KR102668435B1 - Curable resin composition, manufacturing method of curable resin composition, cured film, laminate, manufacturing method of cured film, and semiconductor device - Google Patents

Abstract

A curable resin composition comprising 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 salt thereof, a polymerization initiator, and a solvent, A method for producing the curable resin composition, a cured film formed by curing the curable resin composition, a laminate containing the cured film, a method for producing the cured film, and a semiconductor device containing the cured film or the laminate.

Description

Curable resin composition, manufacturing method of curable resin composition, cured film, laminate, manufacturing method of 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.

A resin obtained by cyclizing and curing 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”). Because it has excellent heat resistance and insulation properties, it is applied to a variety of applications. The above-mentioned use is not particularly limited, but, for example, in semiconductor devices for mounting, it may be used as an insulating film or sealant material, or as a protective film. Additionally, it is also used as a base film or cover lay for flexible substrates.

For example, in the above-mentioned application, the heterocycle-containing polymer precursor is used in the form of a curable resin composition containing the heterocycle-containing polymer precursor. Such a curable resin composition can be applied to a substrate by, for example, coating, and then the heterocycle-containing polymer precursor is cyclized by heating or the like, thereby forming a cured resin on the substrate. Since the curable resin composition can be applied by known application methods, etc., it can be said to have excellent manufacturing adaptability, such as a high degree of freedom in designing the shape, size, and application location of the applied curable resin composition. .

In addition to the high performance of polyimide and the like, from the viewpoint of excellent manufacturing adaptability, industrial application of curable resin compositions containing heterocycle-containing polymer precursors is increasingly expected.

For example, in Patent Document 1, a polyamic acid consisting of a repeating unit of a specific structure in a mixed solvent consisting of water and N-methyl-2-pyrrolidone with a water ratio of 10 to 90% by mass, and imida A polyimide precursor composition prepared by dissolving a basic compound selected from the group consisting of sols and amine compounds is described.

Patent Document 2 discloses a solvent that is a solvent-soluble polyimide of a specific structure, and in which 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. A polyimide resin composition for electrodeposition is described, characterized by comprising a soluble polyimide, water, and a basic compound.

Patent Document 1: Japanese Patent Publication No. 2016-017145 Patent Document 2: Japanese Patent Publication No. 2008-291265

In a curable resin composition containing a heterocycle-containing polymer precursor, there is a desire to provide a curable resin composition that has excellent film strength of the resulting cured product.

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

Examples of representative 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 salt thereof,

a polymerization initiator, and

solvent-containing

Curable resin composition.

[Formula 1]

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 at least 2 of R ¹ to R ³ may be combined to form a ring structure, R ¹ to R ³ do not contain an alkoxysilyl group as a substituent, and when at least one of R ¹ to R ³ is a hydrogen atom, at least one of R ¹ to R ³ is a hydrogen atom. It represents a structure having a branched structure or a cyclic structure.

<2> The basic compound or its weak salt is at least one selected from the group consisting of secondary aliphatic amines, tertiary aliphatic amines, secondary aromatic amines, tertiary aromatic amines, and nitrogen-containing heterocyclic compounds. The curable resin composition according to <1>, which is a basic compound or a weak acid salt thereof.

<3> The curable resin composition according to <1> or <2>, wherein the basic compound or its weak acid salt is a monoamine compound or its weak acid salt.

<4> The curable resin composition according to any one of <1> to <3>, wherein the content of the basic compound or its weak salt is 0.2 to 10% by mass based on the total solid content of the composition.

<5> The curable resin composition according to any one of <1> to <4>, wherein the basic compound or its weak salt 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).

[Formula 2]

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

<7> The curable resin composition according to <6>, wherein at least one of R ¹¹³ and R ¹¹⁴ contains a radical polymerizable group.

<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 based on 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 member selected from the group consisting of an onium salt and a heat base generator.

<12> The curable resin composition according to any one of <1> to <11>, which is used for forming an interlayer insulating film for a redistribution layer.

<13> A method for producing the curable resin composition according to any one of <1> to <12>,

A method for producing a curable resin composition, comprising the step of mixing a composition containing the resin, the polymerization initiator, and the solvent, and a basic compound represented by formula (1-1) or a weak salt thereof.

<14> A cured film formed by curing the curable resin composition according to any one of <1> to <12>.

<15> A laminate comprising two or more layers of the cured film according to <14>, and a metal layer between any of the cured films.

<16> A method for producing a cured film, comprising 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 step of producing the curable resin composition by mixing a composition containing the resin, the polymerization initiator, and the solvent with a basic compound having a structure represented by formula (1-1) or a weak salt thereof, The method for producing a cured film according to <16>, which is included before the film forming step.

<18> The method for producing a cured film according to <16> or <17>, comprising an exposure step of exposing the film and a development step of developing the film.

<19> The method for producing a cured film according to any one of <16> to <18>, including 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 a cured film obtained, a method for producing the curable resin composition, a cured film formed by curing the curable resin composition, a laminate containing the cured film, a method for producing the cured film, and , a semiconductor device including the cured film or the laminate is provided.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.

In this specification, the numerical range indicated using the symbol “~” means a range that includes the numerical values written before and after “~” as the lower limit and upper limit, respectively.

In this specification, the term "process" is meant to include not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended function of the process can be achieved.

In the notation of groups (atomic groups) in this specification, notations that do not describe substitution or unsubstitution include groups (atomic groups) that have substituents as well as groups (atomic groups) that do not have substituents. For example, “alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group with a substituent (substituted alkyl group).

In this specification, unless otherwise specified, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. In addition, the light used for exposure includes active light or radiation such as the bright line spectrum of a mercury lamp, deep ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.

In this specification, “(meth)acrylate” means both “acrylate” and “methacrylate”, or “(meth)acrylate” means “acrylic” and “methacrylate”. "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl".

In this 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 this specification, total solid content refers to the total mass of components excluding the solvent from all components of the composition. In addition, in this specification, solid content concentration refers to the mass percentage of other components excluding the solvent relative to the total mass of the composition.

In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement). In this specification, for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used as the weight average molecular weight (Mw) and number average molecular weight (Mn), and guard column HZ-L and TSKgel Super HZM- are used as columns. It can be obtained by using M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, their molecular weights are assumed to be measured using THF (tetrahydrofuran) as an eluent. In addition, detection in GPC measurement is assumed to be performed using a detector with a wavelength of 254 nm of UV rays (ultraviolet rays), unless otherwise specified.

In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower," it refers to the reference layer among the plurality of layers in focus. Another layer may exist on the upper or lower side. 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 do not need to be in contact. In addition, unless otherwise specified, the direction in which the layers are laminated with respect to the substrate is referred to as "up", or when a photosensitive layer is present, the direction from the substrate to the photosensitive layer is referred to as "up", and vice versa. The direction is called “down.” In addition, such setting of the vertical direction is for convenience in this specification, and in actual embodiments, the “up” direction in this specification may be different from vertically upward.

In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component contained in the composition. In addition, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.

In this specification, unless otherwise specified, the temperature is 23°C and the atmospheric pressure is 101,325 Pa (1 atmosphere).

In this specification, a combination of preferred aspects is a more preferred aspect.

(Curable resin composition)

The curable resin composition of the present invention includes 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 a “specific compound”) includes).

The curable resin composition of the present invention preferably contains a polymerizable compound, and more preferably contains a radically polymerizable compound.

Moreover, it is preferable that the curable resin composition of the present invention further contains at least one selected from the group consisting of onium salts and thermobase generators.

[Formula 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 at least 2 of R ¹ to R ³ may be combined to form a ring structure, R ¹ to R ³ do not contain an alkoxysilyl group as a substituent, and when at least one of R ¹ to R ³ is a hydrogen atom, at least one of R ¹ to R ³ is a hydrogen atom. It 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 resulting cured film.

Although the mechanism by which the above effect is obtained is unclear, it is assumed as follows.

Conventionally, a curable resin composition containing a polymer precursor has been used to obtain a cured film containing a polyimide resin or the like by applying heating to a substrate or the like to cyclize the precursor.

Here, when obtaining a cured film by the above method, the film is cured as cyclization progresses, so additional cyclization occurs due to the movement of the structure contained in the polymer precursor before cyclization in the film being restricted. There were times when it got difficult.

However, the curable resin composition of the present invention contains a specific compound. It is believed that certain compounds promote cyclization of polymer precursors. In addition, since it is thought that a specific compound having a structure represented by formula (1-1) is likely to move even in a film in which cyclization is in progress, additional cyclization of the heterocycle-containing polymer precursor is promoted even in a film in which cyclization is in progress. I think it works. Due to the above mechanism, it is believed that, according to the curable resin composition of the present invention, the cyclization rate of the polymer precursor is improved, and a cured film with excellent film strength is obtained.

