WO2021002383A1

WO2021002383A1 - Curable resin composition, method for producing curable resin composition, cured film, multilayer body, method for producing cured film, and semiconductor device

Info

Publication number: WO2021002383A1
Application number: PCT/JP2020/025783
Authority: WO
Inventors: 敦靖野崎; 悠岩井
Original assignee: 富士フイルム株式会社
Priority date: 2019-07-01
Filing date: 2020-07-01
Publication date: 2021-01-07
Also published as: KR20220013561A; JPWO2021002383A1; JP7422763B2; CN114008526A; TW202110958A

Abstract

Provided is a curable resin composition which comprises: at least one resin that is selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; a basic compound represented by formula (1-1) or a weak acid salt thereof; a polymerization initiator; and a solvent. Also provided are: a method for producing this curable resin composition; a cured film which is obtained by curing this curable resin composition; a multilayer body which comprises this cured film; a method for producing this cured film; and a semiconductor device which comprises this cured film or this multilayer body.

Description

Curable resin composition, method for producing curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device

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

Polymer precursors such as polyimide resin and polybenzoxazole resin (hereinafter, the precursor of polyimide resin and the precursor of polybenzoxazole resin are collectively referred to as "heterocycle-containing polymer precursor") were cyclized and cured. Resin is applied to various uses because it has excellent heat resistance and insulating properties. The above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film or a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.

For example, in the applications described above, the heterocyclic polymer precursor is used in the form of a curable resin composition comprising the heterocyclic polymer precursor. Such a curable resin composition is applied to a base material by, for example, coating, and then the heterocyclic-containing polymer precursor is cyclized by heating or the like to form a cured resin on the base material. Can be done. Since the curable resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the curable resin composition to be applied. It can be said that it has excellent adaptability.
In addition to the high performance of polyimide and the like, from the viewpoint of excellent adaptability in manufacturing, industrial application development of a curable resin composition containing a heterocyclic polymer precursor is expected more and more.

For example, Patent Document 1 describes a polyamic acid composed of water and N-methyl-2-pyrrolidone and a water content of 10 to 90% by mass, a polyamic acid composed of a repeating unit having a specific structure, and imidazoles. A polyimide precursor composition obtained by dissolving a basic compound selected from the group consisting of an amine compound and an amine compound is described.
In Patent Document 2, a solvent-soluble polyimide having a specific structure and 3 to 100% of the total number of moles of diamine or triamine in the specific structure has a sulfonic acid group and / or a sulfinic acid group introduced into the skeleton. Described is an electrodeposited polyimide resin composition comprising solvent-soluble polyimide, water, and a basic compound.

JP-A-2016-017145 Japanese Unexamined Patent Publication No. 2008-291265

In a curable resin composition containing a heterocyclic-containing polymer precursor, it is desired to provide a curable resin composition having excellent film strength of the obtained cured product.

The present invention relates to a curable resin composition having excellent film strength of the obtained cured film, a method for producing the curable resin composition, a cured film obtained by curing the curable resin composition, and a laminate containing the cured film. An object of the present invention is to provide a method for producing the cured film, and a semiconductor device including the cured film or the laminate.

Examples of typical embodiments of the present invention are shown below.
<1> At least one resin selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor.
A basic compound represented by the following formula (1-1) or a weak acid salt thereof,
A curable resin composition containing a polymerization initiator and a solvent.

In formula (1-1), R ¹ to R ³ each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, or a substituted or unsubstituted aromatic group, and R ¹ to R ³ It may form at least two members ring structure of, when R 1 ^~ R ³ does not contain an alkoxysilyl group as a substituent, at least one of hydrogen atoms of ^{^{^{R 1 ~ R 3, R 1}}} ~ one another at least one R ³ represents a structure having a branched structure or a cyclic structure.
<2> The basic compound or its weak acid salt comprises a secondary aliphatic amine, a tertiary aliphatic amine, a secondary aromatic amine, a tertiary aromatic amine, and a nitrogen-containing heterocyclic compound. The curable resin composition according to <1>, which is at least one basic compound selected from the group or a weak acid salt thereof.
<3> The curable resin composition according to <1> or <2>, wherein the basic compound or a weak acid salt thereof is a monoamine compound or a weak acid salt thereof.
<4> 4. Curable resin composition.
<5> The curable resin composition according to any one of <1> to <4>, wherein the basic compound or a weak acid salt thereof has a molecular weight of 60 to 200.
<6> The curable resin composition according to any one of <1> to <5>, wherein the resin is a polyimide precursor having a repeating unit represented by the following formula (1).

In formula (1), A ¹ and A ² 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 Each of R ¹¹⁴ independently represents a hydrogen atom or a monovalent organic group.
<7> At least one of R ¹¹³ and R ¹¹⁴ contains a radically polymerizable group, <6>.
The curable resin composition according to.
<8> The curable resin composition according to any one of <1> to <7>, wherein the acid value of the resin is 8 to 80 mgKOH / g.
<9> The curable resin composition according to any one of <1> to <8>, wherein the water content is 5% by mass or less with respect to the total mass of the solvent.
<10> The curable resin composition according to any one of <1> to <9>, further comprising a radically polymerizable compound.
<11> The curable resin composition according to any one of <1> to <10>, further comprising at least one selected from the group consisting of an onium salt and a thermosetting agent.
<12> The curable resin composition according to any one of <1> to <11>, which is used for forming an interlayer insulating film for a rewiring layer.
<13> The method for producing the curable resin composition according to any one of <1> to <12>.
A method for producing a curable resin composition, which comprises a step of mixing a composition containing the resin, the polymerization initiator, and the solvent with a basic compound represented by the formula (1-1) or a weak acid salt thereof.
<14> A cured film obtained by curing the curable resin composition according to any one of <1> to <12>.
<15> A laminate containing two or more layers of the cured film according to <14> and containing a metal layer between any of the cured films.
<16> A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of <1> to <12> to a substrate to form a film.
<17> A composition containing the resin, the polymerization initiator, and the solvent is mixed with a basic compound having a structure represented by the formula (1-1) or a weak acid salt thereof, and the curable resin composition is prepared. The method for producing a cured film according to <16>, which comprises a step of producing a product before the film forming step.
<18> The method for producing a cured film according to <16> or <17>, which comprises an exposure step of exposing the film and a developing step of developing the film.
<19> The method for producing a cured film according to any one of <16> to <18>, which comprises a heating step of heating the film at 50 to 450 ° C.
<20> A semiconductor device comprising the cured film according to <14> or the laminate according to <15>.

According to the present invention, a curable resin composition having excellent film strength of the obtained cured film, a method for producing the curable resin composition, a cured film obtained by curing the curable resin composition, and the cured film are included. Provided are a laminate, a method for producing the cured film, and a semiconductor device containing the cured film or the laminate.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, the numerical range represented by using the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
In the present specification, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacryl", or , Any of, "(meth) acryloyl" means both "acryloyl" and "methacryloyl", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is above or below the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as "upper". The opposite direction is referred to as "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ° C. and the atmospheric pressure is 101,325 Pa (1 atm).
In the present specification, the combination of preferred embodiments is a more preferred embodiment.

(Curable resin composition)
The curable resin composition of the present invention comprises at least one resin selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and a compound represented by the following formula (1-1) (hereinafter,: , Also referred to as "specific compound").
The curable resin composition of the present invention preferably contains a polymerizable compound, and more preferably contains a radically polymerizable compound.
Further, the curable resin composition of the present invention preferably further contains at least one selected from the group consisting of onium salts and thermosetting agents.

In formula (1-1), R ¹ to R ³ each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, or a substituted or unsubstituted aromatic group, and R ¹ to R ³ It may form at least two members ring structure of, when R 1 ^~ R ³ does not contain an alkoxysilyl group as a substituent, at least one of hydrogen atoms of ^{^{^{R 1 ~ R 3, R 1}}} ~ one another at least one R ³ represents a structure having a branched structure or a cyclic structure.

The curable resin composition of the present invention is excellent in the film strength of the obtained cured film.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.

Conventionally, a curable resin composition containing a polymer precursor has been used for applications such as applying it to a substrate or the like and then heating or the like to cyclize the precursor to obtain a cured film containing a polyimide resin or the like. I came.
Here, when a cured film is obtained by the above method, the film is cured as the cyclization progresses, so that the movement of the structure contained in the polymer precursor before cyclization in the film is restricted. As a result, further cyclization may be less likely to occur.
However, the curable resin composition of the present invention contains a specific compound. The particular compound is believed to promote cyclization of the polymer precursor. Further, since the specific compound having the structure represented by the formula (1-1) is considered to be easily migrated even in the membrane in which cyclization is progressing, it is considered that the specific compound is easily transferred even in the membrane in which cyclization is progressing. It is believed that further cyclization of the heterocyclic-containing polymer precursor is promoted. According to the curable resin composition of the present invention, it is considered that the ring closure rate of the polymer precursor is improved and a cured film having excellent film strength can be obtained by the above mechanism.
Further, according to the curable resin composition of the present invention, since the ring closure rate is improved as described above, it is considered that a cured film having excellent chemical resistance can be easily obtained.
Further, since the specific compound in the curable resin composition of the present invention has a specific structure, it is difficult to promote the cyclization of the polymer precursor when stored at, for example, 20 ° C., and the storage stability is also improved. It is considered to be excellent.
When the curable resin composition has photosensitivity, for example, the composition film formed from the curable resin composition is exposed to a pattern exposure or the like, polymerized, developed, and then heated to be described above. In some cases, cyclization of the polymer precursor of
When the curable resin composition is photosensitive, for example, the polymer precursor has a polymerizable group, the curable resin composition contains a polymerizable compound, or both, and the curable resin composition is cured. Examples thereof include the case where the polymerization initiator in the sex resin composition is a photopolymerization initiator.
When cyclization is performed in such a post-polymerization membrane, the cyclization of the polymer precursor proceeds because the membrane is cured by the polymerization and the movement of the structure contained in the polymer precursor is restricted. It may be difficult to do.
According to the curable resin composition of the present invention, even in the film after the polymerization of such a polymerizable group has proceeded, cyclization is promoted by the specific compound, so that the ring closure rate of the polymer precursor is improved. It is considered that a cured film having excellent film strength can be easily obtained.
In particular, even when the amount of exposure in the above exposure is large and the degree of progress of the above-mentioned polymerization is large, according to the curable resin composition of the present invention, a cured film having excellent film strength can be obtained by promoting cyclization by a specific compound. It is considered easy to obtain.

Here, Patent Document 1 or 2 does not describe or suggest a curable resin composition containing a heterocyclic polymer precursor, a specific compound, a polymerization initiator, and a solvent.
Hereinafter, the components contained in the curable resin composition of the present invention will be described in detail.

<Heterocycle-containing polymer precursor>
The curable resin composition of the present invention contains a heterocyclic polymer precursor.
The curable resin composition of the present invention contains, as the heterocyclic-containing polymer precursor, at least one precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and contains a polyimide precursor. Is preferable.

[Polyimide precursor]
From the viewpoint of the film strength of the obtained cured film, the polyimide precursor preferably has a repeating unit represented by the following formula (1).

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

-A ¹ and A ^2-
A ¹ and A ² in the formula (1) independently represent an oxygen atom or -NH-, and an oxygen atom is preferable.

-R ^111-
R ¹¹¹ in the formula (1) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are combined, and the number of carbon atoms is exemplified. A linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or 2 of these. The group combined as described above is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.

