0 g of 4,4′-oxydibenzoyl chloride was added dropwise over 10 minutes, and stirring was continued for 60 minutes. Subsequently, 25.0 g of pyridine was added, and 5.8 g of methacrylic acid chloride was dropped over 10 minutes while maintaining the temperature at 0 to 5 ° C., and then stirring was continued for 60 minutes.
Next, 0.15 g of 2,6-di-tert-butyl-p-cresol was added to the obtained reaction mixture. Six liters of water was combined to precipitate the polybenzoxazole precursor and the precipitate was stirred at a speed of 200 rpm for 15 minutes. The precipitate after stirring was filtered and dried under reduced pressure at 45 ° C. for 3 days.
The polybenzoxazole precursor had a weight average molecular weight of 34,500 and a number average molecular weight of 10,200.
As in Example 1, the uniformity and storage stability of the content of the polymerization inhibitor were evaluated. The results are shown in Table 5.

Hydroxy 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]
Mix 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 and stir at a temperature of 60 ° C. for 4 hours The diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate was prepared. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes, keeping 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 in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 5 ° C. The mixture was then 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 dried under reduced pressure at 45 ° C. for 3 days.
The polyimide precursor had a weight average molecular weight of 22,800 and a number average molecular weight of 7,400.
As in Example 1, the uniformity and storage stability of the content of the polymerization inhibitor 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, 0.15 g of 2,6-di-tert- as polymerization inhibitor 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, keeping 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 in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 5 ° C. The mixture was then 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 precipitate after stirring was filtered and dried under reduced pressure at 45 ° C. for 3 days.
The polyimide precursor had a weight average molecular weight of 25,300 and a number average molecular weight of 8,000.
As in Example 1, the uniformity and storage stability of the content of the polymerization inhibitor 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]
Mix 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 and stir at a temperature of 60 ° C. for 4 hours The diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate was prepared. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl ₂ was added over 60 minutes, keeping 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 in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10 ± 5 ° C. The mixture was then 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 dried under reduced pressure at 45 ° C. for 3 days. The precipitate after drying was added with 0.15 g of 2,6-di-tert-butyl-p-cresol as a polymerization inhibitor, and stirred for 12 hours.
The polyimide precursor had a weight average molecular weight of 24,900 and a number average molecular weight of 7,700.
As in Example 1, the uniformity and storage stability of the content of the polymerization inhibitor were evaluated. The results are shown in Table 5.

From the above results, the heterocycle-containing polymer precursor materials of Examples 1 to 12 uniformly contained the polymerization inhibitor, and the storage stability was good.
The heterocycle-containing polymer precursor material of Comparative Example 1 in which the polymerization inhibitor was not blended was inferior in storage stability.
In addition, the heterocycle-containing polymer precursor material of Comparative Example 2 in which the polymerization inhibitor is blended in the process of synthesizing the heterocycle-containing polymer precursor does not uniformly contain the polymerization inhibitor, and the storage stability is insufficient. there were.
Furthermore, the heterocyclic ring-containing polymer precursor material of Comparative Example 3 in which a polymerization inhibitor is blended with the dried solid heterocyclic ring-containing polymer precursor also does not contain the polymerization inhibitor uniformly, and storage stability is not good. It was enough.

In addition, 5 mass% or more of any heterocyclic containing polymer precursors were melt | dissolved with respect to tetrahydrofuran and N- methyl pyrrolidone (1st solvent) at 25 degreeC. In addition, none of the heterocycle-containing polymer precursors dissolved in water and methanol (the second solvent) at 25 ° C. in an amount of 5% by mass or less, or did not dissolve 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 (the first solvent) at 5% by mass or more at 25 ° C.

(Example 13)
<Preparation of photosensitive resin composition>
The components described in Table 6 were mixed to prepare a coating solution of a 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 onto a silicon wafer by spinning (1,200 rpm, 30 seconds). The silicon wafer coated with the photosensitive resin composition was dried at 100 ° C. for 5 minutes on a hot plate 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 carried out 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, which is a preferable result. The wavelength is set to 365 nm because it is considered to be one of the appropriate wavelengths for producing a good pattern.

(Examples 14 to 34, Comparative Examples 4 to 6)
In Example 13, as shown in Table 2, the kind and the compounding quantity of each component were changed, and others were performed similarly.

