KR102189432B1 - Resin composition and its application - Google Patents

Abstract

A resin composition capable of providing a photosensitive resin composition having excellent storage stability and high resolution, a photosensitive resin composition using the resin composition, a cured film, a method for producing a cured film, a semiconductor device, and a method for producing a resin composition are provided. A resin composition comprising a heterocycle-containing polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and an acidic compound having a pKa of 4.0 or less, wherein the resin composition is a cured film having a thickness of 10 μm, and at 350° C. for 60 minutes The resin composition in which the volume resistivity of the cured film after heating is 1.0×10 ⁵ Ω·cm or less.

Description

Resin composition and its application

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

Since polyimide and polybenzoxazole are excellent in heat resistance and insulation, they are used for insulating films of semiconductor devices and the like.

In addition, polyimide and polybenzoxazole are used in the state of a precursor (polyimide precursor or polybenzoxazole precursor) before the cyclization reaction with higher solvent solubility, applied to a substrate, etc., and then heated to circulate the precursor to form a cured film. Forming is also being done.

As such a polyimide precursor, for example, Patent Document 1 discloses a negative photosensitive resin composition comprising 100 parts by mass of a polyimide precursor having a predetermined structure, and (B) 0.1 parts by mass to 20 parts by mass of a photopolymerization initiator. .

Patent Document 1: International Publication No. WO2013/168675

Here, it was found that the polyimide precursor and the polybenzoxazole precursor are inferior in stability, and when stored for a long period of time, the ring closure reaction may proceed with the passage of time. For example, the following reaction proceeds.

[Formula 1]

The upper part shows the partial structure of an example of a polyimide precursor (repeating unit represented by Formula (1) described later), A ² represents an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, and R ¹¹⁵ represents 4 Represents a valent organic group, and R ¹¹³ represents a hydrogen atom or a monovalent organic group.

The lower part shows the partial structure of an example of a polybenzoxazole precursor (repeating unit represented by Formula (2) to be described later), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ represents It represents a hydrogen atom or a monovalent organic group.

When the photosensitive resin composition containing such a polyimide precursor or a polybenzoxazole precursor is stored for a long period of time, there is a problem that solids precipitate and the storage stability of the photosensitive resin composition is impaired.

Moreover, even if it is excellent in storage stability, if the resolution of the photosensitive resin composition is inferior, it becomes a problem in the case of forming a pattern by exposure development.

The present invention has an object of solving such a problem, and a resin composition capable of providing a photosensitive resin composition having excellent storage stability and high resolution, and a photosensitive resin composition, cured film, and cured film using the resin composition It aims at providing a method, a semiconductor device, and a manufacturing method of a resin composition.

Under the above problems, as a result of intensive examination by the present inventors, it was found that the above problems can be solved by using an acidic compound having a pKa of 4 or less. Specifically, by the following means <1>, preferably by <2> to <23>, the said subject was solved.

<1> A resin composition comprising a heterocycle-containing polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and an acidic compound having a pKa of 4.0 or less, wherein the resin composition is a cured film having a thickness of 10 μm, and is 350° C. The resin composition, wherein the volume resistivity of the cured film after heating at 60 minutes is 1.0×10 ⁵ Ω·cm or less.

<2> The resin composition according to <1>, wherein the heterocycle-containing polymer precursor contains a repeating unit represented by the following formula (1) or a repeating unit represented by the formula (2);

Equation (1)

[Formula 2]

Equation (2)

[Formula 3]

In formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ are each independently , A hydrogen atom or a monovalent organic group; In formula (2), 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.

<3> The resin composition according to <1> or <2>, wherein the acidic compound has a pKa of 3.5 or less.

<4> The resin composition according to any one of <1> to <3>, wherein the molecular weight of the acidic compound is 100 to 300.

<5> The resin composition according to any one of <1> to <4>, wherein the acidic compound is selected from sulfonic acid and carboxylic acid.

<6> The resin composition according to any one of <1> to <4>, wherein the acidic compound is sulfonic acid.

<7> The resin composition according to any one of <1> to <4>, wherein the acidic compound is selected from p-toluenesulfonic acid, camphorsulfonic acid, and methanesulfonic acid.

The resin composition in any one of <1>-<7> which is <8> powdery form.

<9> As a photosensitive resin composition comprising a heterocycle-containing polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, an acidic compound having a pKa of 4.0 or less, and a photopolymerization initiator, the photosensitive resin composition A photosensitive resin composition having a cured film having a thickness of 10 μm and having a volume resistivity of the cured film after heating at 350°C for 60 minutes is 1.0×10 ⁵ Ω·cm or less.

<10> The photosensitive resin composition according to <9>, wherein the resin composition is the resin composition according to any one of <2> to <7>.

The photosensitive resin composition according to <9> or <10>, which is for <11> negative development.

The photosensitive resin composition in any one of <9> to <11> used for the use of developing using a <12> developer containing an organic solvent.

The photosensitive resin composition in any one of <9>-<12> which is for <13> formation of an interlayer insulating film for redistribution layers.

<14> A cured film obtained by curing the photosensitive resin composition according to any one of <9> to <13>.

The cured film according to <14>, which is an interlayer insulating film for a <15> redistribution layer.

<16> A method for producing a cured film including a step of applying the photosensitive resin composition according to any one of <9> to <13> to a substrate, and a step of curing the photosensitive resin composition applied to the substrate.

<17> The method for producing a cured film according to <16>, further including a step of exposing the cured film to light and negatively developing.

<18> The method for producing a cured film according to <17>, which includes using a developer containing an organic solvent in the development.

<19> A semiconductor device having the cured film according to <14> or <15>.

<20> A method for producing a resin composition comprising a heterocycle-containing polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, comprising a step of adding an acidic compound having a pKa of 4.0 or less, wherein the resin composition is in a powder form Phosphorus, a method for producing a resin composition.

<21> Preparation of a resin composition comprising adding an acidic compound having a pKa of 4.0 or less in the synthesis step of a heterocycle-containing polymer precursor as a method for producing the resin composition according to any one of <1> to <8> Way.

<22> A method for producing a resin composition according to any one of <1> to <8>, comprising adding an acidic compound having a pKa of 4.0 or less after synthesizing the heterocycle-containing polymer precursor. .

The method for producing a resin composition according to any one of <20> to <22>, including adding a carbodiimide compound in the synthesis step of a <23> heterocycle-containing polymer precursor.

According to the present invention, a resin composition capable of providing a photosensitive resin composition having excellent storage stability and high resolving power, and a photosensitive resin composition using the resin composition, a cured film, a method for producing a cured film, a semiconductor device and a method for producing a resin composition It became possible to provide.

1 is a schematic diagram showing a configuration of an embodiment of a semiconductor device.

The description of the constituent elements in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In the notation of the group (atomic group) in the present specification, the notation that does not describe substituted or unsubstituted includes not only having no substituent but also having a substituent. For example, the term "alkyl group" includes not only an alkyl group not having a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "actinic ray" means, for example, a bright ray spectrum of a mercury lamp, far ultraviolet ray typified by an excimer laser, extreme ultraviolet ray (EUV light), X ray, electron ray, and the like. In addition, in the present invention, light means actinic ray or radiation. The term "exposure" in the present specification refers to exposure with far ultraviolet rays, X-rays, EUV light, etc. typified by mercury lamps and excimer lasers, as well as drawing by particle rays such as electron beams and ion beams, unless otherwise specified. Include.

In the present specification, the numerical range indicated by using "~" means a range including a numerical value described before and after "~" as a lower limit value and an upper limit value.

In the present specification, "(meth)acrylate" represents both or any one of "acrylate" and "methacrylate", and "(meth)acryl" refers to "acrylic" and "methacryl". It represents both or either, and "(meth)acryloyl" represents both or any one of "acryloyl" and "methacryloyl".

In the present specification, the term "step" is included in the term as long as the desired action of the step is achieved, not only in an independent step, but also in a case where it is not clearly distinguishable from other steps.

In the present specification, the solid content concentration is a mass percentage of the mass of other components excluding the solvent with respect to the total mass of the composition. In addition, the solid content concentration refers to the concentration at 25°C unless otherwise specified.

In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values by gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, guard column HZ-L, TSK gel Super HZM- using HLC-8220GPC (manufactured by Tosoh Corporation) as a column. It can be obtained by using any one or more of M, TSK gel Super HZ4000, TSK gel Super HZ3000, and TSK gel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, the eluent is measured using THF (tetrahydrofuran). In addition, the detection is assumed to be using a UV ray (ultraviolet) wavelength 254 nm detector unless otherwise specified.

[Resin composition]

The resin composition of the present invention comprises a heterocycle-containing polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor (hereinafter, simply referred to as "heterocycle-containing polymer precursor"), and an acidic compound having a pKa of 4.0 or less. A resin composition containing, wherein the resin composition is a cured film having a thickness of 10 μm, and the volume resistivity of the cured film after heating at 350° C. for 60 minutes is 1.0×10 ⁵ Ω·cm or less. By setting it as such a structure, it becomes possible to provide a photosensitive resin composition excellent in storage stability and high resolution.

This mechanism is presumed, but it is presumed that the addition of an acidic compound having a pKa of 4.0 or less can slow the ring closure reaction of the heterocycle-containing polymer precursor and improve storage stability. Further, it is estimated that by reducing the proportion of the ring closed body in the photosensitive resin composition, the viscosity of the photosensitive resin composition becomes difficult to increase, and the resolution can be improved. In addition, metal corrosion can be more effectively suppressed by using a compound having a molecular weight of 100 or more as the acidic compound.

<Volume resistivity of cured film of resin composition>

The resin composition of the present invention is a cured film having a thickness of 10 μm, and the volume resistivity of the cured film after heating at 350° C. for 60 minutes is 1.0×10 ⁵ Ω·cm or less. By setting it as such a structure, the insulating property of a cured film can be maintained.

The volume resistivity is measured by the method described in Examples to be described later.

<Heterocycle-containing polymer precursor>

The heterocycle-containing polymer precursor used in the present invention is at least one selected from a polyimide precursor and a polybenzoxazole precursor, and is preferably a polyimide precursor.

Each of the polyimide precursor and the polybenzoxazole precursor may contain only one type or may contain two or more types.

<<polyimide precursor>>

The polyimide precursor used in the present invention is not specifically determined such as its kind, but it is preferable to include a repeating unit represented by the following formula (1).

Equation (1)

[Formula 4]

In formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ are each independently , A hydrogen atom or a monovalent organic group.

As for A ¹ and A ² in formula (1), an oxygen atom or NH is preferable, and an oxygen atom is more preferable.

R ¹¹¹ in formula (1) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and 3 to 20 carbon atoms A group consisting of a cyclic aliphatic group, an aromatic group having 6 to 20 carbon atoms, or a combination thereof is preferable, and a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable.

It is preferable that R ¹¹¹ is derived from diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only 1 type may be used for diamine, and 2 or more types may be used.

Specifically, it is preferable that it is a diamine containing a C2-C20 linear or branched aliphatic group, a C3-C20 cyclic aliphatic group, a C6-C20 aromatic group, or a group consisting of a combination thereof, and a C6 It is more preferable that it is a diamine containing a group consisting of -20 aromatic groups. The following is mentioned as an example of an aromatic group.

[Formula 5]

In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) _2- , -NHCO- and a group selected from a combination thereof is preferable, and a single bond or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S -, -SO ₂ -is more preferably a group selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ It is more preferable that it is a divalent group selected from the group consisting of -.

As diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohex three; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane Phosphorus and isophoronediamine; Meta and paraphenylenediamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether , 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-diaminodi Phenylsulfide, 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)hexa Fluoropropane, 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'-diaminoparaterpenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-amino Phenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene , 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3 -Bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-di Methyl-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'-tetraaminobi Phenyl, 3,3',4,4'-tetraaminodiphenylether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'- Diamino bipe Nyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4 ,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetra Methyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-di Aminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester 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-aminophenyl)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) Si)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, parabis(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-tri Fluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-tri) Fluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'- At least one diamine selected from bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine and 4,4'-diaminoquaterphenyl Can be lifted.

Moreover, diamines (DA-1) to (DA-18) shown below are also preferable.

[Formula 6]

[Formula 7]

Moreover, a diamine which has at least 2 or more alkylene glycol units in a main chain is also mentioned as a preferable example. Preferably, it is a diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule, and more preferably a diamine not containing an aromatic ring. As a specific example, Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) EDR -148, Jeffamine (registered trademark) EDR-176, Jeffamine (registered trademark) D-200, Jeffamine (registered trademark) D-400, Jeffamine (registered trademark) D-2000, Jeffamine (registered trademark) D -4000 (the above brand name, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-amino) Propoxy) propan-2-yl) oxy) propane-2-amine and the like, but are not limited thereto.

Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) EDR-148, The structure of Jeffamine (registered trademark) EDR-176 is shown below.

[Formula 8]

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

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

It is preferable that R ¹¹¹ is a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance. In particular, it is more preferable that it is a divalent organic group represented by Formula (61) from the viewpoint of i-ray transmittance and availability.

Equation (51)

[Formula 9]

In formula (51), R ¹⁰ to R ¹⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R ¹⁰ to R ¹⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or a difluoro. It is a methyl group or a trifluoromethyl group.

As a monovalent organic group among R ¹⁰ to R ¹⁷ , an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), etc. are mentioned. I can.

Equation (61)

[Formula 10]

In formula (61), R ¹⁸ and R ¹⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

Examples of the diamine compound giving the structure of formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-di Aminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like. One of these may be used, or two or more may be used in combination.

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

Equation (5)

[Formula 11]

In formula (5), R ¹¹² is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, -NHCO- And, a group selected from a combination thereof is preferably a single bond, or an alkylene group having 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 is -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO _2- More preferred is the selected divalent group.

Equation (6)

[Formula 12]

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in formula (1) include a tetracarboxylic acid residue remaining after the acid dianhydride group has been removed from the tetracarboxylic acid dianhydride. Tetracarboxylic dianhydride may be used alone or in combination of two or more. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (O).

Equation (O)

[Formula 13]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ is R ^115, and accept the formula (1).

Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride. Water, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane Intetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4 '-Benzophenonetetracarboxylic 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-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8 -Naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4- Dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and at least one selected from these alkyl derivatives having 1 to 6 carbon atoms and/or alkoxy derivatives having 1 to 6 carbon atoms are exemplified.

Moreover, tetracarboxylic dianhydride (DAA-1)-(DAA-5) shown below are also mentioned as a preferable example.

[Formula 14]

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 preferably contains a radical polymerizable group, and more preferably both contain a radical polymerizable group. Do. The radical polymerizable group is a group capable of crosslinking reaction by the action of a radical, and preferred examples include a group having an ethylenically unsaturated bond.

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).

[Formula 15]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferable.

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 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group , A dodecamethylene group, and -CH ₂ CH(OH)CH ₂ -are mentioned, and an ethylene group, a propylene group, a trimethylene group, and -CH ₂ CH(OH)CH ₂ -are more preferable.

Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent which improves the solubility of a developer is preferably used.

From the viewpoint of solubility in an aqueous developer, R ¹¹³ or R ¹¹⁴ may be a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an aromatic group and an aralkyl group having one, two or three, preferably one acidic group bonded to carbon constituting the aryl group. Specifically, an aromatic group having an acidic group and having 6 to 20 carbon atoms and an aralkyl group having an acidic group and having 7 to 25 carbon atoms are mentioned. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group are mentioned. The acidic group is preferably an OH group.

It is more preferable that R ¹¹³ or R ¹¹⁴ is 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 an organic solvent, it is preferable that R ¹¹³ or R ¹¹⁴ is a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group is preferably included, and an alkyl group substituted with an aromatic group is more preferable.

The number of carbon atoms in 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, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, iso A propyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group are mentioned. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. As a monocyclic cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned, for example. Examples of polycyclic cyclic alkyl groups include adamantyl group, norbornyl group, bonyl group, campenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camporoyl group, dicyclohexyl group and pinenyl group. Can be lifted. Among them, a cyclohexyl group is most preferred from the viewpoint of compatibility with high sensitivity. Moreover, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group mentioned later is preferable.

As the aromatic group, specifically, a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene 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, pyri Dajin ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizin ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline Ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, cyanthrene ring, chroman ring, xanthene ring, phenoxacyin ring, phenothiazine ring or phenazine ring. The benzene ring is most preferred.

In formula (1), when R ¹¹³ is a hydrogen atom, R ¹¹⁴ may form a tertiary amine compound having a hydrogen ethylenically unsaturated bond and a counter salt. Examples of the tertiary amine compound having such an ethylenically unsaturated bond include N,N-dimethylaminopropyl methacrylate.

Moreover, it is also preferable that a polyimide precursor has a fluorine atom in a structural unit. The fluorine atom content in the polyimide precursor is preferably 1% by mass or more, and preferably 20% by mass or less.

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

It is preferable that the repeating unit represented by Formula (1) is a repeating unit represented by Formula (1-A). That is, it is preferable that at least one type of the polyimide precursor used in the present invention is a precursor having a repeating unit represented by formula (1-A). By setting it as such a structure, it becomes possible to widen the width of exposure latitude more.

Equation (1-A)

[Formula 16]

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

A ^1, A ^2, R ^111, R ¹¹³ and R ¹¹⁴ each independently, is A ^1, A ^2, R ^111, R ¹¹³ and R ^114, and accept in the formula (1), the preferred range is also the same.

R ¹¹² is R ^112, and accept and in the formula (5), a preferred range is also the same.

As for the polyimide precursor, although one type may be sufficient as the repeating structural unit represented by Formula (1), 2 or more types may be sufficient as it. Moreover, you may contain the structural isomer of a repeating unit represented by Formula (1). Moreover, the polyimide precursor may also contain other types of repeating structural units in addition to the repeating unit of said formula (1).

As an embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, 70 mol% or more, particularly 90 mol% or more of the total repeating units is a repeating unit represented by formula (1) is illustrated. do.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000 to 500000, more preferably 5000 to 100000, and still more preferably 10000 to 500,000. Further, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 500,000, further preferably 4000 to 25000, even more preferably 4000 to 15000, even more Preferably, it is 5000-10000.

1.5-4.0 are preferable and, as for the dispersion degree, 2.0-3.5 are more preferable.

The polyimide precursor is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, a dicarboxylic acid or a dicarboxylic acid derivative is halogenated using a halogenating agent, and then obtained by reacting with a diamine.

In the manufacturing method of a polyimide precursor, it is preferable to use an organic solvent at the time of reaction. The organic solvent may be one, or two or more.

As the organic solvent, although it can be appropriately determined depending on the raw material, pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone are exemplified.

In the preparation of the polyimide precursor, in order to further improve the storage stability, the polyimide precursor is sealed with an end-sealing agent such as an acid dianhydride, a monocarboxylic acid, a monoacid chloride compound, and a mono-active ester compound. It is preferable to do it. Among these, it is more preferable to use a monoamine, and as preferable compounds of the monoamine, aniline, 2-ethanylaniline, 3-ethanylaniline, 4-ethanylaniline, and 5-amino-8-hydroxy Quinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-amino Naphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2 -Carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid , 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol , 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of terminal sealing agents.

At the time of production of the polyimide precursor, a step of depositing a solid may be included. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and a polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, whereby a solid can be deposited.

Thereafter, the polyimide precursor is dried to obtain a powdery polyimide precursor.

<<Polybenzoxazole precursor>>

It is preferable that the polybenzoxazole precursor used in the present invention contains a repeating unit represented by the following formula (2).

Equation (2)

[Formula 17]

In formula (2), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In formula (2), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a linear aliphatic group is preferable.

In formula (2), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, it is the same as R ¹¹⁵ in the above formula (1), and the preferred range is also the same.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating units of the above formula (2).

It is preferable to contain a diamine residue represented by the following formula (SL) as another type of repeating structural unit from the viewpoint of being able to suppress the occurrence of a warpage state due to ring closure.

[Formula 18]

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

In formula (SL), preferable Z is that 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 a structure represented by Formula (SL), 500-3,000 are more preferable. The molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, the elastic modulus after dehydration and cyclization of the polybenzoxazole precursor is lowered, and the effect of suppressing the warpage state and the effect of improving solubility can be achieved.

In the case of containing a diamine residue represented by the formula (SL) as another type of repeating structural unit, since the alkali solubility is improved, the remaining tetracarboxylic acid residue after removing the acid dianhydride group from the tetracarboxylic dianhydride is used as the repeating structural unit. It is preferable to further include. As an example of such a tetracarboxylic acid residue, the example of R ¹¹⁵ in Formula (1) is mentioned.

As a polybenzoxazole precursor, from 4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl Obtained polybenzoxazole precursor and polybenzoxazole obtained from 4,4'-oxydibenzoyl chloride, 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and methacrylic acid chloride Precursors are illustrated.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2000 to 500000, more preferably 5000 to 100000, and still more preferably 10000 to 500,000. Further, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 500,000, still more preferably 4000 to 25000, even more preferably 4000 to 15000, particularly preferably It is between 5000 and 10000.

1.5-4.0 are preferable and, as for the dispersion degree, 2.0-3.5 are more preferable.

<Acid compound>

The resin composition of the present invention contains an acidic compound having a pKa of 4.0 or less. Here, pKa represents the logarithmic reciprocal (-Log ₁₀ Ka) of the dissociation constant (Ka) of the proton of the acidic compound. The value of pKa of the acidic compound is measured by the method described in Examples to be described later.

By including such an acidic compound, it becomes possible to provide a photosensitive resin composition having excellent storage stability and high resolution.

The pKa of the acidic compound used in the present invention is preferably 3.5 or less, more preferably 3.0 or less, more preferably 2.5 or less, even more preferably 2.0 or less, particularly preferably 1.0 or less, and most preferably 0.0 or less. Do. Although the lower limit of the pKa is not particularly determined, it is preferably -3.0 or more, more preferably -2.0 or more, and still more preferably -1.0 or more.

An acidic compound having a pKa of 4.0 or less preferably has a molecular weight of 500 or less, more preferably 400 or less, more preferably 300 or less, even more preferably 250 or less, and particularly preferably 200 or less. By using such an acidic compound, the acidic compound is volatilized at the time of curing, and corrosion of metal can be more effectively suppressed in the case of using a cured film as an insulating film. Although it does not specifically set as the lower limit of the said molecular weight, it is preferable that it is 45 or more, it is more preferable that it is 80 or more, and it is more preferable that it is 100 or more.

The type of the acidic compound having a pKa of 4.0 or less is not particularly determined, but is preferably selected from sulfonic acid, carboxylic acid, imidic acid, methic acid, hydrochloric acid, nitric acid and sulfuric acid, and more preferably selected from sulfonic acid and carboxylic acid And, it is more preferable that it is selected from sulfonic acid and polyhydric carboxylic acid of divalent or more, and sulfonic acid is even more preferable.