Moreover, according to the curable resin composition of the present invention, since the conversion ratio is improved as described above, it is thought that a cured film excellent in chemical resistance can be easily obtained.

In addition, since the specific compound in the curable resin composition of the present invention has a specific structure, it is difficult to promote cyclization of the polymer precursor when stored at, for example, 20°C, and it is thought that it is likely to have excellent storage stability. do.

In addition, when the curable resin composition has photosensitivity, for example, the composition film formed from the curable resin composition is subjected to exposure such as pattern exposure, polymerized, developed, and then cyclized by heating or the like to cyclize the polymer precursor described above. there is.

When the curable resin composition has photosensitivity, for example, the polymer precursor has a polymerizable group, the curable resin composition contains a polymerizable compound, or both, and a polymerization initiator in the curable resin composition A case where is a photopolymerization initiator, etc. can be mentioned.

When cyclization is performed on a film after such polymerization, cyclization of the polymer precursor may be difficult to proceed due to reasons such as the movement of the structure contained in the polymer precursor being restricted since the film has been cured through polymerization.

According to the curable resin composition of the present invention, since cyclization is promoted by a specific compound even in the film after polymerization of such polymerizable groups has progressed, the cyclization rate of the polymer precursor is improved, and a cured film with excellent film strength can be obtained. I think it's easy.

In particular, even when the exposure amount in the exposure is large and the progress of the polymerization described above is large, according to the curable resin composition of the present invention, it is easy to obtain a cured film with excellent film strength by promoting cyclization by a specific compound. I think so.

Here, Patent Document 1 or 2 does not describe or suggest a curable resin composition containing a heterocycle-containing 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 heterocycle-containing polymer precursor.

The curable resin composition of the present invention contains, as the heterocycle-containing polymer precursor, at least one precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and preferably includes a polyimide precursor.

[Polyimide precursor]

From the viewpoint of the film strength of the cured film obtained, it is preferable that the polyimide precursor has a repeating unit represented by the following formula (1).

[Formula 4]

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

-A ¹ and A ² -

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

-R ¹¹¹ -

R ¹¹¹ in formula (1) represents a divalent organic group. Examples of the divalent organic group include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or combinations of two or more thereof, and include straight-chain aliphatic groups with 2 to 20 carbon atoms and 3 carbon atoms. A branched aliphatic group of ~20 carbon atoms, a cyclic aliphatic group of 3-20 carbon atoms, an aromatic group of 6-20 carbon atoms, or a combination of two or more of these groups are preferable, and an aromatic group of 6-20 carbon atoms is more preferable.

R ¹¹¹ in formula (1) is preferably derived from diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

Specifically, diamine is a diamine containing a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination of two or more thereof. It is preferable, and it is more preferable that it is diamine containing an aromatic group of 6 to 20 carbon atoms. Examples of groups containing an aromatic group include the following.

[Formula 5]

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

As diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohex. three; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane phosphorus 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'-diaminodiphenylsulfone, 4,4'- or 3,3'-diaminodiphenylmethane Phenyl 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 -aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3) -Hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl) Hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'- Bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy) C) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl Sulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl -4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminoctafluorobiphenyl, 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)ethylmethacryl Late, 2,4- or 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2 , 4,6-trimethyl-metaphenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis( 4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane , 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoro Heptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2 ,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis( trifluoromethyl)phenyl]hexafluoropropane, 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) diphenyl sulfone , 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexa Fluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl , 2,2', 5,5', 6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl.

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

[Formula 6]

[Formula 7]

Additionally, diamines having at least two alkylene glycol units in the main chain can also be cited as preferred examples. Preferably, the diamine contains two or more of one or both of the ethylene glycol chain and the propylene glycol chain in one molecule, and more preferably, the diamine is a diamine that does not contain an aromatic ring. As specific examples, Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) EDR -148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade names above, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy )Ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc., but limited to these. It doesn't work.

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

[Formula 8]

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

R ¹¹¹ in Formula (1) is preferably represented by -Ar ⁰ -L ⁰ -Ar ⁰ - from the viewpoint of flexibility of the resulting cured film. Ar ⁰ is each independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and especially preferably 6 to 10 carbon atoms), and is preferably a phenylene group. L ⁰ is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO-, or a combination of two or more thereof. The preferable range of L ⁰ has the same meaning as A described above.

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

[Formula 9]

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

Examples of the monovalent organic group for R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), etc. You can.

[Formula 10]

In formula (61), R ⁵⁸ and R ⁵⁹ each independently represent a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

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

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

[Formula 11]

-R ¹¹⁵ -

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

[Formula 12]

R ¹¹² has the same meaning as A, and the preferred range is also the same. * Each independently represents a binding site with another structure.

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in Formula (1) include tetracarboxylic acid residues remaining after the acid dianhydride group is removed from tetracarboxylic acid dianhydride.

Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

[Formula 13]

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as R ¹¹⁵ in equation (1).

Specific examples of tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (4,4'-biphthalic anhydride), 3 ,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride Water, 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 dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1 ,4,5,7-naphthalenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride , 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1, 4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4, 5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl ) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzene tetracarboxylic acid dianhydride, and alkyl derivatives thereof having 1 to 6 carbon atoms and carbon atoms At least one type selected from alkoxy derivatives 1 to 6 is exemplified.

Additionally, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below can also be cited as preferred examples.

[Formula 14]

-R ¹¹³ and R ¹¹⁴ -

R ¹¹³ and R ¹¹⁴ in formula (1) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a straight-chain or branched alkyl group, cyclic alkyl group, aromatic group, or polyalkyleneoxy group, and more preferably contains a polyalkyleneoxy group. Moreover, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a radical polymerizable group, and it is more preferable that both contain a radical polymerizable group. The radical polymerizable group is a group that can undergo a crosslinking reaction due to the action of a radical, and a group having an ethylenically unsaturated bond is a preferred example.

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, or a vinylphenyl group, a (meth)acryloyl group, a group represented by the following formula (III), etc. can be mentioned.

[Formula 15]

In formula (III), R ²⁰⁰ 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 preferably has 1 to 12 carbon atoms) 1 to 6 is more preferable, and 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and especially preferably 1 to 3. Additionally, (poly)oxyalkylene group means an oxyalkylene group or polyoxyalkylene group.

Examples of suitable R ²⁰¹ include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group. , alkylene groups such as dodecamethylene group, and -CH ₂ CH(OH)CH ₂ -, and ethylene group, propylene group, trimethylene group, and -CH ₂ CH(OH)CH ₂ - are more preferable.

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

In formula (III), * represents a binding site with another structure.

As a preferred embodiment of the polyimide precursor in the present invention, the monovalent organic group of R ¹¹³ or R ¹¹⁴ is an aliphatic group, an aromatic group, and an arylalkyl group having 1, 2, or 3 acid groups, preferably 1 acid group. etc. can be mentioned. Specifically, an aromatic group having 6 to 20 carbon atoms having an acid group and an arylalkyl group having 7 to 25 carbon atoms having an acid group can be mentioned. 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 solubility in a developing solution is preferably used.

In terms of solubility in an aqueous developer, 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 organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, a straight-chain or branched alkyl group, a cyclic alkyl group, and an aromatic group are preferable, and an alkyl group substituted with an aromatic group is more preferable.

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

As an aromatic group, specifically, a substituted or unsubstituted aromatic hydrocarbon group (cyclic structures constituting the group include a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, and a hepthalene ring. , indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, etc.), or a substituted or unsubstituted aromatic heterocyclic group (constituting the group Ring structures include fluorene ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, Benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, a Cridine ring, phenanthroline ring, cyanthrene ring, chromene ring, xanthene ring, phenoxathyine ring, phenothiazine ring, or phenazine ring).

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

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

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

[Formula 16]

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

The preferred ranges of A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ have the same meaning as the preferred ranges of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1), respectively.

The preferable range of R ¹¹² has the same meaning as R ¹¹² in formula (5), and it is more preferable that it is an oxygen atom.

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

In the polyimide precursor, the number of repeating units represented by formula (1) may be one, or two or more types may be used. Moreover, it may contain a structural isomer of the repeating unit represented by formula (1). Moreover, the polyimide precursor may also contain other types of repeating units in addition to the repeating units of the above formula (1).

As an embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, further 70 mol% or more, and especially 90 mol% or more of the total repeating units are repeating units represented by formula (1) is exemplified. do. 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 still more preferably 10,000 to 50,000. Moreover, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000.

The dispersion degree of the molecular weight of the polyimide precursor is preferably 1.5 to 7.0, and more preferably 1.8 to 6.5.

It is also preferable that the dispersion degree of the molecular weight of the polyimide precursor is 1.5 to 3.5, and more preferably 2 to 3.