R ¹¹¹ in formula (1) is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched-chain aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.

Specifically, the diamine is a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or these. A diamine containing two or more combined groups is preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of groups containing aromatic groups include:

In the formula, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, —O—, —C (= O) −, —S—, —S. (= O) _2- , -NHC (= O)-, or a group obtained by combining two or more of these is preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom. , -O-, -C (= O)-, -S- and S (= O) _2- , more preferably, -CH _2- , -O-, -S-,- It is more preferably a divalent group selected from the group consisting of S (= O) _2- , -C (CF ₃ ) _2- , and -C (CH ₃ ) _2- .

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane or isophoronediamine; meta or paraphenylenediamine, diaminotoluene, 4,4'-or 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-or 3,3'-diaminodiphenylmethane, 4,4'-or 3,3'-diaminodiphenylsulfone , 4,4'-or 3,3'-diaminodiphenyl sulfide, 4,4'-or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-amino) Phenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxy) Phenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4'-diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) ) Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10- Bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis ( 3-Aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-Diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9, 9-Bis (4-aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-Diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone , 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2- (3', 5'-diaminobenzoyloxy) ethyl methacrylate, 2,4- or 2,5-diaminocumen, 2,5-Dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis (3-aminopropyl) tetramethyldi Siloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, diaminobenzoic acid ester, 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] hexafluoro Propane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (tri) Fluoromethyl) 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-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethyl) Phenoxy) phenyl] hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2 , 2', 5,5', 6,6'-hexafluorotridin and at least one diamine selected from 4,4'-diaminoquaterphenyl.

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

Further, a diamine having at least two alkylene glycol units in the main chain is also mentioned as a preferable example. A diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule is preferable, and the diamine is more preferably the diamine and does not contain an aromatic ring. Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, and Jeffamine (registered trademark). ) EDR-148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2)) -Aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propane-2-amine, etc., but are limited to these. Not done.

Jeffamine® KH-511, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148, The structure of Jeffamine® EDR-176 is shown below.

In the above, x, y, and z are arithmetic mean values.

^{R 111} in the formula (1), from the viewpoint of flexibility of the cured film ^obtained, -Ar ^⁰ -L ⁰ -Ar ⁰ - is preferably represented by. Ar ⁰ is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and a phenylene group is preferable. L ⁰ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, —O—, −C (= O) −, −S−, −S (= _O) 2 -, - NHCO-, or represent these two or more combined groups. The preferred range of L ⁰ is synonymous with A above.

R ¹¹¹ in the formula (1) is preferably a divalent organic group represented by the following formula (51) or the formula (61) from the viewpoint of i-ray transmittance. In particular, a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.

In formula (51), R ⁵⁰ to R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a fluoromethyl group. It is a difluoromethyl group or a trifluoromethyl group, and * independently represents a binding site with another structure.

The monovalent organic group of R ⁵⁰ to R ⁵⁷ includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.

In formula (61), R ⁵⁸ and R ⁵⁹ are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.

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

In addition, the following diamines can also be preferably used.

-R ^115-
R ¹¹⁵ in the 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 formula (6) is more preferable.

R ¹¹² is synonymous with A and has the same preferred range. * Independently represent a binding site with another structure.

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in the formula (1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride.
Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

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

Specific examples of the tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride (4,4'-biphthal). Acid dianhydride), 3,3', 4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4, 4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3 , 3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6 7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propanedianhydride, 2,2-bis (2,3-dicarboxyphenyl) propanedianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanedianhydride, 1,3-diphenylhexafluoropropane-3,3,4 4-Tetetracarboxylic 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-phenanthrene Tetetracarboxylic 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 alkoxy derivatives having 1 to 6 carbon atoms are exemplified.

Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also mentioned as preferable examples.

-R ¹¹³ and R ^114-
R ¹¹³ and R ¹¹⁴ in the formula (1) independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group, and more preferably contains a polyalkyleneoxy group. Further, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a radically polymerizable group, and it is more preferable that both of them contain a radically polymerizable group. Examples of the radically polymerizable group include a group capable of a cross-linking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond.

Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acryloyl group, and the following formula ( Examples thereof include groups represented by III).

In formula (III), ^R200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is preferable.

In formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH _2- or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom). ~ 12 is preferable, 1 to 6 is more preferable, 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, 1 to 6 is more preferable, and 1 to 3 is particularly preferable). The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. Such as alkylene group, —CH ₂ CH (OH) CH ₂ −, and ethylene group, propylene group, trimethylene group, −CH ₂ CH (OH) CH ₂ − are more preferable.
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.
In formula (III), * represents a binding site with another structure.
As a preferred embodiment of the polyimide precursor in the present invention, an aliphatic group, an aromatic group and an aryl having one, two or three, preferably one acid group as the monovalent organic group of R ¹¹³ or R ^114. Alkyl groups and the like can be mentioned. Specific examples thereof include an aromatic group having an acid group having 6 to 20 carbon atoms and an arylalkyl group having an acid group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is preferably a hydroxy group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxy group.
As the monovalent organic group represented by R ¹¹³ or R ^114, a substituent that improves the solubility of the developing solution is preferably used.

It is more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, a benzyl group, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group or a 4-hydroxybenzyl group from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group is preferable, and an alkyl group substituted with an aromatic group is more preferable.

The alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group). The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group. , Isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable.

Specific examples of the aromatic group include a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and azulene. Rings, heptalene rings, indacene rings, perylene rings, pentacene rings, acenaphene rings, phenanthrene rings, anthracene rings, naphthacene rings, chrysen rings, triphenylene rings, etc.), or substituted or unsubstituted aromatic heterocyclic groups ( The cyclic structure constituting the group includes a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolin ring, an indol ring, and a benzofuran. Ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, aclysin ring, phenanthrene ring, thianthrene ring, chromene ring , Xanthene ring, phenoxatiin ring, phenothiazine ring or phenazine ring).

It is also preferable that the polyimide precursor has a fluorine atom in the repeating unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or more. There is no particular upper limit, but 50% by mass or less is practical.

Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized in a repeating unit represented by the formula (1). Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.

The repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-A) or the formula (1-B).

A ¹¹ and A ¹² represent an oxygen atom or -NH-, R ¹¹¹ and R ¹¹² each independently represent a divalent organic radical, and R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or 1 Representing a valent organic group, at least one of R ¹¹³ and R ¹¹⁴ is preferably a group containing a radically polymerizable group, and more preferably a radically polymerizable group.

The preferred ranges of A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are synonymous with the preferred ranges of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1), respectively.

A preferred range of R ¹¹² has the same meaning as ^{R 112} in formula (5), and more preferably among others oxygen atoms.

The bonding position of the carbonyl group to the benzene ring in the formula is preferably 4, 5, 3', 4'in the formula (1-A). In formula (1-B), it is preferably 1, 2, 4, 5.

In the polyimide precursor, the repeating unit represented by the formula (1) may be one kind, but may be two or more kinds. Further, the structural isomer of the repeating unit represented by the formula (1) may be contained. Further, the polyimide precursor may contain other types of repeating units in addition to the repeating units of the above formula (1).

As one embodiment of the polyimide precursor in the present invention, 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units are the repeating units represented by the formula (1). Is exemplified. As an upper limit, 100 mol% or less is practical.

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

The degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 to 7.0, more preferably 1.8 to 6.5.
The degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.
In the present specification, the degree of molecular weight dispersion means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).

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

In the method for producing a polyimide precursor, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.

The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.

In order to further improve the storage stability in the method for producing a polyimide precursor or the like, the end of the polyimide precursor or the like is used as an end sealant such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound or a monoactive ester compound. It is preferable to seal. It is more preferable to use monoalcohol, phenol, thiol, thiophenol, and monoamine as the terminal encapsulant.
Preferred compounds of monoalcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, flufuryl alcohol, and isopropanol. , 2-Butanol, cyclohexyl alcohol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, t-butyl alcohol, adamantan alcohol and other tertiary alcohols, and the like. Preferred compounds of phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol and the like.
Preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene. , 1-Hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy- 7-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-amino Examples include benzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Be done. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end sealants.
Further, when sealing the amino group at the end of the resin, it is possible to seal with a compound having a functional group capable of reacting with the amino group. Preferred sealing agents for amino groups include carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic acid anhydride and the like, and carboxylic acid anhydride and carboxylic acid chloride are more preferable. preferable. Preferred compounds of the carboxylic acid anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride and the like. Preferred compounds of carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantancarbonyl chloride. , Heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.

It is preferable to include a step of precipitating a solid in the production of the polyimide precursor. Specifically, the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.

[Polybenzoxazole precursor]
The polybenzoxazole precursor preferably contains a repeating unit represented by the following formula (2).

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

-R ^121-
In formula (2), R ¹²¹ represents a divalent organic group. The divalent organic group includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). Is more preferable, and a group containing at least one of 6 to 12 is particularly preferable). Examples of the aromatic group constituting R ¹²¹ include R ¹¹¹ of the above formula (1). As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably derived from 4,4'-oxydibenzoyl chloride.

-R ^122-
In formula (2), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the above formula (1), and the preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

-R ¹²³ and R ^124-
R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferable range is also the same.

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

It is preferable that the polybenzoxazole precursor further contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.

Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R ^2s. Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of R ^3s , R ^4s , R ^5s , and R ^6s is aromatic. It is a group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and the rest is a hydrogen atom or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms). It is preferably an organic group having 1 to 12 carbon atoms, particularly preferably 1 to 6) carbon atoms, and may be the same or different from each other. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z moiety, preferably, the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a + b is 100 mol%.

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. The molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be lowered, and the effect of suppressing warpage and the effect of improving solubility can be achieved at the same time.

When the polybenzoxazole precursor contains a diamine residue represented by the formula (SL) as another kind of repeating unit, the tetracarboxylic dianhydride is further provided in that it improves the alkali solubility of the curable resin composition. It is preferable that the tetracarboxylic acid residue remaining after the removal of the acid dianhydride group from the product is contained as a repeating unit. Examples of such a tetracarboxylic acid residue include the example of R ¹¹⁵ in the formula (1).

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

The degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

-Acid value-
From the viewpoint of the film strength of the obtained cured film, the acid value of the heterocyclic polymer precursor is preferably 80 mgKOH / g or less, more preferably 50 mgKOH / g or less, and 30 mgKOH / g or less. It is more preferable, and it is particularly preferable that it is 20 mgKOH / g or less. The lower limit of the acid value is preferably 5 mgKOH / g or more, more preferably 8 mgKOH / g or more, and even more preferably 10 mgKOH / g or more.
When the acid value is within the above range, it is considered that the specific compound is suppressed from being neutralized by the acid group, and the cyclization of the heterocyclic polymer precursor is likely to be promoted.
The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.

The content of the heterocycle-containing polymer precursor in the curable resin composition of the present invention is preferably 20% by mass or more, preferably 30% by mass or more, based on the total solid content of the curable resin composition. More preferably, it is more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and further preferably 70% by mass or more. The content of the heterocycle-containing polymer precursor in the curable resin composition of the present invention is preferably 99.5% by mass or less, preferably 99% by mass, based on the total solid content of the curable resin composition. The following is more preferable, 98% by mass or less is further preferable, 97% by mass or less is further preferable, and 95% by mass or less is further preferable.