In addition, the acidic compound having a pKa of 4.0 or less may be a hydrate or may not be a hydrate.

As the sulfonic acid, a monovalent sulfonic acid having one sulfo group per molecule is preferable.

As specific examples of sulfonic acid, toluenesulfonic acid (e.g., p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate), camphorsulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, nonafluoro-1- It is preferably selected from butanesulfonic acid, benzenesulfonic acid, poly(p-styrenesulfonic acid) and 2-naphthalenesulfonic acid, more preferably selected from toluenesulfonic acid, camphorsulfonic acid and methanesulfonic acid, It is more preferable to contain at least toluenesulfonic acid.

The carboxylic acid may be a monovalent carboxylic acid having one carboxyl group per molecule, or a polyvalent carboxylic acid having two carboxyl groups per molecule, and a polyhydric carboxylic acid is preferable. In the case of a polyhydric carboxylic acid, 2-4 are preferable and, as for the number of carboxyl groups in 1 molecule, two are more preferable.

As a specific example of the carboxylic acid, it is preferable to be selected from formic acid, oxalic acid (e.g., oxalic acid dihydrate), maleic acid, malonic acid, pyruvic acid, DL-lactic acid, trifluoroacetic acid, glyoxylic acid and maleic acid methyl ester, Formic acid, oxalic acid, maleic acid, malonic acid, pyruvic acid and DL-lactic acid are more preferred, oxalic acid, maleic acid, malonic acid, pyruvic acid and DL-lactic acid are more preferred, oxalic acid, maleic acid and malonic acid It is even more preferred that it is selected from Ronic acid, and it is particularly preferred that it contains at least oxalic acid.

The resin composition of the present invention preferably contains an acidic compound having a pKa of 4.0 or less in a ratio of 10 to 0.001 parts by mass, and 1 to 0.001 parts by mass with respect to 100 parts by mass of the total of the heterocycle-containing polymer precursor. It is more preferable, and it is more preferable to contain it in the ratio of 0.1 to 0.005 mass parts.

The resin composition of the present invention may contain only one type of acidic compound having a pKa of 4.0 or less, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

Moreover, although the resin composition of this invention may contain the acidic compound whose pKa exceeds 4.0, it is preferable that it does not contain substantially. Substantially not included means, for example, that the amount of such an acidic compound is 1% by mass or less of the total amount of the acidic compound with pKa 4.0 or less contained in the resin composition, preferably 0.1% by mass or less, more Preferably it is 0.01 mass% or less.

<Other components of the resin composition>

The resin composition of the present invention may contain components other than the aforementioned heterocycle-containing polymer precursor and an acidic compound having a pKa of 4.0 or less. Specifically, a solvent, a polymerization inhibitor, etc. are illustrated. For details of the solvent and the polymerization inhibitor, the description of the solvent and the polymerization inhibitor in other components of the photosensitive resin composition described later can be taken into account.

In addition, impurities derived from raw materials used in the synthesis of the heterocycle-containing polymer precursor may be included.

It is preferable that the resin composition of this invention does not contain an acid generator substantially. Substantially not included means, for example, 1% by mass or less of the total amount of the heterocycle-containing polymer precursor contained in the resin composition, preferably 0.1% by mass or less, and more preferably 0.01% by mass or less.

<Form of resin composition>

The form of the resin composition of the present invention may be a liquid form or a powder form.

When the resin composition of the present invention is in a liquid form, it is preferable that 10 to 90% by mass of the resin composition is a solvent. Moreover, it is preferable that content of a heterocycle-containing polymer precursor in a resin composition is 1 to 80 mass %.

When the resin composition of the present invention is in the form of a powder, it is preferable that 80% by mass or more of the resin composition is a heterocycle-containing polymer precursor.

Here, the powdery form refers to a fine solid substance as a main component. The main component refers to the component having the most content in the resin composition, preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, even more preferably 98% by mass or more It refers to the ingredients that occupy. As for the fine solid substance in this invention, it is preferable that the average of the maximum length is 10 mm or less, and it is more preferable that it is 5 mm or less. For example, commercially available powdery resins and polymerizable monomers are included in the fine solid substance in the present invention.

Moreover, although the powdery resin composition may contain a solvent, content of a solvent is 20 mass% or less of the resin composition, 10 mass% or less is preferable, and 5 mass% or less is more preferable.

[Method of manufacturing resin composition]

The manufacturing method of the resin composition of the present invention is a method of manufacturing a resin composition containing a heterocycle-containing polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and includes a step of adding an acidic compound having a pKa of 4.0 or less. .

The acidic compound having a pKa of 4.0 or less may be added in the synthesis step of the heterocycle-containing polymer precursor, or may be added after synthesis of the heterocycle-containing polymer precursor.

Here, the process of synthesizing the heterocycle-containing polymer precursor refers to a process from starting to react the raw material monomer until the reaction of the raw material monomer is completed. Termination refers to a step of filtering the reaction liquid or performing precipitation with a solvent, for example. Therefore, the intention is not to include a step in which a trace amount of components continues to react. On the other hand, the term after synthesis|combining a heterocycle-containing polymer precursor means after completion|finish of a synthesis process.

When an acidic compound having a pKa of 4.0 or less is added in the synthesis step of the heterocycle-containing polymer precursor, the positional dependence of the acidic compound present in the polymer can be reduced.

The acidic compound having a pKa of 4.0 or less is preferably a compound that does not react with the raw material monomer of the heterocycle-containing polymer precursor.

When an acidic compound having a pKa of 4.0 or less is added in the process of synthesizing the heterocycle-containing polymer precursor, the amount of the acidic compound having a pKa of 4.0 or less is 50 to 0.1 mass based on 100 parts by mass of the finally obtained heterocycle-containing polymer precursor. The addition is preferable, and 20-1 mass part is more preferable.

Moreover, in this invention, it is also preferable to add a carbodiimide compound in the synthesis|combination process of a heterocycle-containing polymer precursor. The carbodiimide compound can contribute as a condensing agent of a carboxyl group and an amino group in the reaction of the raw material monomer of the heterocycle-containing polymer.

As a first embodiment using a carbodiimide compound, an acid dianhydride, a compound having a polymerizable group, and a carbodiimide compound are added to react, and then a diamine compound is added to react further to obtain a polyimide precursor. Is illustrated.

When an acidic compound having a pKa of 4.0 or less is added in the synthesis process of a heterocycle-containing polymer precursor, and when a carbodiimide compound is added, the carbodiimide compound is added at a faster stage than an acidic compound having a pKa of 4.0 or less. It is desirable.

As carbodiimide compounds, dicyclohexyl carbodiimide, diisopropyl carbodiimide, diethyl carbodiimide, ethylcyclohexyl carbodiimide, diphenyl carbodiimide, and 1-ethyl-3-(3-di Methylaminopropyl) carbodiimide hydrochloride is illustrated, and at least one of dicyclohexyl carbodiimide and diisopropyl carbodiimide is preferable.

The molecular weight of the carbodiimide compound is preferably 100 to 400.

The addition amount of the carbodiimide compound is preferably 500 to 50 parts by mass, more preferably 250 to 90 parts by mass with respect to 100 parts by mass of the finally obtained heterocycle-containing polymer precursor.

[Photosensitive resin composition]

The photosensitive resin composition of the present invention is a photosensitive resin composition comprising a heterocycle-containing polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, an acidic compound having a pKa of 4.0 or less, and a photopolymerization initiator, The photosensitive resin composition is a cured film having a thickness of 10 μm, and the volume resistivity of the cured film after heating at 350° C. for 60 minutes is 1.0×10 ⁵ Ω·cm or less.

Hereinafter, the details of the photosensitive resin composition of the present invention will be described.

<Volume resistivity of cured film of photosensitive resin composition>

The photosensitive resin composition of the present invention is a cured film having a thickness of 10 μm, and the volume resistivity of the cured film after heating at 350° C. for 60 minutes is 1.0×10 ⁵ Ω·cm or less. By setting it as such a structure, the insulating property of a cured film can be maintained.

The volume resistivity is measured by the method described in Examples to be described later.

<Resin composition>

The photosensitive resin composition of the present invention includes a resin composition containing a heterocycle-containing polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and an acidic compound having a pKa of 4.0 or less.

The resin composition contained in the photosensitive resin composition is a cured film having a thickness of 10 μm, and the volume resistivity of the cured film after heating at 350° C. for 60 minutes is preferably 1.0×10 ⁵ Ω·cm or less, but the photosensitive resin composition itself If the condition of the volume resistivity is satisfied, the resin composition contained in the photosensitive resin composition does not necessarily have to satisfy the volume resistivity.

The details of the heterocycle-containing polymer precursor and the acidic compound having a pKa of 4.0 or less contained in the photosensitive resin composition are the same as those of the resin composition described above, and the preferred range is also the same. Moreover, it is preferable that the resin composition contained in a photosensitive resin composition is a resin composition satisfying the predetermined volume resistivity mentioned above.

The content of the heterocycle-containing polymer precursor in the photosensitive resin composition of the present invention is preferably 20 to 100% by mass, more preferably 50 to 99% by mass, and 60 to 98% by mass with respect to the total solid content of the photosensitive resin composition. % Is more preferable, and 70 to 95 mass% is particularly preferable.

The heterocycle-containing polymer may contain only one type, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

Further, the photosensitive resin composition of the present invention preferably contains an acidic compound having a pKa of 4.0 or less in a ratio of 100 to 0.0001 parts by mass with respect to the total 100 parts by mass of the heterocycle-containing polymer precursor, and a ratio of 10 to 0.001 parts by mass It is more preferable to include as, and it is still more preferable to include in a ratio of 1 to 0.01 parts by mass.

The photosensitive resin composition of the present invention may contain only one type of acidic compound having a pKa of 4.0 or less, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

<Photopolymerization initiator>

There is no restriction|limiting in particular as a photoinitiator which can be used in this invention, It can select suitably from well-known photoinitiators. For example, a photopolymerization initiator having photosensitivity to light from the ultraviolet region to the visible region is preferable. Moreover, it may be an activator that generates an active radical by generating a certain action with a photo-excited sensitizer.

It is preferable that the photoinitiator contains at least one compound having a molar extinction 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 the 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 ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent.

Since the photosensitive resin composition of the present invention contains a photopolymerization initiator, the photosensitive resin composition of the present invention is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then cured due to radicals generated by irradiation with light Thus, the solubility in the light irradiation portion can be reduced. For this reason, there is an advantage in that, for example, by exposing the photosensitive resin composition layer through a photomask having a pattern that masks only the electrode portion, regions having different solubility can be conveniently manufactured according to the pattern of the electrode.

As a photoinitiator, a known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (eg, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide , Hexaarylbiimidazole, oxime derivatives such as oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds , A metallocene compound, an organic boron compound, and an iron arene complex. For these details, description of paragraphs 0165 to 0182 of JP 2016-027357 A can be taken into consideration, and the contents are incorporated herein by reference.

As a ketone compound, the compound described in paragraph 0087 of Japanese Unexamined-Japanese-Patent No. 2015-087611 is illustrated, for example, and this content is incorporated in this specification. In a commercial item, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

As a photoinitiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be used suitably. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 A and the acylphosphine oxide-based initiator described in JP-A-4225898 can also be used.