In this specification, the dispersion of molecular weight refers to the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

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

In the method for producing a polyimide precursor, it is preferable to use an organic solvent during the reaction. The number of organic solvents may be one, and two or more types may be used.

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

In a method for producing a polyimide precursor, etc., in order to further improve storage stability, it is preferable to seal the ends of the polyimide precursor, etc. with an end-sealing agent such as an acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. do. As the end capping agent, it is more preferable to use monoalcohol, phenol, thiol, thiophenol, or monoamine.

Preferred monoalcohol compounds include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol. Primary alcohol, isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, secondary alcohol such as 1-methoxy-2-propanol, tertiary alcohol such as t-butyl alcohol, adamantane alcohol, etc. can be mentioned. Preferred phenol compounds include phenol, methoxyphenol, methylphenol, naphthalen-1-ol, and naphthalen-2-ol.

Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy- 6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid , 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol , 3-aminothiophenol, 4-aminothiophenol, etc. Two or more types of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end capping agents.

Additionally, when sealing the amino group at the resin terminal, it is possible to seal it with a compound having a functional group capable of reacting with the amino group. Preferred sealants for amino groups include carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic anhydride, and sulfonic carboxylic acid anhydride, and more preferably carboxylic acid anhydride and carboxylic acid chloride. Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, and benzoic anhydride. Also, 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-alcohol. Damantane carbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, etc. can be mentioned.

When producing a polyimide precursor, it is preferable to include a step of precipitating solids. Specifically, solid precipitation can be performed by precipitating the polyimide precursor in the reaction liquid in water and dissolving it in a solvent in which polyimide precursors, such as tetrahydrofuran, are soluble.

[Polybenzoxazole precursor]

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

[Formula 17]

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

-R ¹²¹ -

In formula (2), R ¹²¹ represents a divalent organic group. As a divalent organic group, an aliphatic group (carbon number 1-24 is preferable, 1-12 are more preferable, and 1-6 are especially preferable) and an aromatic group (carbon number is 6-22 are preferable, and 6-14 are more preferable) A group containing at least one of 6 to 12 is preferred. Examples of the aromatic group constituting R ¹²¹ include R ¹¹¹ of the above formula (1). As the aliphatic group, a straight-chain 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. As a tetravalent organic group, it has the same meaning as R ¹¹⁵ in the above formula (1), and its 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 each independently represent a hydrogen atom or a monovalent organic group, have the same meaning as R ¹¹³ and R ¹¹⁴ in the above formula (1), and have the same preferable range.

In addition to the repeating unit of formula (2) above, the polybenzoxazole precursor may also contain other types of repeating units.

From the point of being able to suppress the occurrence of warping of the cured film due to ring closure, it is preferable that the polybenzoxazole precursor further contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[Formula 18]

Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R ^2s is 1 carbon atom. It is a hydrocarbon group of ~10 (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 an aromatic group (preferably 6 to 6 carbon atoms). 22, more preferably 6 to 18 carbon atoms, especially preferably 6 to 10 carbon atoms), and the remainder is hydrogen atoms or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, especially Preferably, it is an organic group having 1 to 6 carbon atoms, and each may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z portion, preferably, the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a+b is 100 mol%.

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

When the polybenzoxazole precursor contains a diamine residue represented by the formula (SL) as another type of repeating unit, after removal of the acid dianhydride group from the tetracarboxylic dianhydride, in terms of improving the alkali solubility of the curable resin composition. It is preferable to further include the remaining tetracarboxylic acid residue as a repeating unit. An example of such a tetracarboxylic acid residue is R ¹¹⁵ in 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, and still more preferably 10,000 to 50,000. Moreover, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000.

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

-Sanga-

From the viewpoint of the film strength of the resulting cured film, the acid value of the heterocycle-containing polymer precursor is preferably 80 mgKOH/g or less, more preferably 50 mgKOH/g or less, more preferably 30 mgKOH/g or less, and especially 20 mgKOH/g or less. desirable. Moreover, the lower limit of the acid value is preferably 5 mgKOH/g or more, more preferably 8 mgKOH/g or more, and more preferably 10 mgKOH/g or more.

If the acid value is within the above range, it is thought that neutralization of the specific compound by the acid group is suppressed and cyclization of the heterocycle-containing polymer precursor is easily 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, more preferably 30% by mass or more, and still more 40% by mass or more, based on the total solid content of the curable resin composition. It is preferable, it is more preferable that it is 50 mass % or more, it is still more preferable that it is 60 mass % or more, and it is still more preferable that it is 70 mass % or more. Moreover, 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, more preferably 99% by mass or less, and 98% by mass, based on the total solid content of the curable resin composition. It is more preferable that it is 97 mass% or less, and it is still more preferable that it is 95 mass% or less.

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

<Specific compound>

The curable resin composition of the present invention contains a basic compound represented by formula (1-1) or a weak salt thereof (specific compound).

In the present invention, the weak salt is preferably a salt that exhibits basicity in the curable resin composition of the present invention. Moreover, examples of weak salts include carbonate, acetate, oxalate, and borate.

〔pKa〕

The pKa of the conjugate acid of a specific compound (when the specific compound is a weak salt, the pKa of the conjugate acid of the basic compound dissociated from the weak salt) is preferably 1 to 7, more preferably 2 to 6, and 2 to 7. 5 is more preferable.

The pKa of the conjugate acid refers to the equilibrium constant Ka expressed by the negative common logarithm pKa, considering the dissociation reaction in which hydrogen ions are released from the acid. The smaller the pKa, the stronger the acid. Unless otherwise specified, pKa is a value calculated by ACD/ChemSketch (registered trademark). Alternatively, you may refer to the values published in the "Revised 5th Edition Chemical Handbook Basics" edition of the Japan Chemical Society.

[R ¹ ~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 at least 2 of R ¹ to R ³ may be combined to form a ring structure, R ¹ to R ³ do not contain an alkoxysilyl group as a substituent, and when at least one of R ¹ to R ³ is a hydrogen atom, at least one of R ¹ to R ³ is a hydrogen atom. It represents a structure having a branched structure or a cyclic structure.

In this specification, when simply referred to as “alkyl group”, all alkyl groups formed by linear, branched, cyclic, or combinations thereof are included.

In 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, and are preferably a substituted or unsubstituted alkyl group, Alternatively, it is more preferable that it is a substituted or unsubstituted aromatic heterocyclic group.

As the aliphatic hydrocarbon group for R ¹ to R ³ , an alkyl group having 1 to 20 carbon atoms is preferable, and a straight-chain alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms are more preferred. Preferred, a straight-chain alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclohexyl group are more preferable.

Substituents of the alkyl group in R ¹ to R ³ include an aromatic hydrocarbon group (preferably a phenyl group), an aromatic heterocyclic group (preferably a nitrogen-containing aromatic heterocyclic group such as imidazolyl group and pyridinyl group), and an alkoxy group. , polymerizable groups such as alkyloxycarbonyl group, aryloxycarbonyl group, vinyl group, allyl group, (meth)acrylamide group, and methacryloxy group.

As the aromatic group in R ¹ to R ³ , an aromatic heterocyclic group with a reduction number of 5 to 6 is preferable, and an aromatic heterocyclic group with a reduction number of 6 is more preferable. Moreover, when the aromatic group is an aromatic heterocyclic group, it is preferable that the bonding site with the nitrogen atom in the aromatic heterocyclic group is a carbon atom in the formula (1-1). In addition, the aromatic heterocyclic group includes aromatic heterocyclic groups containing an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, etc. as heteroatoms, but it is preferable that it is a nitrogen-containing aromatic heterocyclic group, and a 4-pyridinyl group is more preferred. desirable.

Examples of the substituent for the aromatic group in R ¹ to R ³ include an alkyl group or a substituent for the alkyl group described above. Moreover, it is preferable that the substituent in the aromatic group does not contain an amino group or a substituted amino group.

In formula (1-1), it is preferable that none of R ¹ to R ³ are hydrogen atoms, or that only one is a hydrogen atom.

When at least one of R ¹ to R ³ is a hydrogen atom, it is preferred that at least one other of R ¹ to R ³ represents a branched structure or a cyclic structure, and the other two represent a branched or cyclic structure. do.

As the structure having the above 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 more preferable, and an isopropyl group is particularly preferable.

Examples of the structure having the cyclic structure include an alkyl group having a cyclic structure, or the substituted or unsubstituted aromatic group described above. An alkyl group having a cyclic structure having 6 to 20 carbon atoms is preferable, and a cycloalkyl group having 6 to 20 carbon atoms is preferable. is more preferable, and a cyclohexyl group is more preferable.