The curable resin composition of the present invention may contain only one type of heterocyclic polymer precursor, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

<Specific compound>
The curable resin composition of the present invention contains a basic compound represented by the formula (1-1) or a weak acid salt (specific compound) thereof.
In the present invention, the weak acid salt is preferably a salt exhibiting basicity in the curable resin composition of the present invention. Examples of the weak acid salt include carbonates, acetates, oxalates and borates.

[PKa]
The pKa of the conjugate acid of the specific compound (when the specific compound is a weak acid salt, the pKa of the conjugate acid of the basic compound dissociated from the weak acid salt) is preferably 1 to 7, and more preferably 2 to 6. It is preferably 2 to 5, and more preferably 2 to 5.
The pKa of the conjugate acid is a dissociation reaction in which hydrogen ions are released from the acid, and its equilibrium constant Ka is represented by its negative common logarithm pKa. The smaller the pKa, the stronger the acid. Unless otherwise specified, pKa is a value calculated by ACD / ChemSketch (registered trademark). Alternatively, the values published in "Revised 5th Edition Chemistry Handbook Basics" edited by the Chemical Society of Japan may be referred to.

[R ¹ to R ³ ]
In formula (1-1), R ¹ to R ³ each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, or a substituted or unsubstituted aromatic group, and R ¹ to R ³ It may form at least two members ring structure of, when R 1 ^~ R ³ does not contain an alkoxysilyl group as a substituent, at least one of hydrogen atoms of ^{^{^{R 1 ~ R 3, R 1}}} ~ one another at least one R ³ represents a structure having a branched structure or a cyclic structure.
In the present specification, the term "alkyl group" is used to include all alkyl groups formed by linear, branched chain, cyclic or a combination thereof.

In the formula (1-1), R ¹ to R ³ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic heterocyclic group, respectively, and are substituted or not substituted. More preferably, it is a substituted alkyl group or a substituted or unsubstituted aromatic heterocyclic group.
As the aliphatic hydrocarbon group in R ¹ to R ³ , an alkyl group having 1 to 20 carbon atoms is preferable, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or an alkyl group having 3 carbon atoms. Cyclic alkyl groups of to 10 are more preferable, and linear alkyl groups having 1 to 4 carbon atoms, branched alkyl groups having 3 to 6 carbon atoms, or cyclohexyl groups are even more preferable.
Examples of the substituent of the alkyl group in R ¹ to R ³ include an aromatic hydrocarbon group (preferably a phenyl group) and an aromatic heterocyclic group (preferably a nitrogen-containing aromatic heterocyclic group such as an imidazolyl group and a pyridinyl group). , Alkoxy group, alkyloxycarbonyl group, aryloxycarbonyl group, vinyl group, allyl group, (meth) acrylamide group, polymerizable group such as methacryloxy group and the like.
As the aromatic group in R ¹ to R ^3, an aromatic heterocyclic group having 5 to 6 ring members is preferable, and an aromatic heterocyclic group having 6 ring members is more preferable. When the aromatic group is an aromatic heterocyclic group, the bond site with the nitrogen atom in the formula (1-1) is preferably a carbon atom in the aromatic heterocyclic group. Examples of the aromatic heterocyclic group include aromatic heterocyclic groups containing an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like as heteroatoms, and a nitrogen-containing aromatic heterocyclic group is preferable. A 4-pyridinyl group is more preferred.
Examples of the substituent of the aromatic group in R ¹ to R ³ include an alkyl group and a substituent in the above-mentioned alkyl group. Further, it is preferable that the substituent in the aromatic group does not contain an amino group or a substituted amino group.

In the formula (1-1), it is preferable that all of R ¹ to R ³ are not hydrogen atoms, or only one is a hydrogen atom.
When at least one of R ¹ to R ³ is a hydrogen atom, at least one of R ¹ to R ³ represents a structure having a branched structure or a cyclic structure, and the other two represent a branched structure or a cyclic structure. It is preferable to represent it.
As the structure having the branched structure, a branched alkyl group is preferable, a branched alkyl group having 3 to 10 carbon atoms is more preferable, a branched alkyl group having 3 to 6 carbon atoms is further preferable, and an isopropyl group is particularly preferable.
Examples of the structure having a cyclic structure include an alkyl group having a cyclic structure and the above-mentioned substituted or unsubstituted aromatic group, and an alkyl group having a cyclic structure having 6 to 20 carbon atoms is preferable, and the alkyl group has 6 carbon atoms. A cycloalkyl group of ~ 20 is more preferred, and a cyclohexyl group is even more preferred.

In the formula (1-1), at least two of R ¹ to R ³ may be bonded to form a ring structure, and the ring structure to be formed is either an aliphatic heterocyclic structure or an aromatic heterocyclic structure. It may be.
As the aliphatic heterocyclic structure, an aliphatic heterocyclic structure having 5 or 6 ring members is preferable, a piperidine ring structure, a piperazine ring structure, and a morpholine ring structure are more preferable, and a piperidine ring structure is further preferable.
As the aromatic heterocyclic structure, an aromatic heterocyclic structure having 5 or 6 ring members is preferable, and examples thereof include an imidazole ring structure, a pyridine ring structure, a pyrimidine ring structure, a pyrazine ring structure, and a pyridazine ring structure. The structure is more preferred.
Further, the ring structure may further have a substituent, and examples of the substituent include a group similar to the above-mentioned substituent of the aromatic group in R ¹ to R ³ .
The ring structure formed by combining at least two of R ¹ to R ³ may be further condensed with another ring structure. Examples of the other ring structure include an aliphatic hydrocarbon ring structure, an aromatic hydrocarbon ring structure, an aliphatic heterocyclic structure, and an aromatic heterocyclic structure, and the aromatic hydrocarbon ring structure or the aliphatic heterocycle structure. A ring structure is preferred. Examples of the compound represented by the formula (1-1) having such a condensed ring structure include 1,2-benzopyrazole and 1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimidine. [1,2-a] Examples thereof include pyrimidine.

[Structure of specific compound]
From the viewpoint of improving the film strength of the obtained cured film, the specific compounds include secondary aliphatic amines, tertiary aliphatic amines, secondary aromatic amines, tertiary aromatic amines, and nitrogen-containing nitrogen. It is preferably at least one basic compound selected from the group consisting of heterocyclic compounds or a weak acid salt thereof.
Among these, a secondary aliphatic amine or a secondary aromatic amine is preferable from the viewpoint of improving the film strength of the obtained cured film.
Further, from the viewpoint of improving the storage stability of the composition, a tertiary aliphatic amine, a tertiary aromatic amine or a nitrogen-containing heterocyclic compound is preferable.

In the present specification, the aliphatic amine means that at least one of the three structures bonded to the amine (that is, R ¹ to R ³ in the formula (1-1)) is an aliphatic hydrocarbon group, and The remaining two are independently hydrogen atoms or aliphatic hydrocarbon groups.
The secondary aliphatic amine means that one of the three structures bonded to the amine is a hydrogen atom and the remaining two are aliphatic hydrocarbon groups. When the specific compound is a secondary aliphatic amine, at least one of the aliphatic hydrocarbon groups has a branched structure or a cyclic structure, and all of the aliphatic hydrocarbon groups have a branched structure or a cyclic structure. It preferably has a structure.
The tertiary aliphatic amine means that all three structures bonded to the amine are aliphatic hydrocarbon groups.
The aliphatic amines, secondary aliphatic amines, or a preferred embodiment of the aliphatic hydrocarbon group in the description of the tertiary aliphatic amine is a preferred embodiment of the aliphatic hydrocarbon group for R ^{1 ~} R ³ above The same is true. The above-mentioned aliphatic hydrocarbon group may further have the above-mentioned substituent.
Further, at least two of the secondary aliphatic amine or the aliphatic hydrocarbon group in the tertiary aliphatic amine may be bonded to form a ring structure. Examples of the ring structure formed include an aliphatic heterocyclic structure.
In the present specification, the aromatic amine means that at least one of the three structures bonded to the amine (that is, R ¹ to R ³ in the formula (1-1)) is an aromatic group, and the rest. The two are independently hydrogen atoms, aliphatic hydrocarbon groups or aromatic groups.
A secondary aromatic amine is one in which only one of the three structures attached to the amine is a hydrogen atom, the other is an aromatic group, and the remaining one is an aliphatic hydrocarbon group or aromatic. It is a family group.
The tertiary aromatic amine means that one of the three structures bonded to the amine is an aromatic group and the other two are an aliphatic hydrocarbon group or an aromatic group.
When the tertiary aliphatic amine has two aliphatic hydrocarbon groups, they may be combined to form a ring structure. Examples of the ring structure formed include an aliphatic heterocyclic structure.
The aromatic amine, secondary aromatic amines, or a preferred embodiment of the aliphatic hydrocarbon group or an aromatic group in the description of the tertiary aromatic amines, aliphatic hydrocarbon group for R ^{1 ~} R ³ above Alternatively, it is the same as the preferred embodiment of the aromatic group. Each of the above-mentioned aliphatic hydrocarbon group or aromatic group may further have the above-mentioned substituent.

-Secondary aliphatic amine-
As the secondary aliphatic amine, dialkylamine is preferable.
As used herein, the dialkylamine refers to an amine compound in which one hydrogen atom and two alkyl groups are bonded to a nitrogen atom. The two alkyl groups in the dialkylamine may combine to form an aliphatic heterocyclic structure.
Of the two alkyl groups in the dialkylamine, at least one is preferably a branched alkyl group or an alkyl group having a cyclic structure, and both are branched alkyl groups or both are alkyl groups having a cyclic structure. More preferably.
The preferred embodiment of the branched alkyl group is the same as the preferred embodiment of the branched alkyl group in the structure having the branched structure described above.
The preferred embodiment of the alkyl group having a cyclic structure is the same as the preferred embodiment of the alkyl group having a cyclic structure in the structure having the cyclic structure described above.

-Third-class aliphatic amine-
As the tertiary aliphatic amine, a trialkylamine or an N-alkyl nitrogen-containing aliphatic heterocyclic compound is preferable.
As used herein, the trialkylamine refers to an amine compound in which three alkyl groups are bonded to a nitrogen atom. At least two alkyl groups in the trialkylamine may combine to form an aliphatic heterocyclic structure.
The three alkyl groups in the trialkylamine may be any of a linear alkyl group, a branched alkyl group and an alkyl group having a cyclic structure, but all of them are preferably linear alkyl groups.
As the linear alkyl group, a linear alkyl group having 1 to 20 carbon atoms is preferable, a linear alkyl group having 1 to 10 carbon atoms is more preferable, and a linear alkyl group having 1 to 4 carbon atoms is further preferable.
The preferred embodiment of the branched alkyl group or the alkyl group having the cyclic structure is the same as the preferred embodiment of the branched alkyl group or the alkyl group having the cyclic structure in the dialkylamine described above.
In the present specification, the N-alkyl nitrogen-containing aliphatic heterocyclic compound means that a hydrogen atom bonded to a nitrogen atom in a nitrogen-containing heterocyclic structure such as a piperidine ring structure, a piperazine ring structure, or a morpholine ring is substituted with an alkyl group. Refers to a compound. One of the nitrogen atoms contained in these nitrogen-containing heterocyclic structures is the nitrogen atom described in the above formula (1-1).
As the alkyl group, a group similar to the linear alkyl group, the branched alkyl group or the alkyl group having a cyclic structure in the above-mentioned trialkylamine is preferable, and among these, the branched alkyl group is more preferable.
Further, as the nitrogen-containing heterocyclic structure, a nitrogen-containing heterocyclic structure having 5 to 10 ring members is preferable, and a nitrogen-containing heterocyclic structure having 6 ring members is more preferable.
The nitrogen-containing heterocyclic structure is preferably a nitrogen-containing saturated heterocyclic structure.
The number of nitrogen atoms in the nitrogen-containing heterocyclic structure is preferably 1 or 2, and more preferably 1.
The nitrogen-containing heterocyclic structure may contain a complex atom other than the nitrogen atom, but preferably does not contain a complex atom other than the nitrogen atom.
As the nitrogen-containing heterocyclic structure, a pyridine ring or a morpholine ring structure is preferable.