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

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

As the aminoacetophenone initiator, the compound described in Japanese Patent Application Laid-Open No. 2009-191179 in which the maximum absorption wavelength is matched to a wavelength light source such as 365 nm or 405 nm can also be used.

Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In addition, commercially available IRGACURE-819 and IRGACURE-TPO (brand names: all manufactured by BASF) can be used.

As a metallocene compound, IRGACURE-784 (made by BASF) etc. are illustrated.

As a photoinitiator, more preferably, an oxime compound is mentioned. By using an oxime compound, it becomes possible to improve the exposure latitude more effectively. The oxime compound has a wide exposure latitude (exposure margin) and is preferable.

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

Preferred oxime compounds include, for example, compounds of the following structures, 3-benzoxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2 -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy) Iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

[Formula 19]

In commercial products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., a photopolymerization initiator described in Japanese Laid-Open Patent Publication No. 2012-014052) 2) is also suitably used. In addition, TR-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (Co., Ltd.) ADEKA) can also be used. In addition, DFI-091 (manufactured by Daito Chemicals Co., Ltd.) can be used.

It is also possible to use an oxime compound further having a fluorine atom. Specific examples of such an oxime compound include compounds described in Japanese Laid-Open Patent Publication No. 2010-262028, compounds 24 and 36 to 40 described in paragraphs 0345 to 0348 of Japanese Laid-Open Patent Publication No. 2014-500852, and Japanese Laid-Open Patent Publication. The compound (C-3) etc. described in paragraph 0101 of 2013-164471 can be mentioned.

As a most preferable oxime compound, an oxime compound which has a specific substituent shown in Unexamined-Japanese-Patent No. 2007-269779, and an oxime compound which has a thioaryl group shown in Unexamined-Japanese-Patent No. 2009-191061, etc. are mentioned.

The photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, and a metallocene from the viewpoint of exposure sensitivity. Compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole Compounds selected from the group consisting of compounds and 3-aryl substituted coumarin compounds are preferred.

Further, preferred photopolymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzo A phenone compound, an acetophenone compound, and at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable. , It is more preferable to use a metallocene compound or an oxime compound, and an oxime compound is particularly preferable.

In addition, the photoinitiator is N,N'-tetraalkyl-4,4'-diaminobenzophenone such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Mihiler's ketone). , 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino- Aromatic ketones such as propanone-1, quinones condensed with aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoin, benzyldimethyl ketal Benzyl derivatives such as may be used. Moreover, a compound represented by the following formula (I) can also be used.

[Formula 20]

In formula (I), R ⁵⁰ represents an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, a halogen atom, a cyclopentyl group , A cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a phenyl group substituted with at least one of an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms interrupted by one or more oxygen atoms, or biphenylyl, R ⁵¹ is a group represented by formula (II), or is the same group as R ^50, and R ⁵² to R ⁵⁴ are each independently alkyl having 1 to 12 carbon atoms, alkoxy or halogen having 1 to 12 carbon atoms.

[Formula 21]

In the formula, R ⁵⁵ to R ⁵⁷ are the same as R ⁵² to R ^{54 in} the formula (I).

Moreover, as a photoinitiator, the compound of paragraphs 0048-0055 of WO2015/0125469 can also be used.

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 5 to 15% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. The photoinitiator may contain only 1 type, and may contain 2 or more types. When two or more types of photopolymerization initiators are contained, it is preferable that the total is within the above range.

<Other components of the photosensitive resin composition>

The photosensitive resin composition of the present invention may contain components other than the aforementioned heterocycle-containing polymer precursor, an acidic compound having a pKa of 4.0 or less, and a photopolymerization initiator. Specifically, a solvent, a polymerization inhibitor, etc. are illustrated. In addition, impurities derived from raw materials used in the synthesis of the heterocycle-containing polymer precursor may be included.

It is preferable that the resin composition of this invention does not contain an acid generator substantially. Here, the term "substantially not included" means that the content of the acid generator contained in the resin composition is 1% by mass or less of the total amount of the heterocycle-containing polymer precursor, preferably 0.1% by mass or less, and more Preferably it is 0.01 mass% or less.

<<Thermal base generator>>

The photosensitive resin composition of the present invention may contain a hot base generator. By using a hot base generator, a base species for accelerating the ring closure reaction can be generated in the heating step of performing the ring closure reaction of the heterocycle-containing polymer precursor, so that the ring closure rate tends to be further improved.

As the hot base generator, the type, etc., is not specifically determined, but an acidic compound that generates a base when heated to 40°C or higher (however, it is a compound having a pKa exceeding 4), and an anion and ammonium having a pKa1 of 0-4. It is preferable to include a hot base generator containing at least one selected from ammonium salts having a cation. Here, pKa1 represents the logarithm of the reciprocal (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the acid.

Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the cyclization reaction of the heterocycle-containing polymer precursor can be accelerated by the base generated from these compounds. The cyclization can be performed at low temperatures. In addition, even if these compounds are coexisted with a heterocycle-containing polymer precursor that is cyclized and cured by a base, cyclization of the heterocycle-containing polymer precursor hardly proceeds unless heated, so that a photosensitive resin composition having excellent storage stability can be prepared. have.

In the present specification, with an acidic compound, 1 g of a compound is collected in a container, 50 mL of a mixture of ion-exchanged water and tetrahydrofuran (mass ratio is water/tetrahydrofuran = 1/4) is added, and 1 The solution obtained by stirring for an hour is a compound having a value of less than 7 measured at 20°C using a pH (power of hydrogen) meter.

In this embodiment, 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 preferably 190°C or less, more preferably 180°C or less, and still more preferably 165°C or less. The lower limit of the base generation temperature is preferably 130°C or higher, and more preferably 135°C or higher.

When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120°C or higher, it is difficult to generate a base during storage, so that a photosensitive resin composition having excellent storage stability can be prepared. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200°C or less, the cyclization temperature of the heterocycle-containing polymer precursor can be lowered. For the base generation temperature, for example, using differential scanning calorimetry, the compound is heated to 250°C at 5°C/min in an internal pressure capsule, and the peak temperature of the lowest exothermic peak is read. The temperature can be measured as the base generation temperature.

In this embodiment, the base generated by the hot base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Since the tertiary amine has high basicity, the cyclization temperature of the polyimide precursor and the polybenzoxazole precursor can be further lowered. Further, the boiling point of the base generated by the hot base generator is preferably 80°C or higher, more preferably 100°C or higher, and still more preferably 140°C or higher. Moreover, as for the molecular weight of the generated base, 80-2000 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 a structural formula.

In this embodiment, the acidic compound (A1) preferably contains at least one selected from ammonium salts and compounds having an ammonium structure represented by Formula (101) or (102) described later.

In this embodiment, it is preferable that the said ammonium salt (A2) is an acidic compound. Further, the ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40° C. or higher (preferably 120 to 200° C.), or at 40° C. or higher (preferably 120 to 200° C.). It may be a compound from which an acidic compound that generates a base upon heating has been removed.

In this embodiment, an ammonium salt means a salt of an anion and an ammonium cation represented by the following formula (101) or (102). The anion may be bonded to a part of the ammonium cation through a covalent bond, or may have it in addition to the molecule of the ammonium cation, but it is preferable to have it in addition to the molecule of the ammonium cation. In addition, that the anion has a molecule other than the molecule of the ammonium cation refers to a case where the ammonium cation and the anion are not bound through a covalent bond. Hereinafter, an anion other than the molecule of the cation part is also referred to as a counter anion.

Equation (101) Equation (102)

[Formula 22]

In formulas (101) and (102), R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ⁷ in formulas (101) and (102) may be bonded to each other to form a ring.

It is preferable that the ammonium cation is represented by any one of the following formulas (Y1-1) to (Y1-5).

[Formula 23]

In the formula (Y1-1) ~ (Y1-5), R ¹⁰¹ is, represents an n-valent organic, R ¹ and R ⁷ is the formula (101), or R ¹ and R ⁷ in the formula (102) and I agree.

In formulas (Y1-1) to (Y1-4), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5.

In this embodiment, it is preferable that the ammonium salt has an anion and an ammonium cation whose pKa1 is 0-4. The upper limit of pKa1 of an anion is more preferably 3.5 or less, and even more preferably 3.2 or less. As for the lower limit, 0.5 or more are preferable and 1.0 or more are more preferable. When the pKa1 of the anion is in the above range, the heterocycle-containing polymer precursor can be cyclized at a lower temperature, and further, the stability of the photosensitive resin composition can be improved. When pKa1 is 4 or less, the stability of the hot base generator is good, generation of a base without heating can be suppressed, and the stability of the photosensitive resin composition is good. When pKa1 is 0 or more, the generated base is difficult to neutralize, and the cyclization efficiency of the heterocycle-containing polymer precursor or the like is good.

The kind of anion is preferably one selected from a carboxylic acid anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because the stability of the salt and thermal decomposition can be compatible. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.

The carboxylic acid 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 can be set as a hot base generator which can improve stability, hardenability, and developability of a photosensitive resin composition more. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the photosensitive resin composition can be further improved.

In this embodiment, it is preferable that the carboxylic acid anion is an anion of a carboxylic acid whose pKa1 is 4 or less. As for pKa1, 3.5 or less are more preferable, and 3.2 or less are still more preferable. According to this aspect, the stability of the photosensitive resin composition can be improved more.

Here, pKa1 is assumed to use a value calculated from the structural formula using software of ACD/pKa (manufactured by ACD/Labs).

It is preferable that the carboxylate anion is represented by the following formula (X1).

[Formula 24]

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

In this embodiment, the electron withdrawing group means that the Hammett substituent constant σm represents a positive value. Here, σm is the review of Yuho Tsuno, Journal of the Association of Organic Synthetic Chemicals Vol. 23, No. 8 (1965) p. It is described in detail in 631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituent described in the above document.

Examples of substituents in which σm represents a positive value include, for example, a CF ₃ group (σm=0.43), a CF ₃ CO group (σm=0.63), a HC≡C group (σm=0.21), and a CH ₂ =CH group (σm= 0.06), Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), PhCO group (σm=0.34), H ₂ NCOCH ₂ group (σm=0.06), etc. I can. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (the same applies hereinafter).

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

[Formula 25]

In formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.

In this embodiment, it is preferable that the carboxylic acid anion is represented by the following formula (XA).

Expression (XA)

[Formula 26]

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

Specific examples of the carboxylic acid anion include maleic acid anion, phthalic acid anion, N-phenylimino diacetic acid anion, and oxalic acid anion.

As a specific example of a hot base generator, the following compounds are mentioned.

[Formula 27]

[Formula 28]

[Chemical Formula 29]

[Formula 30]

When the photosensitive resin composition of the present invention contains a hot base generator, the content of the hot base generator is preferably 0.1 to 50% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, more preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and may be 5% by mass or less, or 4% by mass or less.

One or two or more of the hot base generators can be used. When using two or more types, it is preferable that the total amount is within the above range.

<< solvent >>

It is preferable that the photosensitive resin composition of this invention contains a solvent. As the solvent, a known solvent can be used arbitrarily. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

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 oxyacetic acid (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., 3-alkyloxypropionate methyl, 3-alkyloxypropionate ethyl, etc.) (E.g., 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, 2 -Methyl alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxy Methyl propionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methyl methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. 2-methoxy-2-methyl methylpropionate, 2 -Ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

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 And propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. are mentioned as suitable ones.

As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are mentioned as suitable ones.

As aromatic hydrocarbons, toluene, xylene, anisole, limonene, etc. are mentioned as a suitable thing, for example.