In formula (1-1), at least two of R ¹ to R ³ may combine to form a ring structure, and the ring structure formed may be either an aliphatic heterocyclic structure or an aromatic heterocyclic structure.

As the aliphatic heterocyclic structure, an aliphatic heterocyclic ring structure with a reduction number of 5 or 6 is preferable, a piperidine ring structure, a piperazine ring structure, and a morpholine ring structure are more preferable, and a piperidine ring structure is still more preferable.

As the aromatic heterocycle structure, an aromatic heterocycle structure with a reduction number of 5 or 6 is preferable, and examples include an imidazole ring structure, a pyridine ring structure, a pyrimidine ring structure, a pyrazine ring structure, and a pyridazine ring structure. A polyazole ring structure is more preferable.

In addition, the ring structure may further have a substituent, and examples of the substituent include the same groups as the substituents of the aromatic groups in R ¹ to R ³ described above.

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 structures include an aliphatic hydrocarbon ring structure, an aromatic hydrocarbon ring structure, an aliphatic heterocyclic structure, and an aromatic heterocyclic structure, and an aromatic hydrocarbon ring structure or an aliphatic heterocyclic structure is preferable. Compounds represented by formula (1-1) having such a condensed ring structure include 1,2-benzopyrazole, 1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimide [ 1,2-a] pyrimidine, etc. can be mentioned.

[Structure of a specific compound]

From the viewpoint of improving the film strength of the resulting cured film, specific compounds are selected from the group consisting of secondary aliphatic amines, tertiary aliphatic amines, secondary aromatic amines, tertiary aromatic amines, and nitrogen-containing heterocyclic compounds. It is preferable that it is at least one selected basic compound or a weak salt thereof.

Among these, secondary aliphatic amines or secondary aromatic amines are preferable from the viewpoint of improving the film strength of the resulting cured film.

Additionally, from the viewpoint of improving the storage stability of the composition, tertiary aliphatic amines, tertiary aromatic amines, or nitrogen-containing heterocyclic compounds are preferable.

In this specification, an aliphatic amine means that among the three structures (i.e., R ¹ to R ³ in formula (1-1)) bonded to the amine, at least one is an aliphatic hydrocarbon group, and the remaining two are Each independently refers to a hydrogen atom or an aliphatic hydrocarbon group.

A secondary aliphatic amine refers to one in which one of the three structures bonded to the amine is a hydrogen atom, and the remaining two are aliphatic hydrocarbon groups. Moreover, when the specific compound is a secondary aliphatic amine, it is preferable that at least one of the aliphatic hydrocarbon groups has a branched structure or a cyclic structure, and that all of the aliphatic hydrocarbon groups have a branched structure or a cyclic structure.

A tertiary aliphatic amine refers to one in which all three structures bonded to the amine are aliphatic hydrocarbon groups.

The preferred embodiment of the aliphatic hydrocarbon group in the description of the above-mentioned aliphatic amine, secondary aliphatic amine, or tertiary aliphatic amine is the same as the preferred embodiment of the aliphatic hydrocarbon group for R ¹ to R ³ described above. do. The aliphatic hydrocarbon group may further have the above-mentioned substituents.

Additionally, at least two of the aliphatic hydrocarbon groups in the secondary aliphatic amine or the tertiary aliphatic amine may be combined to form a ring structure. Examples of the ring structure formed include an aliphatic heterocyclic structure.

In this specification, an aromatic amine means that among the three structures (i.e., R ¹ to R ³ in formula (1-1)) bonded to the amine, at least one is an aromatic group, and the remaining two are each independent. This refers to a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic group.

A secondary aromatic amine refers to one in which only one of the three structures bonded to the amine is a hydrogen atom, the other is an aromatic group, and the remaining one is an aliphatic hydrocarbon group or an aromatic group.

A tertiary aromatic amine refers to one in which one of the three structures bonded to the amine is an aromatic group, and the remaining two are aliphatic hydrocarbon groups or aromatic groups.

Additionally, 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.

In the description of the aromatic amine, secondary aromatic amine, or tertiary aromatic amine, preferred embodiments of the aliphatic hydrocarbon group or aromatic group include the aliphatic hydrocarbon group or aromatic group in R ¹ to R ³ described above. It is the same as the preferred aspect of the group. The aliphatic hydrocarbon group or aromatic group may each further have the above-mentioned substituents.

-Secondary aliphatic amine-

As the secondary aliphatic amine, dialkylamine is preferable.

In this specification, dialkylamine refers to an amine compound in which one hydrogen atom and two alkyl groups are bonded to a nitrogen atom. Two alkyl groups in dialkylamine may be combined to form an aliphatic heterocyclic structure.

Of the two alkyl groups in the dialkylamine, it is preferable that at least one is a branched alkyl group or an alkyl group having a cyclic structure, and it is more preferable that both are branched alkyl groups, or both are alkyl groups having a cyclic structure.

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 the cyclic structure is the same as the preferred embodiment of the alkyl group having the cyclic structure in the structure having the cyclic structure described above.

-Tertiary aliphatic amine-

As the tertiary aliphatic amine, trialkylamine or N-alkyl nitrogen-containing aliphatic heterocyclic compound is preferable.

In this specification, trialkylamine refers to an amine compound in which three alkyl groups are bonded to a nitrogen atom. At least two alkyl groups in trialkylamine may be combined to form an aliphatic heterocyclic structure.

The three alkyl groups in the trialkylamine may be any of a straight-chain alkyl group, a branched alkyl group, or an alkyl group with a cyclic structure, but it is preferable that all of them are straight-chain 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 more preferable.

The preferred embodiment of the branched alkyl group or the alkyl group having a cyclic structure is the same as the preferred embodiment of the branched alkyl group or the alkyl group having a cyclic structure in the dialkylamine described above.

In this specification, an N-alkyl nitrogen-containing aliphatic heterocyclic compound refers to a hydrogen atom bonded to a nitrogen atom in a nitrogen-containing heterocycle structure such as a piperidine ring structure, a piperazine ring structure, or a morpholine ring, by an alkyl group. Refers to a substituted compound. One of the nitrogen atoms contained in these nitrogen-containing heterocyclic structures is the nitrogen atom described in the above-mentioned formula (1-1).

The alkyl group is preferably the same as the straight-chain alkyl group, branched alkyl group, or alkyl group having a cyclic structure in the trialkylamine described above, and among these, a branched alkyl group is more preferable.

Moreover, as the nitrogen-containing heterocycle structure, a nitrogen-containing heterocycle structure with a reduction number of 5 to 10 is preferable, and a nitrogen-containing heterocycle structure with a reduction number of 6 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 complex atoms other than nitrogen atoms, but preferably does not contain complex atoms other than nitrogen atoms.

As the nitrogen-containing heterocyclic ring structure, a pyridine ring or a morpholine ring structure is preferable.

-Secondary aromatic amine-

Examples of secondary aromatic amines include diarylamine or alkylarylamine.

In this specification, diarylamine refers to an amine compound in which one hydrogen atom and two aromatic groups are bonded to a nitrogen atom.

In this specification, 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 identical to the aromatic group in R ¹ to R ³ contained in the above-mentioned formula (1-1) is preferable.

The alkyl group in the alkylarylamine is preferably the same as the alkyl group in the trialkylamine described above.

-Tertiary aromatic amine-

Examples of tertiary aromatic amines include dialkylmonoarylamine, monoalkyldiarylamine, and triarylamine. Among these, dialkylmonoarylamine is preferable from the viewpoint of film strength of the resulting cured film.

In this specification, dialkylmonoarylamine refers to an amine compound in which two alkyl groups and one aromatic group are bonded to a nitrogen atom. Two alkyl groups in dialkylmonoarylamine may be combined to form an aliphatic heterocyclic structure.

In this specification, monoalkyldiarylamine refers to an amine compound in which one alkyl group and two aromatic groups are bonded to a nitrogen atom.

In this specification, triarylamine refers to an amine compound in which three aromatic groups are bonded to a nitrogen atom.

The aromatic group in the dialkylmonoarylamine, monoalkyldiarylamine, or triarylamine is preferably the same as the aromatic group for R ¹ to R ³ contained in the formula (1-1) described above. do.

The alkyl group in the dialkylmonoarylamine or the monoalkyldiarylamine is preferably the same as the alkyl group in the trialkylamine described above.

-Nitrogen-containing heterocyclic compounds-

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

<<Nitrogen-containing aromatic heterocyclic compound>>

The reduction number (as described later, in the case of a ring structure condensed with another ring structure, the reduction number of the monocycle containing a nitrogen atom as a reduction) in the nitrogen-containing aromatic heterocyclic compound is preferably 5 to 10, and is 5 or 6. It is more preferable that it is 5, and it is more preferable that it is 5.