-Secondary aromatic amine-
Examples of the secondary aromatic amine include diarylamine and alkylarylamine.
As used herein, diallylamine refers to an amine compound in which one hydrogen atom and two aromatic groups are bonded to a nitrogen atom.
As used herein, the alkylarylamine refers to an amine compound in which one hydrogen atom, one alkyl group and one aromatic group are bonded to a nitrogen atom.
As the aromatic group in the diarylamine or the alkylarylamine, a group similar to the aromatic group in R ¹ to R ³ contained in the above formula (1-1) is preferable.
As the alkyl group in the above-mentioned alkylarylamine, a group similar to the above-mentioned alkyl group in the trialkylamine is preferable.

-Secondary aromatic amine-
Examples of the tertiary aromatic amine include dialkyl monoarylamine, monoalkyldiarylamine, and triarylamine. Among these, dialkyl monoarylamine is preferable from the viewpoint of the film strength of the obtained cured film.
As used herein, the dialkyl monoarylamine refers to an amine compound in which two alkyl groups and one aromatic group are bonded to a nitrogen atom. The two alkyl groups in the dialkyl monoarylamine may be combined to form an aliphatic heterocyclic structure.
As used herein, the monoalkyldiarylamine refers to an amine compound in which one alkyl group and two aromatic groups are bonded to a nitrogen atom.
As used herein, the triarylamine refers to an amine compound in which three aromatic groups are bonded to a nitrogen atom.
As the aromatic group in the dialkyl monoarylamine, the monoalkyldiarylamine, or the triarylamine, the same group as the aromatic group in R ¹ to R ³ contained in the above formula (1-1) is preferable. ..
As the alkyl group in the dialkyl monoarylamine or the monoalkyldiarylamine, the same group as the alkyl group in the trialkylamine is preferable.

-Nitrogen-containing heterocyclic compound-
The nitrogen-containing heterocyclic compound may be a nitrogen-containing aromatic heterocyclic compound or a nitrogen-containing aliphatic heterocyclic compound, but a nitrogen-containing aromatic heterocyclic compound is preferable.

<< Nitrogen-containing aromatic heterocyclic compound >>
The number of ring members in the nitrogen-containing aromatic heterocyclic compound (in the case of a ring structure condensed with another ring structure as described later, the number of ring members of a single ring containing a nitrogen atom as a ring member) shall be 5 to 10. Is preferable, 5 or 6 is more preferable, and 5 is even more preferable.
The number of nitrogen atoms contained in the nitrogen-containing aromatic heterocyclic compound is preferably 1 to 3, preferably 2 or 3, and more preferably 2.
The nitrogen-containing aromatic heterocyclic compound may have a structure in which a nitrogen-containing aromatic heterocyclic structure is condensed with another ring structure. As the other ring structure, an aromatic ring is preferable, an aromatic hydrocarbon ring is more preferable, and a benzene ring is further preferable.
Examples of the nitrogen-containing heteroaromatic ring compound include a substituted or unsubstituted imidazole compound, a substituted or unsubstituted pyrazole compound, and a substituted or unsubstituted benzopyrazole compound.
Examples of the substituent in the imidazole compound, the pyrazole compound, or the benzopyrazole compound include the same groups as the substituents in R ¹ to R ³ in the above formula (1-1).

<< Nitrogen-containing aliphatic heterocyclic compound >>
The number of ring members in the nitrogen-containing aliphatic heterocyclic compound (in the case of a ring structure condensed with another ring structure as described later, the number of ring members of a single ring containing a nitrogen atom as a ring member) shall be 5 to 10. Is preferable, 5 or 6 is more preferable, and 5 is even more preferable.
The number of nitrogen atoms contained in the nitrogen-containing aliphatic heterocyclic compound is preferably 1 to 3, preferably 2 or 3, and more preferably 2.
The nitrogen-containing aliphatic heterocyclic compound may have a structure in which a nitrogen-containing aliphatic heterocyclic structure is condensed with another ring structure. As the other ring structure, an aliphatic ring structure is preferable, and an aliphatic hydrocarbon ring structure may be used, but an aliphatic heterocyclic structure containing a nitrogen atom as a hetero atom is preferable. Further, the aliphatic ring structure may be a saturated aliphatic ring structure or an unsaturated aliphatic ring structure.
Examples of the nitrogen-containing aliphatic aromatic ring compound include 1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimidin [1,2-a] pyrimidine.

The specific compound is also preferably a monoamine compound or a weak acid salt thereof.
As used herein, the monoamine compound refers to a compound having only one substituted or unsubstituted amino group in its structure.
Among these, the specific compound is at least one compound selected from the group consisting of a secondary aliphatic amine, a tertiary aliphatic amine, a secondary aromatic amine, and a tertiary aromatic amine. Alternatively, it is preferably a weak acid salt thereof and a monoamine compound or a weak acid salt thereof.

[Molecular weight]
From the viewpoint of the film strength of the cured film and the insulating property of the obtained cured film, the molecular weight of the specific compound is preferably 60 to 200.
It is considered that when the molecular weight is 200 or less, for example, the specific compound is easily moved during heating, and the effect of promoting the cyclization of the heterocyclic polymer precursor is easily obtained.
Further, when the molecular weight is 200 or less, for example, the specific compound is likely to volatilize during heating, and the amount of the specific compound remaining in the obtained cured film is reduced, so that the film strength of the cured film is likely to be improved. Conceivable.
The lower limit of the molecular weight is preferably 80 or more. The upper limit of the molecular weight is preferably 190 or less, more preferably 180 or less.

〔Concrete example〕
Specific examples of the specific compound include N, N-dimethylcyclohexylamine, triethylamine, 2- (dimethylamino) ethyl methacrylate, dicyclohexylamine, 4-dimethylaminopyridine, diisopropylamine, 1,3,4,6,7, 8-Hexahydro-1-methyl-2H-pyrimid [1,2-a] pyrimidin, imidazole, 1,2-benzopyrazole, methyl 5-methylpyrazole-3-carboxylate, N, N-dimethylaminopyridine, dibenzyl Examples include, but are not limited to, amines, Nt-butylbenzylamine, N-isopropylaniline, 4-morpholinopyridine and the like.

〔Content〕
The content of the specific compound is 0.05 to 20% by mass with respect to the total solid content of the curable resin composition from the viewpoint of improving the storage stability of the composition and the elongation at break of the obtained cured film. Is preferable. The lower limit is more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more. The upper limit is more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 1% by mass or less from the viewpoint of corrosion resistance of a metal (for example, copper used for wiring or the like).
The content of the specific compound with respect to 100 parts by mass of the heterocyclic polymer precursor is 0.5 parts by mass or more from the viewpoint of improving the storage stability of the composition and the elongation at break of the obtained cured film. It is preferably 1 part by mass or more, and further preferably 2 parts by mass or more. From the viewpoint of corrosion resistance of metal (for example, copper used for wiring and the like), the upper limit is preferably, for example, 20 parts by mass or less, more preferably 15 parts by mass or less, and 10 parts by mass. The following is more preferable.
As the specific compound, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.

<Polymerization initiator>
The curable resin composition of the present invention contains a polymerization initiator.
The polymerization initiator may be either a photopolymerization initiator or a thermal polymerization initiator, but preferably contains a photopolymerization initiator.

[Photopolymerization initiator]
The curable resin composition of the present invention preferably contains a photopolymerization initiator.
The photopolymerization initiator may be a photocationic polymerization initiator, but is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.

The photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L · mol ^-1 · cm ^-1 within the range of about 300 to 800 nm (preferably 330 to 500 nm). Is preferable. 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 ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photoradical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, 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 and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description of paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP2015-087611A is exemplified, and the content thereof is incorporated in the present specification. As a commercially available product, KayaCure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.

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

As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF), Omnirad 907, Omnirad 369, and Omnirad 379 (all manufactured by IGM Resin). ) Can be used.

As the aminoacetophenone-based initiator, the compound described in JP-A-2009-191179, in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819, IRGACURE-TPO (trade name: all manufactured by BASF), Omnirad 819 and Omnirad TPO (all manufactured by IGM Resins) can be used.

Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

An oxime compound is more preferable as the photoradical polymerization initiator. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

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

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. In the curable resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group represented by> C = NOC (= O)-in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052). A radical polymerization initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831 and ADEKA ARCULDS NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Corp.) can be used.

An oxime compound having the following structure can also be used.

It is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.

Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator includes a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, and a triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.

More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.

The photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). -2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 and other aromatic ketones, alkylanthraquinone, etc. It is also possible to use quinones fused to the aromatic ring of the above, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. Further, a compound represented by the following formula (I) can also be used.

In formula (I), ^RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like. Alternatively, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, or a carbon number interrupted by one or more oxygen atoms. It is a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 2 to 18 and an alkyl group having 1 to 4 carbon atoms, and ^RI01 is a group represented by the formula (II). It is the same group as R ^I00, and R ^I02 to R ^I04 are independently alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogen atoms.

In the formula, R ^I05 to R ^I07 are the same as R I ⁰² to R I ⁰⁴ of the above formula (I).

Further, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/1254669 can also be used.

When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass.
Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total is preferably in the above range.

[Thermal polymerization initiator]
The curable resin composition of the present invention may contain a thermal polymerization initiator as the polymerization initiator, and may particularly contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the heterocyclic polymer precursor can be allowed to proceed as well as the cyclization of the heterocyclic polymer precursor, so that higher heat resistance can be achieved.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When the thermal radical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. %, More preferably 5 to 15% by mass. Only one type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal radical polymerization initiators are contained, the total is preferably in the above range.

<Solvent>
The curable resin composition of the present invention contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, and alcohols.

The curable resin composition of the present invention preferably has a water content of 5% by mass or less based on the total mass of the solvent from the viewpoints of suppressing coating defects during coating and improving storage stability. ..
The content of the water is preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.1% by mass or less.
Moreover, the content of the said water may be 0 mass%.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Suitable examples include ethyl acid acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, ethyl hexanoate, ethyl heptate, dimethyl malonate, diethyl malonate and the like. ..

Examples of ethers include 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, and propylene glycol. Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.

As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.

As the cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.

As sulfoxides, for example, dimethyl sulfoxide is preferable.

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylisobutyramide, 3-methoxy-N, N- Dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide and the like are preferable.

Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

The solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.

In the present invention, 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- Consists of one solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more. The mixed solvent to be mixed is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. More preferably, the amount is more preferably 10 to 70% by mass, further preferably 20 to 70% by mass, and even more preferably 40 to 70% by mass. .. The solvent content may be adjusted according to the desired thickness and coating method.

The solvent may contain only one type or two or more types. When two or more kinds of solvents are contained, the total is preferably in the above range.

<Onium salt>
The curable resin composition of the present invention may further contain an onium salt.
The type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned.
Among these, an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.

The onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may or may not be bonded via a covalent bond. ..
That is, the onium salt may be an intermolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are different molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
As the cation in the onium salt, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.