As sulfoxides, dimethyl sulfoxide is mentioned as a suitable thing, for example.

As the amides, suitable examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and the like.

The solvent is also preferably a form in which two or more types are mixed from the viewpoint of improving the properties of the coated surface. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone , Cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate A mixed solution composed of two or more types is preferable. The combination of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

The content of the solvent is preferably an amount such that the total solid content concentration of the photosensitive resin composition of the present invention becomes 5 to 80 mass%, more preferably 5 to 70 mass%, and 10 to 60 mass% from the viewpoint of coatability Is particularly preferred. The solvent content may be adjusted by a desired thickness and application method. For example, if the coating method is spin coat or slit coat, the content of the solvent that becomes the solid content concentration in the above range is preferable. If it is a spray coat, it is preferable to set it as an amount to be 0.1 mass%-50 mass %, and it is more preferable to set it as an amount to 1.0 mass%-25 mass %. By adjusting the amount of the solvent by the application method, a photosensitive resin composition layer having a desired thickness can be uniformly formed.

The solvent may contain only 1 type, and may contain 2 or more types. When it contains 2 or more types of solvents, it is preferable that the total is the said range.

<<polymerizable compound>>

It is preferable that the photosensitive resin composition of the present invention contains a polymerizable compound (hereinafter, also referred to as "polymerizable monomer"). By setting it as such a structure, a cured film excellent in heat resistance can be formed.

As the polymerizable monomer, a compound (radical polymerizable compound) having a radical polymerizable group can be used. Examples of the radical polymerizable group include groups having ethylenically unsaturated bonds such as styryl group, vinyl group, (meth)acryloyl group and allyl group. The radical polymerizable group is preferably a (meth)acryloyl group.

Although 1 or 2 or more radical polymerizable groups which a polymerizable monomer has, it is preferable to have 2 or more radical polymerizable groups, and it is more preferable to have 3 or more. As for the upper limit, 15 or less are preferable, 10 or less are more preferable, and 8 or less are still more preferable.

The molecular weight of the polymerizable monomer is preferably 2000 or less, more preferably 1500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more.

From the viewpoint of developability, the photosensitive resin composition of the present invention preferably contains at least one bifunctional or higher polymerizable monomer containing two or more polymerizable groups, and at least one trifunctional or higher polymerizable monomer. More preferable. Further, a mixture of a bifunctional polymerizable monomer and a trifunctional or higher polymerizable monomer may be used. In addition, the number of functional groups of a polymerizable monomer means the number of radical polymerizable groups in one molecule.

Specific examples of the polymerizable monomer include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, and preferably, Esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group, and a monofunctional or polyfunctional isocyanate or epoxy, or a monofunctional or polyfunctional A dehydration condensation reaction product with carboxylic acid is also suitably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group, monofunctional or polyfunctional alcohols, amines, thiols, and halogen groups or tosyloxy groups, etc. Substitution reaction products of unsaturated carboxylic acid esters or amides having a detachable substituent of, and 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 a group of compounds substituted with vinylbenzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether, allyl ether, and the like. As a specific example, description of paragraphs 0113 to 0122 of JP 2016-027357 A can be taken into account, and these contents are incorporated in this specification.

Further, the polymerizable monomer is also preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylol ethane 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(meth)acrylate, trimethylolpropanetri(acryloyloxy) A compound obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as propyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane, and then (meth)acrylated, Japanese announcement Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193, Urethane (meth) acrylates described in each publication, Japanese Unexamined Patent Publication No. 48- 064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490, polyester acrylates described in each publication, epoxy acrylates that are reaction products of epoxy resin and (meth)acrylic acid Polyfunctional acrylates and methacrylates such as, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also suitable. Moreover, a polyfunctional (meth)acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having an ethylenically unsaturated group with a cyclic ether group such as glycidyl (meth)acrylate may be mentioned.

In addition, as other preferable polymerizable monomers, those described in JP 2010-160418A, JP 2010-129825A, JP4364216A, etc., have a fluorene ring and have an ethylenically unsaturated bond. It is also possible to use a compound having two or more groups or a cardo resin.

In addition, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. Hei 1-040337, and Japanese Patent Publication No. Hei 1-040336, and Japanese Unexamined Patent Publication No. Hei 2-025493 The vinylphosphonic acid compound etc. described in are also mentioned. In addition, a compound containing a perfluoroalkyl group described in JP-A 61-022048 A can also be used. Also, the Japanese Adhesives Association, vol. 20, No. 7, 300-308 pages (1984) as photopolymerizable monomers and oligomers can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A can also be preferably used, and these contents are incorporated herein by reference.

In addition, after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in Japanese Patent Application Laid-Open No. Hei 10-062986 together with the specific examples thereof as formulas (1) and (2), (meth)acrylate The compound can also be used as a polymerizable monomer.

In addition, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as a polymerizable monomer, and these contents are incorporated herein by reference.

As a polymerizable monomer, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.) A-TMMT; Shin-Nakamura Chemical Co., Ltd.), Dipentaerythritol penta (meth)acrylate (as a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd. product), Dipentaerythritol hexa (meth)acrylic Rate (KAYARAD DPHA as a commercial product; Nippon Kayaku Co., Ltd. product, A-DPH; Shinnakamura Chemical Co., Ltd. product), and these (meth)acryloyl groups are bonded through ethylene glycol and propylene glycol residues A structure that is present is preferred. These oligomer types can also be used.

Examples of commercially available polymerizable monomers include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and SR-209, manufactured by Sartomer, a bifunctional methacrylate having four ethyleneoxy chains. , DPCA-60, a six-functional acrylate having six pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having three three isobutyleneoxy chains, and NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shinnakamura Kagaku High School), 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.), and Blammer PME400 (manufactured by Nichiyu Corporation), and the like.

Polymerizable monomers are Urete described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. Hei 2-032293, and Japanese Patent Publication No. Hei 2-016765. Phosphorus acrylates, ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, Japanese Patent Publication No. 62-039418 Urethane compounds having a are also suitable. In addition, as a polymerizable monomer, a compound having an amino structure or a sulfide structure in a molecule described in JP-A-63-277653, JP-63-260909, and JP-I-105238 You can also use it.

The polymerizable monomer may be a polymerizable monomer having an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group. The polymerizable monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is polymerizable by reacting a non-aromatic carboxylic acid dianhydride to an unreacted hydroxyl group of the aliphatic polyhydroxy compound to give an acid group. The monomer is more preferred. Particularly preferably, in the polymerizable monomer obtained by reacting a non-aromatic carboxylic acid dianhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol and/or dipenta It is a compound that is erythritol. As a commercial item, M-510, M-520, etc. are mentioned as a polybasic acid-modified acrylic oligomer manufactured by Toa Kosei, for example.

The polymerizable monomers having an acid group may be used singly or in combination of two or more. Further, if necessary, a polymerizable monomer having no acid group and a polymerizable monomer having an acid group may be used in combination.

The preferred acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. When the acid value of the polymerizable monomer is in the above range, it is excellent in manufacturing and handling properties, and furthermore, it is excellent in developability. Moreover, the polymerizability is good.

The content of the polymerizable monomer is preferably 1 to 50% by mass with respect to the total solid content of the photosensitive resin composition of the present invention from the viewpoint of good polymerization and heat resistance. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. Polymerizable monomers may be used singly or in combination of two or more.

In addition, the mass ratio of the heterocycle-containing polymer precursor and the polymerizable monomer (heterocycle-containing polymer precursor/polymerizable monomer) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, , 90/10 to 50/50 are most preferred. When the mass ratio of the heterocycle-containing polymer precursor and the polymerizable monomer is within the above range, a cured film having more excellent polymerization properties and heat resistance can be formed.

In the photosensitive resin composition of the present invention, a monofunctional polymerizable monomer can be preferably used from the viewpoint of suppressing the warpage state by controlling the elastic modulus of the cured film. As monofunctional polymerizable monomers, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate )Acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylenegly (Meth)acrylic acid derivatives such as cholmono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglyci Allyl compounds, such as diether, diallyl phthalate, triallyl trimellitate, etc. are preferably used. As the monofunctional polymerizable monomer, a compound having a boiling point of 100°C or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

The photosensitive resin composition of the present invention may further contain other polymerizable compounds other than the above-described heterocycle-containing polymer precursor and radical polymerizable compound. As another polymerizable compound, a compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; Epoxy compounds; Oxetane compounds; Benzoxazine compounds.

(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.

[Formula 31]

(In the formula, t represents an integer of 1 to 20, R ⁴ represents a t-valent organic group having 1 to 200 carbon atoms, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , and R ⁶ Represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁷ represents an organic group having 1 to 10 carbon atoms.)

It is preferable that the content of the compound represented by formula (AM1) is 5 to 40 parts by mass per 100 parts by mass of the heterocycle-containing polymer precursor. More preferably, it is 10 to 35 mass parts. Moreover, it is also preferable to contain 10 to 90 mass% of the compound represented by following formula (AM4) in the total amount of another polymeric compound, and to contain 10 to 90 mass% of the compound represented by following formula (AM5).

[Formula 32]

(In the formula, R ⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , and R ⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms Represents a group, and R ⁷ represents an organic group having 1 to 10 carbon atoms.)

[Formula 33]

(In the formula, 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 group represented by -OR ⁶ or -OCO-R ⁷ , and R ⁶ represents, Represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁷ represents an organic group having 1 to 10 carbon atoms.)

When the photosensitive resin composition of the present invention is applied on a substrate having irregularities by using the above-described compound having a hydroxymethyl group or the like, the occurrence of cracks can be more effectively suppressed. Further, it is possible to form a cured film having high heat resistance, which is excellent in pattern processability and has a 5% mass reduction temperature of 350°C or higher, and more preferably 380°C or higher. Specific examples of the compound represented by formula (AM4) include 46DMOC, 46DMOEP (above, brand name, manufactured by Asahi Yukizai Kogyo Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML -PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, brand name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 ( Brand name, Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p- Cresols, etc. are mentioned.

In addition, as a specific example of the compound represented by formula (AM5), TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP , HMOM-TPPHBA, HMOM-TPHAP (above, brand name, Honshu Chemical Industry Co., Ltd. product), TM-BIP-A (brand name, Asahi Yukizai High School Co., Ltd. product), NIKALAC MX-280, NIKALAC MX-270 , NIKALAC MW-100LM (above, brand name, manufactured by Sanwa Chemical Co., Ltd.) can be mentioned.

(Epoxy compound (compound having an epoxy group))

As an epoxy compound, it is preferable that it is a compound which has 2 or more epoxy groups in 1 molecule. Since the epoxy group undergoes a crosslinking reaction at 200°C or lower and no dehydration reaction resulting from crosslinking occurs, film shrinkage is unlikely to occur. For this reason, containing an epoxy compound is effective for low-temperature curing of the photosensitive resin composition and suppression of a warpage state.

It is preferable that the epoxy compound contains a polyethylene oxide group. Thereby, the modulus of elasticity is further lowered, and the warpage state can be suppressed. Further, the flexibility of the film is increased, and 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.

As an example of an epoxy compound, a bisphenol A type epoxy resin; Bisphenol F type epoxy resin; Alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; Polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Epoxy group-containing silicones, such as polymethyl (glycidyloxypropyl) siloxane, etc. are mentioned, but are not limited to these. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclone (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) EXA-4710, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclone (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4850-150, Epiclon (registered trademark) EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822 (above brand names) , Dai Nippon Ink Kagaku Kogyo Co., Ltd., Lika Resin (registered trademark) BEO-60E (brand name, Shinnihon Rika Co., Ltd.), EP-4003S, EP-4000S (above brand name, manufactured by ADEKA Co., Ltd.) And the like. Among these, an epoxy resin containing a polyethylene oxide group is preferable from the viewpoint of suppressing the warp state and having excellent heat resistance. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and Licarazine (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.