The number of nitrogen atoms contained in the nitrogen-containing aromatic heterocyclic compound is preferably 1 to 3, more preferably 2 or 3, and still more preferably 2.

The nitrogen-containing aromatic heterocyclic compound may have a structure in which a nitrogen-containing aromatic heterocyclic ring structure and another ring structure are condensed. As said other ring structure, an aromatic ring is preferable, an aromatic hydrocarbon ring is more preferable, and a benzene ring is more preferable.

Examples of nitrogen-containing heteroaromatic compounds include substituted or unsubstituted imidazole compounds, substituted or unsubstituted pyrazole compounds, and substituted or unsubstituted benzopyrazole compounds.

Substituents in the imidazole compound, the pyrazole compound, or the benzopyrazole compound include the same groups as the substituents for R ¹ to R ³ in the formula (1-1) described above.

<<Nitrogen-containing aliphatic heterocyclic compounds>>

The reduction number (as described later, in the case of a ring structure condensed with another ring structure, the reduction number of the monocycle containing a nitrogen atom as a reduction) in the nitrogen-containing aliphatic heterocyclic compound is preferably 5 to 10, and is 5 or 6. It is more preferable that it is 5, and it is more preferable that it is 5.

The number of nitrogen atoms contained in the nitrogen-containing aliphatic heterocyclic compound is preferably 1 to 3, more preferably 2 or 3, and still more preferably 2.

The nitrogen-containing aliphatic heterocyclic compound may have a structure in which a nitrogen-containing aliphatic heterocyclic structure and another ring structure are condensed. As said other ring structure, an aliphatic ring structure is preferable, and an aliphatic hydrocarbon ring structure may be sufficient, but an aliphatic heterocyclic structure containing a nitrogen atom as a hetero atom is preferable. In addition, the aliphatic ring structure may be a saturated aliphatic ring structure or an unsaturated aliphatic ring structure.

Examples of nitrogen-containing aliphatic aromatic compounds include 1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimid[1,2-a]pyrimidine.

The specific compound is also preferably a monoamine compound or a weak salt thereof.

In this specification, a monoamine compound refers to a compound that has 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 secondary aliphatic amines, tertiary aliphatic amines, secondary aromatic amines, and tertiary aromatic amines, or a weak salt thereof, and It is preferable that it is a monoamine compound or a weak salt thereof.

〔Molecular Weight〕

From the viewpoint of the film strength of the cured film and the insulating properties of the resulting cured film, the molecular weight of the specific compound is preferably 60 to 200.

When the molecular weight is 200 or less, it is thought that, for example, the specific compound becomes easy to move during heating, and the effect of promoting cyclization of the heterocycle-containing polymer precursor becomes easy to obtain.

In addition, 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 decreases, so it is thought that the film strength of the cured film is likely to be improved.

The lower limit of the molecular weight is preferably 80 or more. Moreover, the upper limit of the molecular weight is preferably 190 or less, and more preferably 180 or less.

[Specific example]

Specific examples of specific compounds 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]pyrimidine, imidazole, 1,2-benzopyrazole, 5-methylpyrazole-3 -Methyl carboxylate, N, N-dimethylaminopyridine, dibenzylamine, N-t-butylbenzylamine, N-isopropylaniline, 4-morpholinopyridine, etc. are mentioned, but are not limited to these.

〔content〕

The content of the specific compound is preferably 0.05 to 20% by mass based on the total solid content of the curable resin composition from the viewpoint of improving the storage stability of the composition and the breaking elongation of the resulting cured film. As for the lower limit, 0.1 mass% or more is more preferable, 0.2 mass% or more is more preferable, and 0.3 mass% or more is especially preferable. The upper limit is more preferably 10 mass% or less, more preferably 5 mass% or less, and especially preferably 1 mass% or less from the viewpoint of corrosion resistance of metal (for example, copper used in wiring, etc.).

In addition, the content of the specific compound relative to 100 parts by mass of the heterocycle-containing polymer precursor is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, from the viewpoint of improving the storage stability of the composition and the breaking elongation of the resulting cured film. It is preferable, and it is more preferable that it is 2 parts by mass or more. The upper limit is preferably, for example, 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, from the viewpoint of corrosion resistance of metal (e.g., copper used in wiring, etc.). desirable.

One type or two or more types of specific compounds can be used. When using two or more types, it is preferable that the total amount is within the above range.

<Polymerization initiator>

The curable resin composition of the present invention contains a polymerization initiator.

The polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator, but it is preferable that it contains a photopolymerization initiator.

[Photopolymerization initiator]

It is preferable that the curable resin composition of the present invention contains a photopolymerization initiator.

Although the photopolymerization initiator may be a photocationic polymerization initiator, it is preferable that it is a radical photopolymerization initiator. The radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a radical photopolymerization initiator that has photosensitivity to light from the ultraviolet region to the visible region is preferred. Additionally, it may be an activator that produces an active radical by producing some kind of effect with the photo-excited sensitizer.

The radical photopolymerization initiator preferably 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). do. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure the concentration at a concentration of 0.01 g/L using an ethyl acetate solvent using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As a radical photopolymerization initiator, any known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide , oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds. , metallocene compounds, organic boron compounds, iron arene complexes, etc. For these details, reference may be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.

Examples of the ketone compound include compounds described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611, the content of which is incorporated herein by reference. As a commercially available product, Kayacure-DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

As a radical photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent Application Publication No. 4225898 can also be used.

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

As the aminoacetophenone-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 Resins) can be used.

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

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

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

As a radical photopolymerization initiator, an oxime compound is more preferable. By using an oxime compound, it becomes possible to improve the exposure latitude more effectively. Oxime compounds are particularly preferable because they have a wide exposure latitude (exposure margin) and also act as a photocuring accelerator.

Specific examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166.

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy ) Iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the curable resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a radical photopolymerization initiator. The oxime-based photopolymerization initiator has a linking group represented by >C=N-O-C(=O)- in the molecule.

[Formula 19]

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF) and Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd.; optical radicals described in Japanese Patent Application Publication No. 2012-014052). Polymerization initiator 2) is also suitably used. Additionally, TR-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka Ackles NCI-831 and Adeka Ackles NCI-930 (Changzhou Tronly New Electronic Materials Co., Ltd.) (made by ADEKA) can also be used. Additionally, DFI-091 (manufactured by Daito Chemicals Co., Ltd.) can be used.

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

[Formula 20]

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

The most preferable oxime compounds include oxime compounds having a specific substituent shown in Japanese Patent Application Laid-Open No. 2007-269779, oxime compounds having a thioaryl group shown in Japanese Patent Application Laid-Open No. 2009-191061, and the like.

From the viewpoint of exposure sensitivity, the radical photopolymerization initiator is trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, and metal. locene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complex and its salts, halomethyloxa Compounds selected from the group consisting of diazole compounds and 3-aryl substituted coumarin compounds are preferred.

More preferable radical photopolymerization initiators include trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium salt compounds. , a benzophenone compound, an acetophenone compound, and at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound. It is preferable, it is more preferable to use a metallocene compound or an oxime compound, and an oxime compound is even more preferable.

In addition, the radical photopolymerization initiator is N,N'-tetraalkyl-4,4'-diamino such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), etc. Benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholy Aromatic ketones such as no-propanone-1, quinones condensed with an aromatic ring such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyldimethylsiloxane. Benzyl derivatives such as methyl ketal can also be used. Moreover, a compound represented by the following formula (I) can also be used.

[Formula 21]

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or an alkyl group having 1 to 20 carbon atoms. Alkyl group, alkoxy group with 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group with 2 to 12 carbon atoms, alkyl group with 2 to 18 carbon atoms and 1 to 4 carbon atoms interrupted by one or more oxygen atoms. ^is a ^{phenyl group} or ^biphenyl group substituted with at least one of the alkyl groups of It is an alkoxy group or halogen atom with 1 to 12 carbon atoms.

[Formula 22]

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 in the above formula (I).

Moreover, as a radical photopolymerization initiator, the compound described in paragraphs 0048-0055 of International Publication No. 2015/125469 can also be used.

When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% by mass, based on the total solid content of the curable resin composition of the present invention. It is mass%, and is more preferably 1.0 to 10 mass%.

Only one type of photopolymerization initiator may be contained, and two or more types may be contained. When containing two or more types of photopolymerization initiators, it is preferable that the total is within the above range.

[Thermal polymerization initiator]

The curable resin composition of the present invention may contain a thermal polymerization initiator as a polymerization initiator, and may especially contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals using heat energy to initiate or promote the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the heterocycle-containing polymer precursor can be advanced along with cyclization of the heterocycle-containing polymer precursor, making it possible to achieve a higher degree of heat resistance.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-063554.