The onium salt used in the present invention may be a thermobase generator described later.
The thermal base generator refers to a compound that generates a base by heating, and examples thereof include a compound that generates a base when heated to 40 ° C. or higher.

[Ammonium salt]
In the present invention, the ammonium salt means a salt of an ammonium cation and an anion.

-Ammonium cation-
As the ammonium cation, a quaternary ammonium cation is preferable.
Further, as the ammonium cation, a cation represented by the following formula (101) is preferable.

In formula (101), R ¹ to R ⁴ each independently represent a hydrogen atom or a hydrocarbon group, and at least two of R ¹ to R ⁴ may be bonded to each other to form a ring.

In the formula (101), R ¹ to R ⁴ are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms or 6 to 6 carbon atoms. It is more preferably 12 aryl groups. R ¹ to R ⁴ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group.
When at least two of R ¹ to R ⁴ are bonded to each other to form a ring, the ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom.

The ammonium cation is preferably represented by any of the following formulas (Y1-1) and (Y1-2).

In the formula (Y1-1) and ^{(Y1-2), R 101} represents an n-valent organic group, ^{R 1} has the same meaning as ^{R 1} in the formula ^{(101), Ar 101} and ^{Ar 102} are each independently , Represents an aryl group, and n represents an integer of 1 or more.
In the formula (Y1-1), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
In the formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In the formula (Y1-2), Ar ¹⁰¹ and Ar ¹⁰² are preferably phenyl groups or naphthyl groups, respectively, and more preferably phenyl groups.

-Anion-
As the anion in the ammonium salt, one selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfate anion is preferable, and a carboxylic acid anion is more preferable because both salt stability and thermal decomposability can be achieved. 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 a divalent or higher carboxylic acid anion having two or more carboxy groups, and more preferably a divalent carboxylic acid anion. According to this aspect, the stability, curability and developability of the curable resin composition can be further improved. In particular, by using a divalent carboxylic acid anion, the stability, curability and developability of the curable resin composition can be further improved.

The carboxylic acid anion is preferably represented by the following formula (X1).

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

In the present embodiment, the electron-attracting group means that the substituent constant σm of Hammett shows a positive value. Here, σm is a review article by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642. The electron-attracting group in the present embodiment is not limited to the substituent described in the above document.
Examples of substituents in which σm shows a positive value are CF ₃ groups (σm = 0.43), CF ₃ C (= O) groups (σm = 0.63), and HC≡C groups (σm = 0. 21), CH ₂ = CH group (σm = 0.06), Ac group (σm = 0.38), MeOC (= O) group (σm = 0.37), MeC (= O) CH = CH group ( σm = 0.21), PhC (= O) group (σm = 0.34), H ₂ NC (= O) CH ₂ group (σm = 0.06) and the like. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same applies).

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

In the formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxy group, and Ar is an aromatic group. Represents.

In the present invention, the carboxylic acid anion is preferably represented by the following formula (XA).

In the formula ^{(XA), L 10} represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR ^X - represents and divalent connecting group selected from the group consisting a combination thereof, ^{R X} is , Hydrogen atom, alkyl group, alkenyl group or aryl group.

Specific examples of the carboxylic acid anion include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion.

The onium salt in the present invention contains an ammonium cation as a cation from the viewpoint that the cyclization of the heterocyclic polymer-containing precursor is easily carried out at a low temperature and the storage stability of the curable resin composition is easily improved. As the anion, the salt preferably contains an anion having a pKa (pKaH) of 2.5 or less, and more preferably 1.8 or less.
The lower limit of pKa is not particularly limited, but it is preferably -3 or more, preferably -2 or more, from the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of the heterocyclic polymer-containing precursor or the like is improved. The above is more preferable.
The above pKa includes Determination of Organic Strategies by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, F.C.; See Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 19). Can be done. For compounds not described in these documents, the values calculated from the structural formulas using software of ACD / pKa (manufactured by ACD / Labs) shall be used.

Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto.

[Iminium salt]
In the present invention, the iminium salt means a salt of an iminium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Iminium cation-
As the iminium cation, a pyridinium cation is preferable.
Further, as the iminium cation, a cation represented by the following formula (102) is also preferable.

In formula (102), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, R ⁷ represents a hydrocarbon group, and at least two of R ⁵ to R ⁷ are bonded to each other to form a ring. It may be formed.
In the formula (102), R ⁵ and R ⁶ have the same meaning as R ¹ to R ⁴ in the above formula (101), and the preferred embodiment is also the same.
In formula (102), R ⁷ preferably combines with at least one of R ⁵ and R ⁶ to form a ring. The ring may contain a heteroatom. Examples of the hetero atom include a nitrogen atom. Further, as the ring, a pyridine ring is preferable.

The iminium cation is preferably represented by any of the following formulas (Y1-3) to (Y1-5).

In Formula ^{(Y1-3) ~ (Y1-5),} R 101 represents an n-valent organic group, ^{R 5} has the same meaning as ^{R 5} in the formula (102), ^{R 7} is R in the formula (102) Synonymous with ⁷ , n and m represent integers of 1 or more.
In the formula (Y1-3), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
In the formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In the formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.

Specific examples of the iminium salt include the following compounds, but the present invention is not limited thereto.

[Sulfonium salt]
In the present invention, the sulfonium salt means a salt of a sulfonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Sulfonium cation-
As the sulfonium cation, a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable.
Further, as the sulfonium cation, a cation represented by the following formula (103) is preferable.

In formula (103), R ⁸ to R ¹⁰ each independently represent a hydrocarbon group.
Each of R ⁸ to R ¹⁰ is preferably an alkyl group or an aryl group independently, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
R ⁸ to R ¹⁰ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have 10 alkoxy groups.
R ⁸ to R ¹⁰ may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.

Specific examples of the sulfonium salt include the following compounds, but the present invention is not limited thereto.

[Iodonium salt]
In the present invention, the iodonium salt means a salt of an iodonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Iodonium cation-
As the iodonium cation, a diallyl iodonium cation is preferable.
Further, as the iodonium cation, a cation represented by the following formula (104) is preferable.

In formula (104), R ¹¹ and R ¹² each independently represent a hydrocarbon group.
R ¹¹ and R ¹² are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
R ¹¹ and R ¹² may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have an alkoxy group of.
R ¹¹ and R ¹² may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.

Specific examples of the iodonium salt include the following compounds, but the present invention is not limited thereto.

[Phoenium salt]
In the present invention, the phosphonium salt means a salt of a phosphonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Phosnium cation-
As the phosphonium cation, a quaternary phosphonium cation is preferable, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation.
Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.

In formula (105), R ¹³ to R ¹⁶ independently represent a hydrogen atom or a hydrocarbon group.
Each of R ¹³ to R ¹⁶ is preferably an alkyl group or an aryl group independently, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
R ¹³ to R ¹⁶ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have an alkoxy group of.
R ¹³ to R ¹⁶ may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.

Specific examples of the phosphonium salt include the following compounds, but the present invention is not limited thereto.

When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, further 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, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
As the onium salt, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.

<Thermal base generator>
The curable resin composition of the present invention may further contain a thermosetting agent.
The other thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
Examples of the thermobase generator other than the above-mentioned onium salt include nonionic thermobase generators.
Examples of the nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).

In formulas (B1) and (B2), Rb ¹ , Rb ² and Rb ³ are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. Further, none of Rb ¹ , Rb ² and Rb ³ has a carboxy group. In the present specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.

In formulas (B1) and (B2), it is preferable that at least one of Rb ¹ , Rb ² and Rb ³ contains a cyclic structure, and it is more preferable that at least two contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable. The single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring. As the monocycle, a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ~ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have substituents as long as the effects of the present invention are exhibited. Rb ¹ and Rb ² may be coupled to each other to form a ring. As the ring to be formed, a 4- to 7-membered nitrogen-containing heterocycle is preferable. Rb ¹ and Rb ² are particularly linear, branched, or cyclic alkyl groups that may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent. A cyclohexyl group which may be used is more preferable.

As Rb ³ , an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6). ~ 10 is more preferable), alkoxy group (2 to 24 carbon atoms are preferable, 2 to 12 is more preferable, 2 to 6 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable). Preferably, 7 to 12 is more preferable), an arylalkenyl group (8 to 24 carbon atoms is preferable, 8 to 20 is more preferable, 8 to 16 is more preferable), and an alkoxyl group (1 to 24 carbon atoms is preferable, 2 to 2 to 24). 18 is more preferable, 3 to 12 is more preferable), an aryloxy group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), or an arylalkyloxy group (7 to 12 carbon atoms is more preferable). 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is further preferable). Among them, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable. Rb ³ may further have a substituent as long as the effect of the present invention is exhibited.

The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in the formula (B1), respectively.
Rb ¹³ has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effects of the present invention are exhibited. Of these, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms). , 2 to 8 are more preferable, 2 to 3 are more preferable), aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable), arylalkyl groups (7 to 7 to carbon atoms are more preferable). 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is further preferable), and a hydrogen atom is preferable.

Rb ³⁵ has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 12 carbon atoms, 3 to 12 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable). , 7-12 is more preferable), and an aryl group is preferable.

As the compound represented by the formula (B1-1), the compound represented by the formula (B1-1a) is also preferable.

Rb ¹¹ and ^{Rb 12} have the same meanings as ^{Rb 11} and ^{Rb 12} in the formula (B1-1).
Rb ¹⁵ and Rb ¹⁶ are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), aryl group (6 to 22 carbon atoms are preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7). ~ 19 is more preferable, and 7 to 11 is more preferable), and a hydrogen atom or a methyl group is preferable.
Rb ¹⁷ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 12 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.

The molecular weight of the nonionic thermobase generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Among the above-mentioned onium salts, specific examples of compounds that are thermal base generators or specific examples of thermal base generators other than the above-mentioned onium salts include the following compounds.

The content of the other thermosetting agent is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less. As the thermobase generator, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.

<Polymerizable compound>
[Radical polymerizable compound]
The curable resin composition of the present invention preferably further contains a polymerizable compound.
As the polymerizable compound, a radically polymerizable compound can be used. The radically polymerizable compound is a compound having a radically polymerizable group. Examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group. The radically polymerizable group is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.

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

The molecular weight of the radically polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.

From the viewpoint of developability, the curable resin composition of the present invention preferably contains at least one bifunctional or higher functional radical polymerizable compound containing two or more radical polymerizable groups, and is preferably a trifunctional or higher functional radical polymerizable compound. It is more preferable to contain at least one kind. Further, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound. For example, the number of functional groups of a bifunctional or higher-functional polymerizable monomer means that the number of radically polymerizable groups in one molecule is two or more.

Specific examples of the radically polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and preferred examples thereof. Esters of unsaturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyhydric amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amines or thiols, and a halogeno group. Substitution reactions of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.

Further, as the radically polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (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, trimethylpropantri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993. Urethane (meth) acrylates, such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.

Further, as a preferable radically polymerizable compound other than the above, it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. It is also possible to use a compound having two or more groups having the above, or a cardo resin.

Further, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Square Root 01-040337, and Japanese Square Root 01-040336, and JP-A-02-025493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, Japan Adhesion Association magazine vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents thereof are described in the present specification. Incorporated into the book.

Further, the compound described in Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is also (meth) acrylated. It can be used as a radically polymerizable compound.

Further, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as radically polymerizable compounds, and their contents are incorporated in the present specification.