(A) Heterocycle-Containing Polymer Precursor Material A-1 to A-15: Heterocycle-Containing Polymer Precursor Material Produced in Examples 1 to 12 and Comparative Examples 1 to 3

(B) Polymerizable compound B-1: NK ester M-40G (manufactured by Shin-Nakamura Chemical Co., Ltd. monofunctional methacrylate following structure)
B-2: NK ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd., bifunctional methacrylate, structure shown below)
B-3: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional acrylate, structure shown below)

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

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

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

(E) Additive E-1: 1 H-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 low exposure energy required to form a good pattern and high sensitivity.
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 required to form a good pattern and low sensitivity.

Example 100
The photosensitive resin composition of Example 15 was spun (3500 rpm, 30 seconds) on a resin substrate on which a thin copper layer was formed. 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). The exposure was performed with a high pressure mercury lamp, and the exposure energy at a wavelength of 365 nm was measured. After exposure, the image was developed for 75 seconds with cyclopentanone.
It was then heated at 180 ° C. for 20 minutes. Thus, an interlayer insulating film for rewiring layer was formed.
The interlayer insulation film for the redistribution layer was excellent in insulation.
Moreover, when the semiconductor device was manufactured using this interlayer insulation film for rewiring layers, it confirmed that it operate | moveed without a problem.

100: semiconductor devices 101a to 101d: semiconductor elements 101: laminates 102b to 102d: through electrodes 103a to 103e: metal bumps 105: rewiring layers 110, 110a, 110b: underfill layer 115: insulating layer 120: wiring substrate 120a: Surface electrode

Claims (10)

A composition containing a heterocycle-containing polymer precursor and a first solvent is compounded with a polymerization inhibitor, or a composition containing a heterocycle-containing polymer precursor is compounded with a first solvent and a polymerization inhibitor And,
Incorporating a second solvent into the composition containing the polymerization inhibitor, and depositing the heterocycle-containing polymer precursor and the polymerization inhibitor in the second solvent;
The heterocyclic-containing polymer precursor is selected from a polyimide precursor having a polymerizable group and a polybenzoxazole precursor having a polymerizable group ,
5% by mass or more of the heterocycle-containing polymer precursor is dissolved in the first solvent at 25 ° C.,
In the first solvent, 5% by mass or more of the polymerization inhibitor is dissolved at 25 ° C.,
A method for producing a heterocycle-containing polymer precursor material, wherein the second solvent is a poor solvent for a heterocycle-containing polymer precursor. The method for producing a heterocycle-containing polymer precursor according to claim 1, wherein the heterocycle-containing polymer precursor dissolves in 5% by mass or less at 5 ° C. or does not dissolve at all in the second solvent. The method for producing a heterocycle-containing polymer precursor material according to claim 1 or 2 , wherein the amount of the polymerization inhibitor to be blended is 0.001 to 10% by mass of the heterocycle-containing polymer precursor. The method for producing a heterocycle-containing polymer precursor material according to any one of claims 1 to 3 , wherein the first solvent is tetrahydrofuran. The heterocycle-containing polymer according to any one of claims 1 to 4 , wherein the production method comprises blending a first solvent and a polymerization inhibitor in a composition containing the heterocycle-containing polymer precursor. Method of manufacturing precursor material. The method includes blending a polymerization inhibitor into a composition containing the heterocycle-containing polymer precursor and a first solvent, and
The heterocycle-containing polymer precursor according to any one of claims 1 to 4 , wherein the composition containing the heterocycle-containing polymer precursor and the first solvent is a synthesis reaction solution of the heterocycle-containing polymer precursor. Method of manufacturing material. The manufacturing method of the heterocyclic containing polymer precursor material of any one of Claims 1-6 whose said 2nd solvent is water or alcohol. The heterocycle according to any one of claims 1 to 7 , wherein the heterocyclic-containing polymer precursor contains a repeating unit represented by the following formula (2) or a repeating unit represented by the following formula (3). Method for producing containing polymer precursor material
Formula (2)
Formula (3)
In formula (2), each of A ¹ and A ² independently represents 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 ^{114 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 represent a hydrogen atom or a monovalent organic group. And at least one of R ¹²³ and R ¹²⁴ is a polymerizable group. The heterocycle-containing polymer precursor material according to claim 8 , 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 polymerization inhibitor has a phenolic hydroxyl group, the manufacturing method of the heterocycle-containing polymer precursor material according to any one of claims 1-9.