When a thermal radical polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 5% by mass, based on the total solid content of the curable resin composition of the present invention. It is ~15% by mass. The thermal radical polymerization initiator may contain only one type, and may contain two or more types. When containing two or more types of thermal radical polymerization initiators, it is preferable that the total is within the above range.

<Solvent>

The curable resin composition of the present invention contains a solvent. As the solvent, any known solvent can be used arbitrarily. The solvent is preferably an organic solvent. Examples of organic solvents 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 viewpoint of suppressing coating defects during application and improving storage stability.

The water content is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less.

Additionally, the water content may be 0% by mass.

As esters, for example, 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, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methoxy Methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., 3-alkyloxypropionic acid methyl, 3-alkyloxy Ethyl propionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (e.g. For example, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2 -methyl ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. 2-methoxy-2-methylpropionate) methyl, 2-ethoxy-2-methylethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, Suitable examples include ethyl heptanoate, dimethyl malonate, and diethyl malonate.

As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and 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, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, etc. can be mentioned as a suitable one.

Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone. You can.

Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

Suitable examples of sulfoxides include dimethyl sulfoxide.

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyl Suitable examples include amide, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide.

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 Colmonomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono Phenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

It is also preferable that two or more types of solvents are mixed 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-heptane. cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and One type of solvent selected from propylene glycol methyl ether acetate, or a mixed solvent consisting of two or more types is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of applicability, the solvent content is preferably such that the total solid concentration of the curable resin composition of the present invention is 5 to 80% by mass, and more preferably 5 to 75% by mass, It is more preferable to set it as an amount of 10 to 70 mass%, even more preferably to set it to 20 to 70 mass%, and even more preferably to set it to 40 to 70 mass%. The solvent content can be adjusted depending on the desired thickness and application method.

Only one type of solvent may be contained, and two or more types may be contained. When containing two or more types of solvents, it is preferable that the total is within the above range.

<Onium salt>

The curable resin composition of the present invention may further contain an onium salt.

The type of onium salt is not specifically determined, but ammonium salts, iminium salts, sulfonium salts, iodonium salts, or phosphonium salts are preferably used.

Among these, ammonium salts or iminium salts are preferable from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts, or phosphonium salts are preferable from the viewpoint of compatibility with polymers.

Additionally, an onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may be bonded through a covalent bond or may not be bonded through a covalent bond.

That is, the onium salt may be an intramolecular salt having a cationic moiety and an anionic moiety in the same molecular structure, or it may be an intermolecular salt in which a cationic molecule and an anionic molecule, which are separate molecules, are ionically bonded. However, it is preferable that the onium salt is an intermolecular salt. Moreover, in the curable resin composition of the present invention, the cationic moiety or cationic molecule and the anionic moiety or anionic molecule may be bound by an ionic bond or may be dissociated.

As the cation in the onium salt, ammonium cation, pyridinium cation, sulfonium cation, iodonium cation or phosphonium cation are preferable, and is selected from the group consisting of tetraalkylammonium cation, sulfonium cation and iodonium cation. At least one cation is more preferred.

The onium salt used in the present invention may be a heat base generator described later.

A thermobase generator refers to a compound that generates a base when heated, and examples include compounds that generate a base when heated to 40°C or higher.

[Ammonium salt]

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

-Ammonium cation-

As the ammonium cation, quaternary ammonium cation is preferable.

Moreover, as the ammonium cation, a cation represented by the following formula (101) is preferable.

[Formula 23]

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 each be bonded to form a ring.

In formula (101), R ¹ to R ⁴ are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and more preferably an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 12 carbon atoms. . R ¹ to R ⁴ may have a substituent, and examples of substituents include hydroxy group, aryl group, alkoxy group, aryloxy group, aryl carbonyl group, alkyl carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, and acyloxy group. etc. can be mentioned.

When at least two of R ¹ to R ⁴ are combined 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 either of the following formulas (Y1-1) and (Y1-2).

[Formula 24]

In formulas (Y1-1) and (Y1-2), R ¹⁰¹ represents an n-valent organic group, R ¹ has the same meaning as R ¹ in formula (101), and Ar ¹⁰¹ and Ar ¹⁰² are each independent. represents an aryl group, and n represents an integer of 1 or more.

In formula (Y1-1), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the structure to which they are bonded, and is preferably a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene, or It is more preferable that it is a group obtained by removing n hydrogen atoms from naphthalene.

In the formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and still more preferably 1.

In formula (Y1-2), Ar ¹⁰¹ and Ar ¹⁰² are each independently preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

-Anion-

As the anion in the ammonium salt, one type selected from carboxylic acid anion, phenol anion, phosphate anion, and sulfate anion is preferable, and carboxylic acid anion is more preferable because it can achieve both salt stability and thermal decomposition. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.

The carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and is more preferably an anion of a divalent carboxylic acid. According to this aspect, the stability, curability, and developability of the curable resin composition can be further improved. In particular, by using the anion of divalent carboxylic acid, 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).

[Formula 25]

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

In this embodiment, an electron withdrawing group means that Hammett's substituent constant σm shows a positive value. Here, σm is explained in detail in Yuho Tsuno's review, Journal of Organic Synthetic Chemistry, Volume 23, Number 8 (1965), pages 631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituents described in the above document.

Examples of substituents in which σm represents a positive value include CF ₃ group (σm=0.43), CF ₃ C(=O) group (σm=0.63), HC≡C group (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), etc. Additionally, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (the same applies hereinafter).

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

[Formula 26]

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

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

[Formula 27]

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

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

From the viewpoint of easy cyclization of the heterocycle-containing polymer precursor at low temperatures and easy improvement in storage stability of the curable resin composition, the onium salt in the present invention contains an ammonium cation as a cation, and the onium salt contains an ammonium cation as a cation. The anion preferably contains an anion whose pKa (pKaH) of the conjugate acid is 2.5 or less, and more preferably contains an anion whose pKa (pKaH) is 1.8 or less.

The lower limit of the pKa is not particularly limited, but from the viewpoint of making it difficult for the generated base to be neutralized and improving the cyclization efficiency of heterocycle-containing polymer precursors, etc., it is preferably -3 or more, and more preferably -2 or more.

As the pKa, Determination of Organic Structures by Physical Methods (author: Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; edited by: Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955) , the values described in Data for Biochemical Research (author: Dawson, R. M. C. et al; Oxford, Clarendon Press, 1959) can be referred to. For compounds not described in these documents, the value calculated from the structural formula using ACD/pKa (manufactured by ACD/Labs) software is used.

Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these.

[Formula 28]

[Iminium salt]

In the present invention, iminium salt means a salt of an iminium cation and an anion. Examples of the anion include the same anion as the anion in the ammonium salt described above, and the preferred embodiments are also the same.

-Iminium cation-

As the iminium cation, pyridinium cation is preferable.

Also, as the iminium cation, a cation represented by the following formula (102) is also preferable.

[Formula 29]

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 may each be bonded to form a ring. .

In formula (102), R ⁵ and R ⁶ have the same meaning as R ¹ to R ⁴ in formula (101) described above, and their preferred embodiments are also the same.

In formula (102), R ⁷ is preferably combined with at least one of R ⁵ and R ⁶ to form a ring. The ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom. Moreover, as said ring, a pyridine ring is preferable.

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

[Formula 30]

In formulas (Y1-3) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, R ⁵ has the same meaning as R ⁵ in formula (102), and R ⁷ has the same meaning as R 5 in formula (102). has the same meaning as R ⁷ , and 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 the structure to which they are bonded, and is preferably a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene, or It is more preferable that it is a group obtained by removing n hydrogen atoms from naphthalene.

In the formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and still more preferably 1.

In the formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and still more preferably 1.

Specific examples of iminium salts include the following compounds, but the present invention is not limited to these.

[Formula 31]

[Sulfonium salt]

In the present invention, sulfonium salt means a salt of a sulfonium cation and an anion. Examples of the anion include the same anion as the anion in the ammonium salt described above, and the preferred embodiments are also the same.

-Sulfonium cation-

As the sulfonium cation, a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable.

Moreover, as the sulfonium cation, a cation represented by the following formula (103) is preferable.

[Formula 32]

In formula (103), R ⁸ to R ¹⁰ each independently represent a hydrocarbon group.

R ⁸ to R ¹⁰ are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 12 carbon atoms, more preferably an aryl group with 6 to 12 carbon atoms, and a phenyl group. It is more preferable to be

R ⁸ to R ¹⁰ may have a substituent, and examples of substituents include hydroxy group, aryl group, alkoxy group, aryloxy group, aryl carbonyl group, alkyl carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, and acyloxy group. etc. can be mentioned. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and more preferably a branched alkyl group with 3 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms. .

R ⁸ to R ¹⁰ may be the same or different, but from the viewpoint of synthetic aptitude, it is preferable that they are the same group.