Examples of the radically polymerizable compound include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku). Made by A-TMMT Co., Ltd .: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa ( Meta) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups contain ethylene glycol residues or propylene glycol residues. A structure that is bonded via a structure is preferable. These oligomer types can also be used.

Commercially available products of the radically polymerizable compound include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209, which is a bifunctional methacrylate having four ethyleneoxy chains. , 231, 239, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- 10, UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H ( Nippon Kayaku Co., Ltd., UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.

Examples of the radically polymerizable compound include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765. , Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Further, as the radically polymerizable compound, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. It can also be used.

The radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxy group or a phosphoric acid group. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A radically polymerizable compound having a group is more preferable. Particularly preferably, in a radical polymerizable compound in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipenta. It is a compound that is erythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toa Synthetic Co., Ltd.

The preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radically polymerizable compound is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good. The acid value is measured according to the description of JIS K 0070: 1992.

For the curable resin composition of the present invention, it is preferable to use bifunctional metaacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
Specific examples of the compound include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and PEG200 diacrylate (polyethylene glycol diacrylate having a formula of polyethylene glycol chain). (About 200), PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1, 5-Pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol dimethacrylate, dimethylol-tricyclodecanediacrylate, dimethylol-tricyclodecanedimethacrylate, EO (ethylene oxide) adduct of bisphenol A Diacrylate, EO adduct dimetallilate of bisphenol A, PO adduct diacrylate of bisphenol A, EO adduct dimetallilate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified diacrylate Meacrylate, other bifunctional acrylate having a urethane bond, and bifunctional methacrylate having a urethane bond can be used. If necessary, two or more of these can be mixed and used.
Other examples of the bifunctional or higher functional radical cross-linking agent include diallyl phthalate and triallyl trimellitate.
From the viewpoint of suppressing warpage associated with controlling the elastic modulus of the cured film, a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound. Examples of the monofunctional radically polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). (Meta) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and the like (meth) ) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether are preferably used. As the monofunctional radical polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

[Polymerizable compounds other than the radically polymerizable compounds described above]
The curable resin composition of the present invention can further contain a polymerizable compound other than the radically polymerizable compound described above. Examples of the polymerizable compound other than the above-mentioned radically polymerizable compound include a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.

-Compounds 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), (AM4) or (AM5) is preferable.

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

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

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

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry 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 (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKARAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc. Be done.

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

-Epoxy compounds (compounds with epoxy groups)-
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the curable resin composition.

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

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidi). Examples thereof include, but are not limited to, epoxy group-containing silicones such as loxypropyl) siloxane. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron® EXA-4816, Epicron® EXA-4822, Epicron® EXA-830LVP, Epicron® EXA-8183, Epicron (Registered Trademark) EXA-8169, Epicron (Registered Trademark) N-660, Epicron (Registered Trademark) N-665-EXP-S, Epicron (Registered Trademark) N-740, Rica Resin (Registered Trademark) BEO-20E (the above products) Name, manufactured by DIC Co., Ltd., Rikaresin (registered trademark) BEO-60E, Rikaresin (registered trademark) HBE-100, Rikaresin (registered trademark) DME-100, Rikaresin (registered trademark) L-200 (trade name, New Japan) Rika Co., Ltd., EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade name, manufactured by ADEKA Co., Ltd.), seroxide (registered trademark) 2021P, seroxide (registered trademark) 2081, seroxide (registered Trademarks) 2000, EHPE3150, Epolide (registered trademark) GT401, Epolide (registered trademark) PB4700, Epolide (registered trademark) PB3600 (trade name, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC- 3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN- 502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned. .. Among these, an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance. For example, Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain polyethylene oxide groups.

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

-Benzodizepine compound (compound having a benzoxazolyl group)-
Since the benzoxazine compound is a cross-linking reaction derived from the ring-opening addition reaction, degassing does not occur during curing, and the heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.

Preferred examples of the benzoxazine compound include BA type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, FA type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), poly. Examples thereof include a benzoxazine adduct of a hydroxystyrene resin and a phenol novolac type dihydrobenzoxazine compound. These may be used alone or in combination of two or more.

When a polymerizable compound is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

One type of polymerizable compound may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.

<Migration inhibitor>
The curable resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the curable resin composition layer.

The migration inhibitor is not particularly limited, but is a heterocycle (pyrazole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc. Pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and sulfanyl group compounds, hindered phenolic compounds , Pyrazole acid derivative compound, hydrazide derivative compound and the like. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Alternatively, an ion trap agent that traps anions such as halogen ions can also be used.

Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.

Specific examples of the migration inhibitor include the following compounds.

When the curable resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the curable resin composition, and is 0. It is more preferably 0.05 to 2.0% by mass, and further preferably 0.1 to 1.0% by mass.

The migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.

<Polymerization inhibitor>
The curable resin composition of the present invention preferably contains a polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'. -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine 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) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-tert-butyl) phenylmethane, o-methoxyphenol, N-nitrosophenylhydroxyamine first cerium salt, 1,3,5-tris (4-t-butyl-3-hydroxy) -2,6-Dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1- Oxyl-free radical, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxyl An amine ammonium salt or the like is preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

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

When the curable resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is, for example, 0.01 to 20.0% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferable that it is 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and further preferably 0.05 to 2.5% by mass. Further, when the storage stability of the curable resin composition solution is required, the embodiment of 0.02 to 15.0% by mass is preferably raised, and more preferably 0.05 to 10.0% by mass in that case. Is.

The polymerization inhibitor may be only one type or two or more types. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.

<Metal adhesion improver>
The curable resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesion improver include silane coupling agents, aluminum-based adhesive aids, titanium-based adhesive aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds. And so on.

Examples of the silane coupling agent include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992. Compounds described in 0063 to 0071, compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594. Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glyceride. Sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltri Methoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N- 2- (Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine , N-phenyl-3-aminopropyltrimethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Examples thereof include isocyanatepropyltriethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

Further, as the metal adhesiveness improving agent, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..

[Aluminum-based adhesive aid]
Examples of the aluminum-based adhesive aid include aluminum tris (ethylacetacetate), aluminumtris (acetylacetoneate), ethylacetacetate aluminum diisopropirate, and the like.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further, with respect to 100 parts by mass of the heterocyclic polymer precursor. It is preferably in the range of 0.5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are good. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.

<Other additives>
The curable resin composition of the present invention can be used with various additives such as a thermoacid generator, a sensitizer such as N-phenyldiethanolamine, and a chain transfer agent, if necessary, as long as the effects of the present invention can be obtained. , Surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, antiaggregating agents and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.

[Sensitizer]
The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electron-excited state. The sensitizer in the electron-excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine. In addition, benzophenone type, Michler's ketone type, coumarin type, pyrazole azo type, anilino azo type, triphenylmethane type, anthracene type, anthracene type, anthrapyridone type, benzylidene type, oxonor type, pyrazole triazole azo type, pyridone azo type Compounds such as cyanine-based, phenothiazine-based, pyrrolopyrazoleazomethine-based, xanthene-based, phthalocyanine-based, penzopyran-based, and indigo-based compounds can be used.
For example, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, 2,6-bis (4'-diethylaminobenzal) cyclohexanone, 2,6- Bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminosinnamiridene indanone, p- Dimethylaminobenzylene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylbinylene) isonaftthiazole, 1,3 -Bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethyl Aminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7- (diethylamino) ) Cumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-Dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3', 4'-dimethylacetanilide, etc. Can be mentioned.
Moreover, you may use a sensitizing dye as a sensitizer.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.

When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer may be 0.01 to 20% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass. The sensitizer may be used alone or in combination of two or more.

[Chain transfer agent]
The curable resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. Examples of the chain transfer agent include RAFT (Reversible Addition Fragmentation chain Transfer), a group of compounds having -S-S-, -SO ₂ -S-, -N-O-, SH, PH, SiH, and GeH in the molecule. ) Dithiobenzoate, trithiocarbonate, dithiocarbamate, xantate compound and the like having a thiocarbonylthio group used for polymerization are used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, a thiol compound can be preferably used.

Further, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used.

When the curable resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition of the present invention. Preferably, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable. The chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.

[Surfactant]
Each type of surfactant may be added to the curable 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-based surfactants can be used. The following surfactants are also preferable. In the following formula, the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.

Further, as the surfactant, the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.

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

[Higher fatty acid derivative]
The curable resin composition of the present invention has a curable resin composition in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of an object.

Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used.

When the curable resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is 0.1 to 10% by mass based on the total solid content of the curable resin composition of the present invention. Is preferable. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.

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

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

Further, as a method for reducing metal impurities unintentionally contained in the curable resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the curable resin composition of the present invention. Methods such as filtering the raw materials constituting the curable resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.

Considering the use as a semiconductor material, the curable resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.

A conventionally known storage container can be used as the storage container for the curable resin composition of the present invention. Further, as the storage container, for the purpose of suppressing contamination of impurities in the raw material and the curable resin composition, a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a bottle having a layered structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

<Use of curable resin composition>
The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.
In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.

(Manufacturing method of curable resin composition)
The method for producing the curable resin composition of the present invention is preferably a production method including a step of mixing the above-mentioned components contained in the curable resin composition. The mixing method is not particularly limited, and a conventionally known method can be used.
Further, in the method for producing a curable resin composition of the present invention, a composition containing a heterocyclic-containing polymer precursor, the above-mentioned polymerization initiator, and the above-mentioned solvent (hereinafter, also referred to as a precursor composition) and a specific compound are used. It is also preferable that the production method includes a step of mixing. The mixing method is not particularly limited, and a conventionally known method can be used.
If necessary, the precursor composition may further contain each component contained in the curable resin composition of the present invention, such as the above-mentioned radical polymerizable compound, onium salt, and thermosetting agent.
As the precursor composition, a composition obtained by removing a specific compound from the curable resin composition of the present invention is preferable.
In the production method using the precursor composition, the precursor composition may be obtained by means such as purchase, or the above production method mixes each component contained in the precursor composition to form a precursor. It may further include the step of preparing the body composition. The mixing method is not particularly limited, and a conventionally known method can be used.
In the production method using the precursor composition, the specific compound can be added, for example, immediately before forming a film with the curable resin composition.

Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the curable resin composition. The filter pore diameter may be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressure to be pressurized is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , 0.05 MPa or more and 0.3 MPa or less is more preferable.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. 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, laminate, semiconductor device, and manufacturing method thereof)
Next, a cured film, a laminate, a semiconductor device, and a method for manufacturing them will be described.

The cured film of the present invention is obtained by curing the curable resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.

The cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. It is preferable that the laminate of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable. The first cured film and the second cured film are both cured films of the present invention. For example, both the first cured film and the second cured film are curable of the present invention. An embodiment in which the resin composition is a cured film is preferable. The curable resin composition of the present invention used for forming the first cured film and the curable resin composition of the present invention used for forming the second cured film have the same composition. It may be present, or it may be a composition having a different composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

Examples of applicable fields of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. In addition, a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above may be patterned by etching. For these applications, for example, Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008, Masaaki Kakimoto / supervision, CMC technical library "Basics and development of polyimide materials" November 2011 You can refer to "Latest Polyimide Basics and Applications", NTS, August 2010, etc., published by Japan Polyimide / Aromatic Polymer Research Association / ed.

The cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially microelectronics.