The content of the epoxy compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass per 100 parts by mass of the heterocycle-containing polymer precursor. When the content of the epoxy compound is 5 parts by mass or more, the warp state of the resulting cured film can be further suppressed, and when it is 50 parts by mass or less, pattern embedding caused by reflow at the time of curing can be more suppressed.

(Oxetane compound (compound having an oxetanyl group))

As an oxetane compound, a compound having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy ]Methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. are mentioned. . As a specific example, Aaron Oxetane series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toa Kosei Co., Ltd. can be suitably used, and these can be used alone or in two or more You may mix.

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 per 100 parts by mass of the heterocycle-containing polymer precursor.

(Benzoxazine compound (compound having a benzoxazolyl group))

The benzoxazine compound is preferable because degassing does not occur at the time of curing due to a crosslinking reaction resulting from a ring-opening addition reaction, and since the occurrence of a warped state is suppressed by reducing heat shrinkage.

Preferred examples of the benzoxazine compound include Ba-type benzoxazine, Bm-type benzoxazine (above, brand name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, and phenol novolak-type dihydrobenz Oxazine compounds. These may be individual or may be mixed 2 or more types.

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.

<<migration inhibitor>>

It is preferable that the photosensitive resin composition further contains a migration inhibitor. By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer.

The migration inhibitor is not particularly limited, but heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine A compound having a ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring and a 6H-pyran ring, a triazine ring), thiourea and mercapto group Compounds having, hindered phenolic compounds, salicylic acid derivatives, and hydrazide derivatives. In particular, triazole compounds such as triazole (eg, 1,2,4-triazole) and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole can be preferably used.

Further, an ion trapping agent that captures anions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compound described in paragraphs 0073 to 0076 of JP 2009-283711 A, the compound described in paragraph 0052 of JP 2011-059656 A, The compounds described in paragraphs 0114, 0116 and 0118 of JP 2012-194520 A can be used.

Specific examples of migration inhibitors include 1H-1,2,3-triazole and 1H-tetrazole.

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0% by mass relative to the total solid content of the photosensitive resin composition. More preferable.

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

<< polymerization inhibitor >>

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

Examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol (1,4-methoxyphenol), di-tert-butyl-paracresol, pyrogallol, p-tert-butylcatechol, and parabenzoquinone ( 1,4-benzoquinone), diphenyl-parabenzoquinone, 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, ethylenediamine tetraacetic acid, 1,2-cyclo Hexediamine tetraacetic acid, glycoletherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2 -Naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxy Ammonium amine salts, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, and the like are suitably used. Moreover, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A, and the compounds described in paragraphs 0031 to 0046 of WO2015/0125469 can also be used.

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

[Formula 34]

When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the photosensitive resin composition of the present invention.

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

<<Metal adhesion improver>>

It is preferable that the photosensitive resin composition of this invention contains a metal adhesiveness improving agent for improving the adhesiveness with metal materials used for an electrode, wiring, etc. As a metal adhesion improving agent, a silane coupling agent etc. are mentioned.

As an example of a silane coupling agent, the compound described in paragraphs 0062-0073 of JP 2014-191002 A, the compound described in paragraphs 0063-0071 of WO2011/080992A1, paragraphs 0060-0061 of JP 2014-191252 The compounds described in, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, and the compounds described in paragraph 0055 of International Publication No. WO2014/097594 are mentioned. Moreover, it is also preferable to use two or more types of silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulas, Et represents an ethyl group.

[Formula 35]

In addition, as the metal adhesion improving agent, a compound described in paragraphs 0046 to 0049 of JP 2014-186186 A, and a sulfide compound described in paragraphs 0032 to 0043 of JP 2013-072935 A can also be used.

The content of the metal adhesion improving agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass per 100 parts by mass of the heterocycle-containing polymer precursor. By setting it as 0.1 mass part or more, the adhesiveness between the cured film after a hardening process and a metal layer becomes favorable, and by setting it as 30 mass parts or less, heat resistance and mechanical properties of the cured film after a hardening process become favorable. Only one type of metal adhesion improving agent may be sufficient, and two or more types may be used. When using two or more types, it is preferable that the total is within the above range.

<<Other additives>>

The photosensitive resin composition of the present invention is provided with various additives, such as a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, a higher fatty acid derivative, an inorganic particle, and a curing agent, if necessary, within a range that does not impair the effects of the present invention. , A curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, and the like can be blended. When blending these additives, the total blending amount is preferably 3% by mass or less of the solid content of the photosensitive resin composition.

(Heat acid generator)

The photosensitive resin composition of the present invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating and promotes cyclization of the heterocycle-containing polymer precursor to further improve the mechanical properties of the cured film. Examples of the thermal acid generator include compounds described in paragraph 0059 of JP2013-167742A.

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. By containing 0.01 parts by mass or more of the thermal acid generator, since the crosslinking reaction and the cyclization of the heterocycle-containing polymer precursor are promoted, the mechanical properties and chemical resistance of the cured film can be further improved. In addition, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less from the viewpoint of the electric insulation of the cured film.

Thermal acid generators may be used alone or in combination of two or more. When using two or more types, it is preferable that the total amount falls within the above range.

(Sensitizing pigment)

The photosensitive resin composition of this invention may contain a sensitizing dye. The sensitizing dye absorbs specific actinic radiation and enters an electron excited state. The sensitizing dye in an electron-excited state comes into contact with a hot base generator, a thermal radical polymerization initiator, a radical polymerization initiator, and the like, and functions such as electron transfer, energy transfer, and heat generation occur. Thereby, the thermal base generator, the thermal radical polymerization initiator, and the radical polymerization initiator cause a chemical change and decompose to generate a radical, an acid or a base. For details of the sensitizing dye, the description of paragraphs 0161 to 0163 of JP 2016-027357 A can be referred to, and this content is incorporated herein by reference.

When the photosensitive resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the photosensitive resin composition of the present invention. , 0.5-10 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 this invention may contain a chain transfer agent. Chain transfer agents are defined, for example, on pages 683-684 of the 3rd edition of the Polymer Dictionary (Edition of the Polymer Society, 2005). As the chain transfer agent, a group of compounds having SH, PH, SiH, and GeH in the molecule is used, for example. These can donate hydrogen to a low-activity radical to generate a radical, or can generate a radical by deprotonating after being oxidized. In particular, thiol compounds (e.g., 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 3-mercaptotriazole, 5-mercaptotetrazole Etc.) can be preferably used.

When the photosensitive resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. , 1-5 parts by mass is more preferable. One type of chain transfer agent may be sufficient, and two or more types may be used. When the chain transfer agent is 2 or more types, it is preferable that the total is in the above range.

(Surfactants)

Each type of surfactant may be added to the photosensitive resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. Moreover, the following surfactant is also preferable.

[Formula 36]

When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the photosensitive resin composition of the present invention. . One type of surfactant may be sufficient, and two or more types may be used. When there are two or more surfactants, it is preferable that the total is in the above range.

(Higher fatty acid derivative)

In the photosensitive resin composition of the present invention, in order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added, and it may be unevenly distributed on the surface of the photosensitive resin composition in the process of drying after application.

When the photosensitive resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition of the present invention. One type of higher fatty acid derivative may be sufficient, and two or more types may be used. When there are two or more kinds of higher fatty acid derivatives, it is preferable that the total is within the above range.

<<Restrictions on other substances contained>>

The moisture content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of coating surface properties.

The metal content of the photosensitive resin composition of the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass from the viewpoint of insulating properties. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are included, it is preferable that the total of these metals is within the above range.

In addition, as a method of reducing metal impurities unintentionally contained in the photosensitive resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the photosensitive resin composition of the present invention, or the photosensitive resin composition of the present invention is constructed. A method such as performing filter filtration with respect to the raw material described above, or distilling under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like may be mentioned.

In the photosensitive resin composition of the present invention, the content of the halogen atom is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and particularly preferably less than 200 ppm by mass from the viewpoint of wiring corrosiveness. Among them, what is present in a halogen ion state is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass. As a halogen atom, a chlorine atom and a bromine atom are mentioned. It is preferable that the total of the chlorine atom and the bromine atom, or the chlorine ion and the bromine ion is in the above range, respectively.

<Preparation of photosensitive resin composition>

The photosensitive resin composition of this invention can be prepared by mixing each said component. The mixing method is not particularly limited and can be performed by a conventionally known method.

In addition, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the photosensitive resin composition. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. You may use the filter previously washed with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel to be used. When using a plurality of types of filters, filters having different pore diameters and/or materials may be used in combination. Further, various materials may be filtered a plurality of times. In the case of filtering a plurality of times, circulation filtration may be employed. Moreover, you may pressurize and perform filtration. When performing filtration by pressurization, the pressure to be pressurized is preferably 0.05 MPa or more and 0.3 MPa or less.

In addition to filtration using a filter, a treatment for removing impurities using an adsorbent may be performed. You may combine filter filtration and impurity removal treatment using an adsorbent. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

[Cured film and manufacturing method of cured film, and application of cured film]

The photosensitive resin composition of the present invention can be cured and used as a cured film. As a field to which the method for producing a cured film of the present invention is applicable, an insulating film for a semiconductor device, in particular, an interlayer insulating film for a redistribution layer, etc. are mentioned.

The photosensitive resin composition of this invention is suitable for negative-type development. Moreover, it is suitable for use in developing using a developer containing an organic solvent. As an organic solvent used for a developer, an organic solvent which may be blended into the photosensitive resin composition is illustrated, and cyclopentanone is preferred.

That is, the present invention also includes a cured film obtained by curing the photosensitive resin composition of the present invention, and a semiconductor device having the cured film.

In addition, in the present invention, a method for producing a cured film including a step of applying the photosensitive resin composition of the present invention to a substrate and a step of curing the photosensitive resin composition applied to the substrate is disclosed. In addition, the method for producing the cured film preferably includes a step of exposing the cured film and negatively developing, and more preferably, the development is performed using a developer containing an organic solvent.

In addition, the cured film in the present invention can also be used for photoresist for electronics (galvanic (electrolytic) resist, etching resist, solder top resist) or the like.

In addition, the cured film in the present invention can also be used for the production of a plate surface such as an offset plate surface or a screen plate surface, use for etching of molded parts, and the production of protective lacquers and dielectric layers in electronics, particularly microelectronics.

Next, an embodiment of a semiconductor device in which the photosensitive resin composition is used for an interlayer insulating film for a redistribution layer will be described.

The semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a laminate 101 in which a plurality of semiconductor elements (semiconductor chips) 101a to 101d are stacked is disposed on a wiring board 120 .

In addition, in this embodiment, the case where the number of stacked semiconductor elements (semiconductor chips) is four is mainly described, but the number of stacked semiconductor elements (semiconductor chips) is not particularly limited, and for example, two layers, eight layers, The 16th floor, the 32nd floor, etc. may be sufficient. Moreover, it may be the first floor.

Each of the plurality of semiconductor elements 101a to 101d is made of a semiconductor wafer such as a silicon substrate.

The uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof.

The semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) integrally provided with the through electrodes are provided on both surfaces of each semiconductor element.

The stacked body 101 has a structure in which a semiconductor element 101a having no through electrodes and semiconductor elements 101b to 101d having through electrodes 102b to 102d are flip-chip connected.

That is, the electrode pad of the semiconductor element 101a not having a through electrode and the connection pad on the side of the semiconductor element 101a of the semiconductor element 101b having the through electrode 102b adjacent thereto are metal bumps such as solder bumps. The connection pad on the other side of the semiconductor element 101b connected by 103a and having the through electrode 102b is on the side of the semiconductor element 101b of the semiconductor element 101c having the through electrode 102c adjacent thereto. The connection pads are connected with metal bumps 103b such as solder bumps. 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, and solder It is connected by metal bumps 103c such as bumps.

An underfill layer 110 is formed in the gap between each of the semiconductor elements 101a to 101d, and each of the semiconductor elements 101a to 101d is stacked through the underfill layer 110.

The laminate 101 is laminated on the wiring board 120.

As the wiring board 120, a multilayer wiring board using an insulating substrate such as a resin substrate, a ceramics substrate, and a glass substrate as a base material is used. As the wiring board 120 to which a resin substrate is applied, a multilayer copper clad laminate (multilayer printed wiring board), etc. are mentioned.

A surface electrode 120a is provided on one surface of the wiring board 120.

An insulating film 115 having a redistribution layer 105 is disposed between the wiring board 120 and the stacked body 101, and the wiring board 120 and the stacked body 101 have a redistribution layer 105 It is electrically connected through. The insulating film 115 is formed by using the photosensitive resin composition in 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 side of the redistribution layer 105 through a metal bump 103d such as a solder bump. In addition, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board through a metal bump 103e such as a solder bump.

And an underfill layer 110a is formed between the insulating film 115 and the laminated body 101. In addition, an underfill layer 110b is formed between the insulating film 115 and the wiring board 120.

In addition to the above, the cured film in the present invention can be widely adopted for various applications using polyimide or polybenzoxazole.

In addition, since polyimide and polybenzoxazole are resistant to heat, the cured film in the present invention is also used as a transparent plastic substrate for display devices such as liquid crystal displays and electronic paper, automobile parts, heat-resistant paints, coatings, and films. It can be used suitably.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. Materials, usage, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Acid compound>

The following acidic compounds were used.

<<Measurement of pKa of acidic compound>>

The measurement of pKa used the value calculated from the structural formula using software of ACD/pKa (manufactured by ACD/Labs).

[Table 1]

<Synthesis of heterocycle-containing polymer precursor composition (resin composition)>

(Synthesis Example 1)

[Synthesis of polyimide precursor composition A-1 from 4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and diamine (a) shown below]

42.4 g of 4,4'-oxydiphthalic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed, and at a temperature of 60° C. for 4 hours Stirred. Then, the reaction mixture was cooled to -10°C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5°C for 60 minutes, and the mixture Was stirred for 30 minutes. Subsequently, a solution in which 76.0 g of diamine (a) shown below was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5° C. for 60 minutes, and the mixture was stirred for 1 hour, 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, the polyimide precursor was precipitated, filtered, and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polyimide precursor was a weight average molecular weight of 26500 and a number average molecular weight of 9300.

Diamine (a)

[Formula 37]

(Synthesis Example 2)

[Synthesis of polyimide precursor composition A-2 from 4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate, and diamine (a)]

42.4 g of 4,4'-oxydiphthalic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed, and at a temperature of 60° C. for 4 hours Stirred. Then, the reaction mixture was cooled to -10°C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5°C for 60 minutes, and the mixture Was stirred for 30 minutes. Subsequently, a solution in which 76.0 g of diamine (a) was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5° C. for 60 minutes, and the mixture was stirred for 1 hour, and then 3.0 g of Oxalic acid, 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, the polyimide precursor was precipitated, filtered, and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polyimide precursor had a weight average molecular weight of 25100 and a number average molecular weight of 8500.

(Synthesis Example 3)

[Synthesis of polyimide precursor composition A-3 from 4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and diamine (a)]

42.4 g of 4,4'-oxydiphthalic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed, and at a temperature of 60° C. for 4 hours Stirred. Then, the reaction mixture was cooled to -10°C, a solution in which 34.35 g of diisopropylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5°C for 60 minutes, and the mixture Was stirred for 30 minutes. Subsequently, a solution in which 76.0 g of diamine (a) was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5° C. for 60 minutes, and the mixture was stirred for 1 hour, and then 3.0 g of Methanesulfonic acid, 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, the polyimide precursor was precipitated, filtered, and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polyimide precursor was a weight average molecular weight of 26800 and a number average molecular weight of 9400.

(Synthesis Example 4)

[Synthesis of polyimide precursor composition A-4 from pyromellitic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl ]

29.8 g of pyromellitic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed, followed by stirring at a temperature of 60° C. for 4 hours. Then, the reaction mixture was cooled to -10°C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5°C for 60 minutes, and the mixture Was stirred for 30 minutes. Subsequently, a solution in which 40.2 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl was dissolved in 200 mL of γ-butyrolactone was dissolved at -10±5° C. for 60 minutes. It was added dropwise to the reaction mixture, and after stirring the mixture for 1 hour, 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, the polyimide precursor was precipitated, filtered, and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polyimide precursor was a weight average molecular weight of 24900 and a number average molecular weight of 8400.

(Synthesis Example 5)

[Synthesis of polyimide precursor composition A-5 from pyromellitic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl ]

29.8 g of pyromellitic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed, followed by stirring at a temperature of 60° C. for 4 hours. Then, the reaction mixture was cooled to -10°C, and a solution in which 34.35 g of dicyclohexylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5°C for 60 minutes, and the mixture Was stirred for 30 minutes. Subsequently, a solution in which 40.2 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl was dissolved in 200 mL of γ-butyrolactone was dissolved at -10±5° C. for 60 minutes. It was added dropwise to the reaction mixture, and after stirring the mixture for 1 hour, 3.0 g of formic acid, 20 mL of ethyl alcohol, and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, the polyimide precursor was precipitated, filtered, and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polyimide precursor had a weight average molecular weight of 25200 and a number average molecular weight of 8800.

(Synthesis Example 6)

[Synthesis of polyimide precursor composition A-6 from pyromellitic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl ]

14.9 g of pyromellitic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme (diethylene glycol dimethyl ether) were mixed, The mixture was stirred at a temperature of 60°C for 4 hours. Then, the reaction mixture was cooled to -10°C and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at -10±5°C. After diluting with 50 mL of N-methylpyrrolidone, 20.1 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl was dissolved in 100 mL of N-methylpyrrolidone. The solution was added dropwise to the reaction mixture at -10±5° C. for 60 minutes, and the mixture was stirred for 1 hour, and 3.0 g of 10-camphorsulfonic acid and 20 mL of ethyl alcohol were added. 6 L of water was added to the obtained reaction solution to precipitate a polyimide precursor, and the solid was filtered and dissolved in 380 g of tetrahydrofuran. 6 L of water was added to the obtained solution to precipitate a polyimide precursor, and the solid was filtered again and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polyimide precursor had a weight average molecular weight of 23900 and a number average molecular weight of 8000.

(Synthesis Example 7)

[Synthesis of polyimide precursor composition A-7 from 4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diaminodiphenyl ether]

42.4 g of 4,4'-oxydiphthalic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed, and at a temperature of 60° C. for 4 hours Stirred. Then, the reaction mixture was cooled to -10°C, a solution in which 34.35 g of diisopropylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5°C for 60 minutes, and the mixture Was stirred for 30 minutes. Then, a solution in which 25.1 g of 4,4'-diaminodiphenyl ether was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5° C. for 60 minutes, and the mixture was stirred for 1 hour. After that, 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, the polyimide precursor was precipitated, filtered, and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polyimide precursor had a weight average molecular weight of 25400 and a number average molecular weight of 8500.

(Synthesis Example 8)

[Synthesis of polyimide precursor composition A-8 from 4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]

42.4 g of 4,4'-oxydiphthalic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed, and at a temperature of 60° C. for 4 hours Stirred. Then, the reaction mixture was cooled to -10°C, a solution in which 34.35 g of diisopropylcarbodiimide was dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5°C for 60 minutes, and the mixture Was stirred for 30 minutes. Then, a solution in which 25.1 g of 4,4'-diaminodiphenyl ether was dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at -10±5° C. for 60 minutes, and the mixture was stirred for 1 hour. After that, 3.0 g of p-toluenesulfonic acid monohydrate, 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, the polyimide precursor was precipitated, filtered, and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polyimide precursor was a weight average molecular weight of 24800 and a number average molecular weight of 8800.

(Synthesis Example 9)

Polyimide precursor composition A from [4,4'-oxydiphthalic dianhydride, 2-hydroxyethylmethacrylate and 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl Synthesis of -9]

21.2 g of 4,4'-oxydiphthalic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme were mixed, and at a temperature of 60° C. for 4 hours Stirred. Then, the reaction mixture was cooled to -10°C and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at -10±5°C. After diluting with 50 mL of N-methylpyrrolidone, 20.1 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl was dissolved in 100 mL of N-methylpyrrolidone. The solution was added dropwise to the reaction mixture at -10±5° C. for 60 minutes, and after the mixture was stirred for 1 hour, 20 mL of ethyl alcohol was added. 6 L of water was added to the obtained reaction solution to precipitate a polyimide precursor, and the solid was filtered and dissolved in 380 g of tetrahydrofuran. 6 L of water was added to the obtained solution to precipitate a polyimide precursor, and the solid was filtered again and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polyimide precursor was a weight average molecular weight of 24400 and a number average molecular weight of 8400.

(Synthesis Example 10)

Polyimide precursor composition A from [4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl Synthesis of -10]

21.2 g of 4,4'-oxydiphthalic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme were mixed, and at a temperature of 60° C. for 4 hours Stirred. Then, the reaction mixture was cooled to -10°C and 17.0 g of SOCl ₂ was added over 60 minutes while maintaining the temperature at -10±5°C. After diluting with 50 mL of N-methylpyrrolidone, 20.1 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl was dissolved in 100 mL of N-methylpyrrolidone. The solution was added dropwise to the reaction mixture at -10±5° C. for 60 minutes, and the mixture was stirred for 1 hour, and then 3.0 g of p-toluenesulfonic acid monohydrate and 20 mL of ethyl alcohol were added. 6 L of water was added to the obtained reaction solution to precipitate a polyimide precursor, and the solid was filtered and dissolved in 380 g of tetrahydrofuran. 6 L of water was added to the obtained solution to precipitate a polyimide precursor, and the solid was filtered again and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polyimide precursor was a weight average molecular weight of 24400 and a number average molecular weight of 8400.

(Synthesis Example 11)

[Synthesis of polybenzoxazole precursor composition A-11 from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydibenzoyl chloride]

28.0 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was stirred and dissolved in 200 mL of N-methylpyrrolidone. Subsequently, 25.0 g of 4,4'-oxydibenzoyl chloride was added dropwise for 10 minutes while maintaining the temperature at 0 to 5°C, and then stirring was continued for 60 minutes. 6 L of water was added to the obtained reaction solution to precipitate a polybenzoxazole precursor, and the solid was filtered and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polybenzoxazole precursor had a weight average molecular weight of 28500 and a number average molecular weight of 9800.