Specific examples of sulfonium salts include the following compounds, but the present invention is not limited to these.

[Formula 33]

[Iodonium salt]

In the present invention, iodonium salt means a salt of an iodonium cation and an anion. Examples of the anion include the same anion as the anion in the ammonium salt described above, and the preferred embodiments are also the same.

-iodonium cation-

As the iodonium cation, diaryliodonium cation is preferable.

Moreover, as the iodonium cation, a cation represented by the following formula (104) is preferable.

[Formula 34]

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 with 1 to 10 carbon atoms or an aryl group with 6 to 12 carbon atoms, more preferably an aryl group with 6 to 12 carbon atoms, and a phenyl group. It is more preferable to be

R ¹¹ and R ¹² may have a substituent, and examples of substituents include hydroxy group, aryl group, alkoxy group, aryloxy group, aryl carbonyl group, alkyl carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, and acyloxy group. etc. can be mentioned. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and more preferably a branched alkyl group with 3 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms.

R ¹¹ and R ¹² may be the same or different, but from the viewpoint of synthetic aptitude, it is preferable that they are the same group.

Specific examples of iodonium salts include the following compounds, but the present invention is not limited to these.

[Formula 35]

[Phosphonium salt]

In the present invention, phosphonium salt means a salt of a phosphonium cation and an anion. Examples of the anion include the same anion as the anion in the ammonium salt described above, and the preferred embodiments are also the same.

-phosphonium cation-

As the phosphonium cation, a quaternary phosphonium cation is preferable, and examples thereof include tetraalkylphosphonium cation and triarylmonoalkylphosphonium cation.

Moreover, as the phosphonium cation, a cation represented by the following formula (105) is preferable.

[Formula 36]

In formula (105), R ¹³ to R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group.

R ¹³ to R ¹⁶ are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 12 carbon atoms, more preferably an aryl group with 6 to 12 carbon atoms, and a phenyl group. It is more preferable to be

R ¹³ to R ¹⁶ may have a substituent, and examples of substituents include hydroxy group, aryl group, alkoxy group, aryloxy group, aryl carbonyl group, alkyl carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, and acyloxy group. etc. can be mentioned. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and more preferably a branched alkyl group with 3 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms.

R ¹³ to R ¹⁶ may be the same or different, but from the viewpoint of synthetic aptitude, it is preferable that they are the same group.

Specific examples of phosphonium salts include the following compounds, but the present invention is not limited to these.

[Formula 37]

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 with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5 mass% or more, more preferably 0.85 mass% or more, and even more preferably 1 mass% or more. The upper limit is more preferably 30 mass% or less, further preferably 20 mass% or less, even more preferably 10 mass% or less, may be 5 mass% or less, and may be 4 mass% or less.

One type or two or more types of onium salts can be used. When using two or more types, it is preferable that the total amount is within the above range.

<Thermobase generator>

The curable resin composition of the present invention may further contain a thermobase generator.

The other heat base generator may be a compound corresponding to the above-mentioned onium salt, or may be a heat base generator other than the above-mentioned onium salt.

Examples of heat base generators other than the above-mentioned onium salts include nonionic heat base generators.

Nonionic thermobase generators include compounds represented by formula (B1) or formula (B2).

[Formula 38]

In formulas (B1) and (B2), Rb ¹ , Rb ² and Rb ³ each independently represent an organic group, a halogen atom or a hydrogen atom without a tertiary amine structure. However, Rb ¹ and Rb ² never become hydrogen atoms at the same time. In addition, Rb ¹ , Rb ² and Rb ³ do not all have a carboxyl group. In addition, in this specification, the tertiary amine structure refers to a structure in which all three bonding hands of a trivalent nitrogen atom are covalently bonded to hydrocarbon-based carbon atoms. Therefore, an exception is made when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when it forms an amide group 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 of them 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 fused together is preferred. The monocycle is preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring is more preferable. As for a single ring, a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and more preferably 3 to 12), or an alkenyl group (preferably having 2 to 24 carbon atoms) , 2 to 18 are more preferable, 3 to 12 are more preferable), an aryl group (carbon numbers are preferably 6 to 22, more preferably 6 to 18, and 6 to 10 are more preferable), or an arylalkyl group ( It is preferable that the number of carbon atoms is 7 to 25, more preferably 7 to 19, and more preferably 7 to 12. These groups may have substituents within the range that exhibits the effects of the present invention. Rb ¹ and Rb ² may be bonded 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 preferably a straight-chain, branched, or cyclic alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent. , a cycloalkyl group that may have a substituent (carbon number is preferably 3 to 24, more preferably 3 to 18, and 3 to 12 are more preferable), and a cyclohexyl group that may have a substituent is more preferable. do.

Rb ³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 are more preferable), alkenyl group (carbon atoms are preferably 2 to 24, more preferably 2 to 12, and 2 to 6 are more preferable), arylalkyl group (carbon atoms are preferably 7 to 23, and 7 to 19 is more preferable, 7 to 12 are more preferable), arylalkenyl group (carbon number is preferably 8 to 24, 8 to 20 is more preferable, and 8 to 16 are more preferable), alkoxyl group (carbon number is 1 to 1) 24 is preferable, 2 to 18 are more preferable, and 3 to 12 are more preferable), an aryloxy group (carbon number is preferably 6 to 22, more preferably 6 to 18, and 6 to 12 are more preferable) , or an arylalkyloxy group (carbon atoms of 7 to 23 are preferable, 7 to 19 carbon atoms are more preferable, and 7 to 12 carbon atoms are more preferable). Among them, a cycloalkyl group (carbon number 3 to 24 is preferable, 3 to 18 are more preferable, and 3 to 12 are still more preferable), an arylalkenyl group, and an arylalkyloxy group are preferable. Rb ³ may further have a substituent within the range that produces the effect of the present invention.

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

[Formula 39]

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in formula (B1), respectively.

Rb ¹³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18, more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and 3 ~12 is more preferable), aryl group (carbon number is preferably 6 to 22, more preferably 6 to 18, more preferably 6 to 12), arylalkyl group (carbon number is preferably 7 to 23, 7 to 19) is more preferable, and 7 to 12 is more preferable), and may have a substituent within the range showing the effect of the present invention. Among them, Rb ¹³ is preferably an arylalkyl group.

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

Rb ³⁵ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more 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 are more preferable), aryl group (carbon number is preferably 6 to 22, more preferably 6 to 18, and 6 to 12 are more preferable), arylalkyl group (carbon number is preferably 7 to 23, and 7 to 19 is more preferable, 7 to 12 are more preferable), and an aryl group is preferable.

The compound represented by the formula (B1-1) is also preferably a compound represented by the formula (B1-1a).

[Formula 40]

Rb ¹¹ and Rb ¹² have the same meaning as Rb ¹¹ and Rb ¹² in formula (B1-1).

Rb ¹⁵ and Rb ¹⁶ are a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and more preferably 1 to 3), or an alkenyl group (preferably having 2 to 12 carbon atoms, and 2 to 6 carbon atoms) It is more preferable, 2 to 3 is more preferable), aryl group (carbon number is 6 to 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), arylalkyl group (carbon number is 7 to 23) preferred, 7 to 19 are more preferred, and 7 to 11 are further preferred), and a hydrogen atom or a methyl group is preferred.

Rb ¹⁷ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 3 to 8), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 12, 3) ~8 is more preferable), aryl group (carbon number is preferably 6 to 22, more preferably 6 to 18, more preferably 6 to 12), arylalkyl group (carbon number is preferably 7 to 23, 7 to 19) is more preferable, and 7 to 12 is more preferable), and among them, an aryl group is 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 heat base generators, or specific examples of heat base generators other than the above-mentioned onium salts, include the following compounds.

[Formula 41]

[Formula 42]

[Formula 43]

The content of the other heat base generator 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, and more preferably 1% by mass or more. As for the upper limit, 30 mass % or less is more preferable, and 20 mass % or less is more preferable. One type or two or more types of thermobase generators can be used. When using two or more types, it is preferable that the total amount is within the above range.

<Polymerizable compound>

[Radically polymerizable compound]

It is preferable that the curable resin composition of the present invention further contains a polymerizable compound.

As the polymerizable compound, a radically polymerizable compound can be used. A 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 radical polymerizable group is preferably a (meth)acryloyl group, and from a reactive viewpoint, a (meth)acryloxy group is more preferable.

The number of radically polymerizable groups in the radically polymerizable compound may be 1 or 2 or more, but the radically polymerizable compound preferably has 2 or more radically polymerizable groups, and more preferably has 3 or more. The upper limit is preferably 15 or less, more preferably 10 or less, and still 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 still more preferably 900 or less. The lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.