The method for producing a cured film of the present invention (hereinafter, also simply referred to as "the method for producing the present invention") includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film. Is preferable.
The method for producing a cured film of the present invention may include a step of mixing the above-mentioned precursor composition and a specific compound to produce the curable resin composition of the present invention before the above-mentioned film forming step. preferable.
The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film.
Further, the method for producing a cured film of the present invention more preferably includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450 ° C.
Specifically, it is also preferable to include the following steps (a) to (d). Moreover, you may include the step (a') before (a) if necessary.
(A') Composition manufacturing step of mixing a precursor composition and a specific compound to produce the curable resin composition of the present invention (a) Applying the curable resin composition to a substrate to form a film (curable) A film forming step of forming the resin composition layer) (b) An exposure step of exposing the film after the film forming step (c) A developing step of developing the exposed film (d) 50 to the developed film Heating step of heating at 450 ° C. By heating in the above heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed to obtain sufficient curability.

The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention. The method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after the cured film is formed according to the above-mentioned method for producing the cured film. )-(D). In particular, it is preferable to perform each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion where the cured film is provided, between the cured films, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to (d). ) Can be performed a plurality of times to obtain a laminated body of the cured film.
When the step (a) is performed a plurality of times, the step (a') may be further performed before each step (a), or the curability produced in one step (a') may be performed. The resin composition may be used in a plurality of steps (a).

<Film formation process (layer formation process)>
The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the curable resin composition is applied to a substrate to form a film (layered).

The type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film transistor. There are no particular restrictions on magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, and plasma display panel (PDP) electrode plates.
In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material and a molded resin base material are more preferable.
Further, as the base material, for example, a plate-shaped base material (board) is used.

When the curable resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a base material.

Coating is preferable as a means for applying the curable resin composition to the base material.

Specifically, as the means to apply, the dip coating method, the air knife coating method, the curtain coating method, the wire bar coating method, the gravure coating method, the extrusion coating method, the spray coating method, the spin coating method, the slit coating method, etc. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method.
Further, the coating method can be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it may be applied at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds, and it may be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. it can. Further, in order to obtain the uniformity of the film thickness, a plurality of rotation speeds can be combined and applied.
Further, it is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned applying method onto a base material.
Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.

<Drying process>
The production method of the present invention may include a step of forming the film (curable resin composition layer), followed by a film forming step (layer forming step), and then drying to remove the solvent. The preferred drying temperature is 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes. If the amount of solvent in the curable resin composition solution is large, vacuum drying and heat drying can also be combined. A hot plate, a hot air oven, or the like is used for heat drying, and the heating and drying is not particularly limited.

<Exposure process>
The production method of the present invention may include an exposure step of exposing the film (curable resin composition layer). The amount of exposure is not particularly determined as long as the curable resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm ^{2 in} terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ /. It is more preferable to irradiate with cm ² .

The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

In relation to the light source, the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, and the like. The curable resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained. From the viewpoint of handling and productivity, a broad (three wavelengths of g, h, and i rays) light source of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.

<Development process>
The production method of the present invention may include a developing step of developing (developing the above film) the exposed film (curable resin composition layer). By performing the development, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.

Development is performed using a developer. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.

In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.

The organic solvent includes, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl propionate ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionate (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Ethyl acid acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. , Ke Tons include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and cyclic hydrocarbons include, for example, aromatics such as toluene, xylene and anisole. Hydrocarbons, cyclic terpenes such as limonene, and dimethyl sulfoxides are preferable as sulfoxides.

In the present invention, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable.
Further, the developing solution may contain a surfactant.

The developing solution preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Further, the developing solution may be 100% by mass of an organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly specified, but is usually 20 to 40 ° C.

After the treatment with the developing solution, further rinsing may be performed. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, propylene glycol monomethyl ether acetate can be mentioned. The rinsing time is preferably 5 seconds to 5 minutes. Further, a step of applying both a developer and a rinse solution may be included between the development and the rinse. The time of the above step is preferably 1 second to 5 minutes. For example, it can be rinsed with a solvent contained in the curable resin composition. The rinsing time is preferably 5 seconds to 1 minute.

<Heating process>
The production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ° C.
The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, for example, the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the heterocyclic polymer precursor proceeds. Further, the curable resin composition of the present invention may contain a radically polymerizable compound other than the heterocyclic polymer precursor, but may also cure a radically polymerizable compound other than the unreacted heterocyclic polymer precursor. It can be advanced in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.

The heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, the cured film can be prevented. Residual stress can be relaxed.

The temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the curable resin composition is applied onto a substrate and then dried, the temperature of the film (layer) after drying is higher than, for example, the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually raise the temperature from a temperature as low as 30 to 200 ° C.

The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.

Especially when forming a multi-layered laminate, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C. from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the heterocyclic polymer precursor between the layers are undergoing a cross-linking reaction at this temperature.

Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed. The heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C, and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.

Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

It is preferable that the heating step is carried out in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon or under a vacuum in order to prevent decomposition of the heterocyclic polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

<Metal layer forming process>
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (curable resin composition layer).

As the metal layer, existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. More preferred.

The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.

The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm at the thickest portion.

<Laminating process>
The production method of the present invention preferably further includes a laminating step.

In the laminating step, (a) film forming step (layer forming step), (b) exposure step, (c) developing step, and (d) heating step are performed again on the surface of the cured film (resin layer) or metal layer. , A series of steps including performing in this order. However, the mode may be such that only the film forming step (a) is repeated.
Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated curable resin composition layers all at once. Further, the (c) developing step may be followed by the (e) metal layer forming step, and even if the heating is performed each time (d), the steps of (d) are collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step, and the like as appropriate.

When the laminating step is further performed after the laminating step, the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. An example of the surface activation treatment is plasma treatment.

The laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.

For example, a configuration in which the resin layer is 3 or more and 7 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and 3 or more and 5 or less are more preferable.

In the present invention, it is particularly preferable to form a cured film (resin layer) of the curable resin composition so as to cover the metal layer after the metal layer is provided. Specifically, a mode in which (a) a film forming step, (b) an exposure step, (c) a developing step, (e) a metal layer forming step, and (d) a heating step are repeated in this order, or (a) film forming. Examples thereof include an embodiment in which the steps, (b) exposure steps, (c) development steps, and (e) metal layer forming steps are repeated in this order, and (d) heating steps are collectively provided at the end or in the middle. By alternately performing the laminating step of laminating the curable resin composition layer (resin layer) and the metal layer forming step, the curable resin composition layer (resin layer) and the metal layer can be laminated alternately.

The present invention also discloses a semiconductor device containing the cured film or laminate of the present invention. As specific examples of the semiconductor device in which the curable resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 and the description in FIG. 1 of JP-A-2016-0273557 are taken into consideration. Yes, these contents are incorporated herein.

The present invention will be described in more detail with reference to examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. 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. Unless otherwise specified, "part" and "%" are based on mass.

<Synthesis example 1>
[A-1: Synthesis of polyimide precursor resin A-1 from oxydiphthalic anhydride, 4,4'-biphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]
9.49 g (32.25 mmol) of 4,4'-biphthalic anhydride, oxydiphthalic dianhydride while removing water in a drying reactor with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. 10.0 g (32.25 mmol) of the product was suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 18 hours. The mixture was then cooled to −20 ° C. and then 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature, stirred for 2 hours and then added 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) to give a clear solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added to the obtained transparent liquid by dropping over 1 hour. Then 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 3 days. The obtained polyimide precursor A-1 had a weight average molecular weight of 24,800 and a number average molecular weight of 10,500.
The acid value of the obtained polyimide precursor A-1 was 11.5 mgKOH / g.

<Synthesis example 2>
[A-2: Synthesis of polyimide precursor resin A-2 from oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]
20.0 g (64.5 mmol) of oxydiphthalic dianhydride was suspended in 140 mL of diglyme while removing water in a drying reactor with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. .. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.08 g of pure water and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 18 hours. The mixture was then cooled to −20 ° C. and then 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature, stirred for 2 hours and then added 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) to give a clear solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added to the obtained transparent liquid by dropping over 1 hour. Then 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of the obtained polyimide precursor A-2 was 23,500, and the number average molecular weight was 8,800.
The acid value of the obtained polyimide precursor A-2 was 15.8 mgKOH / g.

<Synthesis example 3>
[Synthesis of polybenzoxazole precursor A-3 from A-3: 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-oxydibenzoyl chloride]
28.0 g (76.4 mmol) of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 200 g of N-methylpyrrolidone with stirring. Subsequently, 12.1 g (153 mmol) of pyridine was added, and 20.7 g (70.1 mmol) of 4,4'-oxydibenzoyl chloride was added to 75 g of N-methylpyrrolidone while keeping the temperature at -10 to 0 ° C. The dissolved solution was added dropwise over 1 hour. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was further stirred for 60 minutes. The polybenzoxazole precursor resin was then precipitated in 6 liters of water and the water-polybenzoxazole precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polybenzoxazole precursor resin was obtained by filtration, stirred again in 6 liters of water for 30 minutes and filtered again. Then, the obtained polybenzoxazole precursor resin was dried under reduced pressure at 45 ° C. for 3 days. The obtained polybenzoxazole precursor A-3 had a weight average molecular weight of 21,500 and a number average molecular weight of 9,500.
The acid value of the obtained polybenzoxazole precursor A-3 was 190 mgKOH / g.

<Synthesis example 4>
[Synthesis of polyimide precursor (A-4: polyimide precursor having radical polymerizable group) from 4,4'-oxydiphthaldioic anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate]
155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine with stirring at room temperature. After the exotherm by the reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for another 16 hours.

Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and the mixture was stirred for 1 hour. Then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polymer A-4. The weight average molecular weight (Mw) of this polymer A-4 was measured and found to be 20,000.

<Synthesis example 5>
[3,3', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and polyimide precursor from 2-hydroxyethyl methacrylate (A-5: Polyimide having a radically polymerizable group) Synthesis of precursor)]
Synthesis Example 4 except that 147.1 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride was used in place of 155.1 g of 4,4'-oxydiphthalic acid dianhydride. Polymer A-5 was obtained by carrying out the reaction in the same manner as described in 4. The weight average molecular weight (Mw) of this polymer A-5 was measured and found to be 22,000.

<Examples and Comparative Examples>
In each of the examples described as "at the time of liquid preparation" in the column of "method of adding a specific compound", the components shown in Table 1 or Table 2 below were mixed to obtain each curable resin composition. .. Further, in each comparative example, the components shown in Table 2 below were mixed to obtain each comparative composition.
In each of the examples described as "immediately before film formation" in the column of "method for adding the specific compound", the components shown in Table 1 or Table 2 other than the specific compound were mixed to obtain a precursor composition. .. Then, immediately before forming the curable resin composition layer in each evaluation, the specific compounds shown in Table 1 or Table 2 were mixed with the precursor composition to obtain a curable resin composition.
Specifically, the content of the components shown in Table 1 was the amount shown in "Mass parts" in Table 1.
The obtained curable resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm.
In Table 1, for example, the descriptions of "A-1 / A-2" and "16/16" indicate that A-1 is contained in 16 parts by mass and A-2 is contained in 16 parts by mass.
Further, in Table 1, the description of "-" indicates that the composition does not contain the corresponding component.

Details of each component listed in Table 1 are as follows.