(Synthesis Example 12)

[Synthesis of polybenzoxazole precursor composition A-12 from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydibenzoyl 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, 25.0 g of 4,4'-oxydibenzoyl chloride was added dropwise for 10 minutes, then stirring was continued for 60 minutes, and 3.0 g of maleic acid was added. 6 L of water was added to the obtained reaction solution to precipitate a polybenzoxazole precursor, and the solid was filtered and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polybenzoxazole precursor was a weight average molecular weight of 26900 and a number average molecular weight of 9700.

(Synthesis Example 13)

[Synthesis of polybenzoxazole precursor composition A-13 from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydibenzoyl 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, 25.0 g of 4,4'-oxydibenzoyl chloride was added dropwise for 10 minutes, followed by stirring for 60 minutes, and 3.0 g of p-toluenesulfonic acid monohydrate. Added. 6 L of water was added to the obtained reaction solution to precipitate a polybenzoxazole precursor, and the solid was filtered and dried at 45° C. for 2 days under reduced pressure. The obtained powdery polybenzoxazole precursor was a weight average molecular weight of 26900 and a number average molecular weight of 9700.

<Volume resistivity of resin composition>

Each resin composition prepared in Synthesis Examples 1 to 13 was used as a cured film having a thickness of 10 μm, and the volume resistivity of the cured film after heating at 350°C for 60 minutes was measured.

The volume resistivity was measured by the double ring electrode method using an insulation resistance meter (manufactured by Advan Test Co., Ltd., brand name R8340). The coating film was placed on a circular electrode, the electrical resistance was measured with an insulation resistance meter, and the volume resistivity was calculated from the shape of the electrode. As an insulation resistance meter, Advan test make, brand name R8340 was used.

When the resin composition was in a liquid state, it was applied on a substrate, the solvent was dried to obtain a cured film having the above thickness, and the volume resistivity after heating was measured. When the viscosity is high, after the resin composition is dissolved in a solvent that dissolves at 25°C, it is applied onto a substrate, and the solvent is dried to obtain a cured film having the above thickness, and the volume resistivity after heating is measured.

When the resin composition is in the form of a powder, the resin composition is dissolved in a solvent that dissolves at 25°C, then applied on a substrate, and the solvent is dried to obtain a cured film having the above thickness, and the volume resistivity after heating is measured. did.

In the case of using any resin composition, the heterocycle-containing polymer precursor was sufficiently cyclized with respect to the obtained cured film, and the volume resistivity was 1.0×10 ⁵ Ω·cm or less.

<Preparation of photosensitive resin composition>

Each component shown in following Table 2 or Table 3 was mixed, and it was set as a uniform solution, and the photosensitive resin composition was prepared. The photosensitive resin composition obtained above was subjected to pressure filtration through a filter having a fine pore width of 0.8 μm.

<<Volume resistivity of photosensitive resin composition>>

It carried out similarly to the volume resistivity of the said resin composition, and measured the volume resistivity of a photosensitive resin composition. Also in the case of using any photosensitive resin composition, in the obtained cured film, the heterocycle-containing polymer precursor was sufficiently cyclized, and the volume resistivity was 1.0×10 ⁵ Ω·cm or less.

<<Resolution>>

The photosensitive resin composition was applied by spinning (1200 rpm, 30 seconds) on a silicon wafer having a thickness of 250 μm and a diameter of 100 mm. The silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100° C. for 5 minutes to form a film having a thickness of 10 μm on the silicon wafer. Next, the film applied on the silicon wafer was subjected to pattern exposure using an aligner (Karl-Suss MA150) and an exposure mask (line/space=1/1). Exposure was performed with a high-pressure mercury lamp, and irradiated with 500 mJ/cm ^{2 in} terms of exposure energy at a wavelength of 365 nm. After irradiation, the image was developed for 75 seconds with cyclopentanone. The obtained pattern was observed, and the minimum line width at which a line and a space were separated and resolved was taken as the resolution.

<<conservation stability>>

10 g of the photosensitive resin composition was sealed in a container (material of container: light-shielding glass, capacity: 100 mL), and left standing in an environment of 25°C and 65% relative humidity. Stability was evaluated in the time until a solid precipitated from the photosensitive resin composition. The longer the time, the higher the stability of the photosensitive resin composition, and a preferable result. The precipitation of the solid was filtered under pressure with a mesh having a pore diameter of 0.8 μm, and the presence or absence of foreign matter on the mesh was visually observed.

A: Even if it exceeded 120 days, precipitation of a solid was not seen.

B: More than 60 days and within 120 days, a solid precipitated.

C: More than 30 days and within 60 days, a solid precipitated.

D: A solid precipitated within 30 days.

<<metal corrosiveness>>

The photosensitive resin composition was applied by spinning (1200 rpm, 30 seconds) on a copper substrate having a thickness of 250 μm. The copper substrate to which the photosensitive resin composition was applied was dried on a hot plate at 100° C. for 5 minutes, and a film having a thickness of 10 μm was formed on the copper substrate. Then, it heated up at a temperature rising rate of 10 degreeC/min under nitrogen atmosphere, and after reaching 230 degreeC, it held for 3 hours. After cooling, the film on the copper substrate was physically peeled off. The copper substrate was visually observed, the area ratio colored in reddish brown was calculated, and the metal corrosiveness was evaluated. The smaller the area ratio, the less corrosive to the metal.

A: 1% or less.

B: More than 1% and less than 5%.

C: More than 5% and less than 10%.

D: More than 10%.

[Table 2]

[Table 3]

(A) Resin (heterocycle-containing polymer precursor composition)

A-1 to A-13: Heterocycle-containing polymer precursor composition prepared in Synthesis Examples 1 to 13

(B) polymerizable compound

B-1: NK ester M-40G (made by Shinnakamura Kagaku High School)

B-2: SR-209 (manufactured by Satomer)

B-3: NK ester A-9300 (made by Shinnakamura Kagaku High School)

B-4: A-TMMT (manufactured by Shinnakamura Kagaku High School)

(C) photopolymerization initiator

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

C-2: IRGACURE OXE 02 (manufactured by BASF)

C-3: IRGACURE OXE 04 (manufactured by BASF)

C-4: IRGACURE-784 (manufactured by BASF)

C-5: NCI-831 (manufactured by ADEKA Co., Ltd.)

(D) Hot base generator

D-1: the following compound

D-2: the following compound

D-3: the following compound

[Formula 38]

(E) polymerization inhibitor

E-1: 1,4-benzoquinone

E-2: 1,4-methoxyphenol

(F) additive

F-1: 1,2,4-triazole

F-2: 1H-tetrazole

(G) Silane coupling agent

G-1: the following compound

G-2: the following compound

G-3: the following compound

[Formula 39]

(H) solvent

H-1: γ-butyrolactone

H-2: dimethyl sulfoxide

H-3: N-methyl-2-pyrrolidone

H-4: ethyl lactate

In addition, for the solvent in Table 2 or Table 3, for example, if the column of type is "H-1/H-2" and the column of mass% is "48+12", H-1 is It means containing 48 mass% and 12 mass% of H-2.

(I) acidic compounds

I-1: formic acid

I-2: oxalic acid

I-3: maleic acid

I-4: malonic acid

I-5: pyruvic acid

I-6: DL-lactic acid

I-7: p-toluenesulfonic acid monohydrate

I-8: 10-camphorsulfonic acid

I-9: methanesulfonic acid

I-10: acetic acid

As is clear from the results of Table 2 or Table 3, the photosensitive resin composition using the resin composition of the present invention has high resolving power and excellent storage stability.

In particular, by using a pKa3.5 or less, further 3.0 or less, particularly 2.0 or less, as an acidic compound, the effect of the present invention is further improved.

Moreover, by using a thing with a molecular weight of 100 or more as an acidic compound, the effect of suppressing metal corrosivity was improved more effectively.

100: semiconductor device
101a~101d: semiconductor device
101: laminate
102b~102d: through electrode
103a~103e: metal bump
105: redistribution layer
110, 110a, 110b: under fill layer
115: insulating film
120: wiring board
120a: surface electrode

Claims (23)

A photosensitive resin composition comprising a polybenzoxazole precursor and a polyimide precursor containing a repeating unit represented by the following formula (1), a resin composition containing an acidic compound having a pKa of 4.0 or less, and a photopolymerization initiator As a resin composition,
The acidic compound is selected from carboxylic acid, imide acid, methic acid, nitric acid and sulfuric acid,
The photosensitive resin composition, wherein the photosensitive resin composition is a cured film having a thickness of 10 μm, and the volume resistivity of the cured film after heating at 350° C. for 60 minutes is 1.0×10 ⁵ Ω·cm or less:
Equation (1)

In formula (1), A ¹ and A ² each independently represent an oxygen atom or NH,
R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, 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 radical polymerizable group Include. The method according to claim 1,
The photosensitive resin composition in which the said polybenzoxazole precursor contains a repeating unit represented by following formula (2);
Equation (2)

In formula (2), 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. The method according to claim 1 or 2,
The photosensitive resin composition, wherein the acidic compound has a pKa of 3.5 or less. The method according to claim 1 or 2,
The molecular weight of the acidic compound is 100 to 300, photosensitive resin composition. delete delete delete delete delete The method according to claim 1,
The acidic compound is selected from formic acid, oxalic acid dihydrate, maleic acid, malonic acid, pyruvic acid, DL-lactic acid, sulfuric acid and acetic acid. The method according to claim 1,
A photosensitive resin composition for negative development. The method according to claim 1,
A photosensitive resin composition used for developing using a developer containing an organic solvent. The method according to claim 1,
A photosensitive resin composition for forming an interlayer insulating film for a redistribution layer. A cured film obtained by curing the photosensitive resin composition according to claim 1. The method of claim 14,
Cured film, which is an interlayer insulating film for redistribution layers. A method for producing a cured film comprising a step of applying the photosensitive resin composition according to claim 1 to a substrate, and a step of curing the photosensitive resin composition applied to the substrate. The method of claim 16,
A method for producing a cured film, further comprising a step of exposing the cured film to light and developing a negative type. The method of claim 17,
In the above development, a method for producing a cured film, comprising using a developer containing an organic solvent. A semiconductor device having the cured film according to claim 14 or 15. A method for producing a photosensitive resin composition comprising a polybenzoxazole precursor and a heterocyclic-containing polymer precursor selected from a polyimide precursor containing a repeating unit represented by the following formula (1), wherein pKa is 4.0 or less, and a carboxylic acid or imide acid , A step of adding an acidic compound selected from methic acid, nitric acid and sulfuric acid, and a step of adding a photopolymerization initiator, wherein the photosensitive resin composition is in powder form:
Equation (1)

In formula (1), A ¹ and A ² each independently represent an oxygen atom or NH,
R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, 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 radical polymerizable group Include. As a method for producing the photosensitive resin composition according to claim 1 or 2,
A method for producing a photosensitive resin composition, comprising adding an acidic compound having a pKa of 4.0 or less and selected from carboxylic acid, imide acid, methide acid, nitric acid and sulfuric acid in the step of synthesizing a heterocycle-containing polymer precursor. As a method for producing the photosensitive resin composition according to claim 1 or 2,
After synthesizing the heterocycle-containing polymer precursor, a method for producing a photosensitive resin composition, comprising adding an acidic compound having a pKa of 4.0 or less and selected from carboxylic acid, imide acid, methic acid, nitric acid and sulfuric acid. The method of claim 20,
A method for producing a photosensitive resin composition, comprising adding a carbodiimide compound in the step of synthesizing a heterocycle-containing polymer precursor.

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