[Heterocycle-containing polymer precursor]
-A-1 to A-5: A-1 to A-5 synthesized above

[Specific compound]
-BE-1: N, N-dimethylcyclohexylamine-BE-2: triethylamine-BE-3: 2- (dimethylamino) ethyl methacrylate-BE-4: dicyclohexylamine-BE-5: 4-dimethylaminopyridine- BE-6: Diisopropylamine, BE-7: 1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimid [1,2-a] pyrimidin, BE-8: imidazole, BE-9 : 1,2-benzopyrazole, BE-10: 5-methylpyrazole-3-carboxylate methyl, BE-11: N-isopropylaniline, B-1: 3-aminopropyltriethoxysilane Compound B-1 is alkoxy It is a compound containing a silyl group and does not correspond to a specific compound.
B-2: Diethylamine compound B-2 is a compound having a hydrogen atom and not having a branched structure or a cyclic structure, and is not a specific compound.

[Photopolymerization initiator]
・ OXE-01: IRGACURE OXE 01 (manufactured by BASF)
-OXE-02: IRGACURE OXE 02 (manufactured by BASF)

〔solvent〕
-DMSO: dimethyl sulfoxide-GBL: γ-butyrolactone-ethyl lactate-NMP: N-methylpyrrolidone In Table 1, DMSO / GBL is described as DMSO and GBL in the ratio of DMSO: GBL = 20: 80 (mass ratio). It shows that it was mixed.
The description of NMP / ethyl lactate in Table 1 indicates that ethyl lactate and N-methylpyrrolidone were mixed in a ratio of ethyl lactate: N-methylpyrrolidone = 20:80 (mass ratio).

[Polymerizable compound]
-SR-209: SR-209 (manufactured by Sartmer)
-SR-231: SR-231 (manufactured by Sartmer)
-SR-239: SR-239 (manufactured by Sartmer)
・ A-DPH: Dipentaerythritol hexaacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

[Onium salt or thermobase generator]
-F-1 or F-2: A compound having the following structure.

[Polymerization inhibitor]
・ G-1: 1,4-benzoquinone ・ G-2: 4-methoxyphenol ・ G-3: 1,4-dihydroxybenzene ・ G-4: 2-nitroso-1-naphthol (Tokyo Chemical Industry Co., Ltd.) ) Made)

[Metal adhesion improver]
-H-1 to H-4: The following compounds Et represent an ethyl group.

[Migration inhibitor]
I-1: 1H-tetrazole

〔Additive〕
・ J-1: N-Phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

In any of the curable resin compositions in the examples, the water content with respect to the total mass of the solvent was 0.1% by mass or less.
The water content was measured using a Karl Fischer moisture meter (product name "MKC-710M", manufactured by Kyoto Denshi Kogyo Co., Ltd., Karl Fischer titration formula).

<Evaluation>
[Evaluation of film strength (break elongation)]
In each Example and Comparative Example, a curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a curable resin composition layer having a uniform thickness of about 15 μm on the silicon wafer. The entire surface of the curable resin composition layer on the silicon wafer was exposed to i-rays with an exposure energy of 500 mJ / cm ² using a stepper (Nikon NSR 2005 i9C). The curable resin composition layer (resin layer) after the above exposure is heated at a heating rate of 10 ° C./min under a nitrogen atmosphere to reach the temperature described in the column of curing temperature (° C.) in Table 1. After that, it was heated for 3 hours. The cured resin layer (cured film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured film was peeled off from the silicon wafer. The peeled cured film was punched out using a punching machine to prepare a test piece having a sample width of 3 mm and a sample length of 30 mm. The obtained test piece was subjected to a film in accordance with JIS-K6251 using a tensile tester (Tensilon) at a crosshead speed of 300 mm / min and in an environment of 25 ° C. and 65% RH (relative humidity). The elongation at break in the longitudinal direction was measured. The evaluation was carried out 5 times each, and the arithmetic mean value of the elongation rate (break elongation rate) when the film was broken was used as an index value.
The above index values were evaluated according to the following evaluation criteria, and the evaluation results are shown in the “Film strength” column of Table 1. It can be said that the larger the index value is, the better the film strength (break elongation) of the obtained cured film is.

-Evaluation criteria-
A: The above index value was 60% or more.
B: The index value was 55% or more and less than 60%.
C: The above index value was 50% or more and less than 55%.
D: The above index value was less than 50%.

[Evaluation of storage stability (rate of change in membrane)]
-Measurement of pre-aging film thickness-
In each Example and Comparative Example, a curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a curable resin composition layer having a uniform thickness of about 15 μm on the silicon wafer. The film thickness of the curable resin composition layer on the silicon wafer was measured, and this value was taken as the pre-aging film thickness. The film thickness was determined as an arithmetic mean value obtained by measuring the film thickness at 10 points on the coated surface with an ellipsometer (KT-22 manufactured by Foothill).

-Measurement of film thickness after aging-
In each of the Examples and Comparative Examples, the curable resin composition or the comparative composition (in the Examples described as "immediately before film formation" in the column of "Addition method of specific compound", the precursor composition. ) Is placed in a glass container, sealed, and allowed to stand in a light-shielded environment at 25 ° C. for 14 days. A substance (in the example described as "immediately before film formation" in the column of "method of adding specific compound", the specific compound was mixed with the precursor composition immediately before film formation) was siliconized by a spin coat method. It was applied on a wafer to form a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a curable resin composition layer having a uniform thickness on the silicon wafer. The film thickness of the obtained curable resin composition layer was measured by the same method as the film thickness measuring method in the above-mentioned pre-aging film thickness measuring method, and this value was taken as the post-aging film thickness.

-Film thickness change rate-
The film thickness change rate was calculated by the following formula.
Film thickness change rate (%) = | Pre-aging film thickness-Post-aging film thickness | / Pre-aging film thickness x 100
The calculated film thickness change rate was evaluated according to the following evaluation criteria, and the evaluation results are shown in the "Storage stability" column of Table 1. It can be said that the smaller the rate of change in film thickness, the better the storage stability of the curable resin composition.

-Evaluation criteria-
A: The rate of change in film thickness was less than 10%.
B: The rate of change in film thickness was 10% or more and less than 15%.
C: The film thickness change rate was 15% or more and less than 20%.
D: The film thickness change rate was 20% or more.

[Evaluation of chemical resistance (rate of film change)]
In each Example and Comparative Example, a curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a curable resin composition layer having a uniform thickness of 15 μm on the silicon wafer. The curable resin composition layer on the silicon wafer was exposed to i-rays with an exposure energy of 500 mJ / cm ² using a stepper (Nikon NSR 2005 i9C), and the exposed curable resin composition layer (resin layer) was subjected to i-ray exposure. The temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and the mixture was heated at the temperatures shown in Table 1 for 3 hours to obtain a cured layer (resin layer) of the curable resin composition layer.
The obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
Chemical solution: A mixture of dimethyl sulfoxide (DMSO) and a 25 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio) Evaluation conditions: The resin layer is immersed in the above chemical solution at 75 ° C. for 15 minutes before and after. The film thicknesses were compared and the dissolution rate (nm / min) was calculated. The film thickness was determined as an arithmetic mean value obtained by measuring the film thickness at 10 points on the coated surface with an ellipsometer (KT-22 manufactured by Foothill).
The evaluation was performed according to the following evaluation criteria, and the evaluation results are listed in the "Chemical resistance" column of Table 1. It can be said that the smaller the value of the dissolution rate, the better the chemical resistance of the obtained cured film (resin layer).

-Evaluation criteria-
A: The dissolution rate was less than 200 nm / min.
B: The dissolution rate was 200 nm / min or more and less than 300 nm / min.
C: The dissolution rate was 300 nm / min or more and less than 400 nm / min.
D: The dissolution rate was 400 nm / min or more.

From the above results, it can be seen that the curable resin composition containing the heterocyclic polymer precursor, the specific compound, the polymerization initiator and the solvent according to the present invention is excellent in the film strength of the cured film.
The curable resin compositions according to Comparative Examples 1 to 6 do not contain a specific compound. It can be seen that the curable resin compositions according to Comparative Examples 1 to 6 are inferior in film strength of the cured film.

<Example 101>
The curable resin composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin base material having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 5 minutes. After forming a curable resin composition layer having a thickness of 20 μm, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 μm). After exposure, it was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a layer pattern.
Then, it was heated at 230 ° C. for 3 hours to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating property.
Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Claims

At least one resin selected from the group consisting of polyimide precursors and polybenzoxazole precursors,
A basic compound represented by the following formula (1-1) or a weak acid salt thereof,
A curable resin composition containing a polymerization initiator and a solvent.

In formula (1-1), R 1 to R 3 each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, or a substituted or unsubstituted aromatic group, and R 1 to R 3 It may form at least two members ring structure of, when R 1 ~ R 3 does not contain an alkoxysilyl group as a substituent, at least one of hydrogen atoms of R 1 ~ R 3, R 1 ~ one another at least one R 3 represents a structure having a branched structure or a cyclic structure.
The basic compound or a weakened salt thereof is selected from the group consisting of a secondary aliphatic amine, a tertiary aliphatic amine, a secondary aromatic amine, a tertiary aromatic amine, and a nitrogen-containing heterocyclic compound. The curable resin composition according to claim 1, which is at least one basic compound or a weak acid salt thereof.
The curable resin composition according to claim 1 or 2, wherein the basic compound or a weak acid salt thereof is a monoamine compound or a weak acid salt thereof.
The curable resin composition according to any one of claims 1 to 3, wherein the content of the basic compound or a weak acid salt thereof is 0.2 to 10% by mass with respect to the total solid content of the composition. ..
The curable resin composition according to any one of claims 1 to 4, wherein the basic compound or a weak acid salt thereof has a molecular weight of 60 to 200.
The curable resin composition according to any one of claims 1 to 5, wherein the resin is a polyimide precursor having a repeating unit represented by the following formula (1).

In formula (1), A 1 and A 2 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 Each of R 114 independently represents a hydrogen atom or a monovalent organic group.
The curable resin composition according to claim 6, wherein at least one of R 113 and R 114 contains a radically polymerizable group.
The curable resin composition according to any one of claims 1 to 7, wherein the acid value of the resin is 8 to 80 mgKOH / g.
The curable resin composition according to any one of claims 1 to 8, wherein the water content is 5% by mass or less with respect to the total mass of the solvent.
The curable resin composition according to any one of claims 1 to 9, further comprising a radically polymerizable compound.
The curable resin composition according to any one of claims 1 to 10, further comprising at least one selected from the group consisting of an onium salt and a thermosetting agent.
The curable resin composition according to any one of claims 1 to 11, which is used for forming an interlayer insulating film for a rewiring layer.
The method for producing a curable resin composition according to any one of claims 1 to 12.
A method for producing a curable resin composition, which comprises a step of mixing a composition containing the resin, the polymerization initiator, and the solvent with a basic compound represented by the formula (1-1) or a weak acid salt thereof.
A cured film obtained by curing the curable resin composition according to any one of claims 1 to 12.
A laminate containing two or more layers of the cured film according to claim 14 and containing a metal layer between any of the cured films.
A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of claims 1 to 12 to a substrate to form a film.
A composition containing the resin, the polymerization initiator, and the solvent is mixed with a basic compound having a structure represented by the formula (1-1) or a weak acid salt thereof to produce the curable resin composition. The method for producing a cured film according to claim 16, further comprising the step of forming the film before the film forming step.
The method for producing a cured film according to claim 16 or 17, which comprises an exposure step for exposing the film and a developing step for developing the film.
The method for producing a cured film according to any one of claims 16 to 18, which comprises a heating step of heating the film at 50 to 450 ° C.
A semiconductor device comprising the cured film according to claim 14 or the laminate according to claim 15.