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

Specific examples of radically polymerizable compounds include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably , esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, addition reaction products between unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxy, amino, or sulfanyl groups and monofunctional or polyfunctional isocyanates or epoxies, or monofunctional Alternatively, dehydration condensation reactants with polyfunctional carboxylic acids are also suitably used. In addition, addition reactants of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group and monofunctional or polyfunctional alcohols, amines, or thiols, as well as halogeno groups or tosyloxy groups. Substitution reactants of unsaturated carboxylic acid esters or amides having a dissociable substituent such as monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. Also, as another example, instead of the above unsaturated carboxylic acid, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. As a specific example, the description of paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357 can be referred to, and these contents are incorporated in this specification.

Additionally, the radically polymerizable compound is also preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol. Tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol(meth)acrylate, trimethylol propane tri(acryloyloxy) Compound obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as propyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, or trimethylolethane, and then turning them into (meth)acrylates, Japanese notice. Urethane (meth)acrylates as described in Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Application Publication No. 51-037193, Japanese Patent Application Publication No. 51-037193. Polyester acrylates described in Japanese Patent Publications No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490, and epoxy acrylate, which is a reaction product of epoxy resin and (meth)acrylic acid. Examples include polyfunctional acrylates and methacrylates, and mixtures thereof. Additionally, the compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also suitable. Moreover, polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond can also be mentioned.

Preferred radically polymerizable compounds other than those described above include those described in JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc., which have a fluorene ring and are ethylenic. It is also possible to use a compound having two or more groups with an unsaturated bond or a cardo resin.

In addition, other examples include specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. 01-040336, and Japanese Patent Publication No. 02-025493. Vinylphosphonic acid-based compounds described in No. 1, etc. can also be mentioned. Additionally, a compound containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. 61-022048 can also be used. Also, Journal of the Japan Adhesive Association, vol. 20, no. 7, pages 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, the contents of which are incorporated herein by reference.

In addition, ethylene oxide or propylene oxide is added to the polyfunctional alcohol described with specific examples as formula (1) and formula (2) in Japanese Patent Application Laid-Open No. 10-062986, followed by (meth)acrylate. The compound can also be used as a radically polymerizable compound.

In addition, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as radically polymerizable compounds, the contents of which are incorporated herein by reference.

As the radically polymerizable compound, dipentaerythritol triacrylate (as a commercial product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product: KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) ) agent, A-TMMT: manufactured by Shinnakamura Chemical Industry Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa. (meth)acrylate (commercially available products include KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.; A-DPH; manufactured by Shinnakamura Chemical Co., Ltd.), and their (meth)acryloyl group is an ethylene glycol residue or propylene glycol A structure in which they are bonded via a cole residue is preferable. These oligomeric types can also be used.

Commercially available radical polymerizable compounds include, for example, SR-494, a tetrafunctional acrylate with four ethyleneoxy chains, manufactured by Sartomer, and SR-, a bifunctional methacrylate with four ethyleneoxy chains, manufactured by Sartomer. 209, 231, 239, DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, and TPA-330, a trifunctional acrylate with three isobutyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd. Lethene oligomer UAS-10, UAB-140 (manufactured by Nippon Seishi Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shinnakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Kagaku Co., Ltd.), Blemmer PME400 (manufactured by Nippon Kayaku Co., Ltd.) Heoyu Co., Ltd.) and the like can be mentioned.

As a radically polymerizable compound, it is described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765. The same urethane acrylates and ethylene 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. Urethane compounds having an oxide-based skeleton are also suitable. In addition, as a radically polymerizable compound, it has an amino structure or a sulfide structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238. Compounds 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 is a radical polymerizable compound obtained by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxy group of the aliphatic polyhydroxy compound to give an acid group. Compounds are more preferred. Particularly preferably, in a radically 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 dipentaerythritol. It is a phosphorus compound. Commercially available products include, for example, polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.

The preferred 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. If the acid value of the radically polymerizable compound is within the above range, the handleability in manufacturing is excellent and, furthermore, the developability is excellent. Additionally, it has good polymerizability. The acid value is measured based on the description of JIS K 0070:1992.

The curable resin composition of the present invention preferably uses bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.

Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate (polyethylene glycol It is cold diacrylate, and the content of the polyethylene glycol chain is about 200), PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol. Lycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol Diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) of bisphenol A Adduct diacrylate, EO adduct of bisphenol A Dimethacrylate, PO adduct of bisphenol A Diacrylate, EO adduct of bisphenol A Dimethacrylate, 2-hydroxy-3-acryloyloxypropyl Methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates with a urethane bond, and bifunctional methacrylates with a urethane bond. can be used. These can be used in combination of two or more types as needed.

In addition, as bifunctional or higher radical crosslinking agents, diallyl phthalate, triallyl trimellitate, etc. can be mentioned.

From the viewpoint of suppressing bending by controlling the elastic modulus of the cured film, a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound. Monofunctional radically polymerizable compounds include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and carbitol ( Meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol (meth)acrylic acid derivatives such as lycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinyl caprolactam, allyl glycol Allyl compounds such as sidyl ether are preferably used. As monofunctional radically polymerizable compounds, compounds having a boiling point of 100°C or higher under normal pressure are also preferred 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 may further contain polymerizable compounds other than the radically polymerizable compounds described above. Polymerizable compounds other than the radically polymerizable compounds described above include compounds having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; epoxy compounds; oxetane compounds; and benzoxazine compounds.

-Compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group-

As a 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.

[Formula 44]

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

[Formula 45]

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

[Formula 46]

(In the formula, u represents an integer of 3 to 8, R ⁵⁰⁴ represents a u-valent organic group having 1 to 200 carbon atoms, R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ , and R ⁵⁰⁶ represents, It 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 compounds represented by formula (AM4) include 46DMOC, 46DMOEP (trade name, Asahi Yukizai Kogyo Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML -PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, brand name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKALAC MX-290 ( Brand name (manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc.

Additionally, specific examples of compounds represented by formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP. , HMOM-TPPHBA, HMOM-TPHAP (above, brand name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), TM-BIP-A (brand name, manufactured by Asahi Yukizai Kogyo Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270 , NIKALAC MW-100LM (above, brand name, manufactured by Sanwa Chemical Co., Ltd.).

-Epoxy compound (compound having an epoxy group)-

The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at temperatures below 200°C, and since dehydration reactions resulting from crosslinking do not occur, membrane shrinkage is unlikely to occur. For this reason, containing an epoxy compound is effective in suppressing low-temperature curing and warping 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 bending can be suppressed. A polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and it is preferable that the number of repeating units is 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resin; Bisphenol F-type epoxy resin; Alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; Polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Silicones containing epoxy groups such as polymethyl (glycidyloxypropyl) siloxane may be mentioned, but are not limited to these. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) EXA-4710, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclon (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4850-150, Epiclon (registered trademark) EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP- S, Epiclon (registered trademark) N-740 (trade name above, manufactured by DIC Corporation), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE- 100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (brand name, manufactured by New Nippon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (or more) Product name, manufactured by ADEKA Co., Ltd.), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, Celoxide (registered trademark) 2000, EHPE3150, Epolyde (registered trademark) GT401, Epolyde (registered trademark) ) PB4700, Epolide (registered trademark) PB3600 (trade name above, 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, Examples include 104S, CER-1020, EPPN-201, BREN-S, and BREN-10S (trade names above, manufactured by Nippon Kayaku Co., Ltd.). Among these, an epoxy resin containing a polyethylene oxide group is preferable because it suppresses warping and is excellent in heat resistance. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and Lyca Resin (registered trademark) BEO-60E are preferred because they contain a polyethylene oxide group.

-Oxetane compound (compound having an oxetanyl group)-

Examples of oxetane compounds 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, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. . As a specific example, the Aaronoxetane series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be suitably used, either alone or in combination of two or more types. You can mix it.

-Benzoxazine compound (compound having a benzoxazolyl group)-

Benzoxazine compounds are preferable because they prevent degassing during curing due to a crosslinking reaction resulting from a ring-opening addition reaction, and also reduce heat shrinkage and suppress the occurrence of warping.

Preferred examples of benzoxazine compounds include B-a-type benzoxazine, B-m-type benzoxazine, P-d-type benzoxazine, F-a-type benzoxazine (above, brand name, manufactured by Shikoku Chemical Industry Co., Ltd.), and benzoxazine of polyhydroxystyrene resin. Oxazine adducts and phenol novolak-type dihydrobenzoxazine compounds can be mentioned. These may be used individually, or two or more types may be mixed.

When containing a polymerizable compound, its content 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. As for the lower limit, 5 mass% or more is more preferable. As for the upper limit, it is more preferable that it is 50 mass % or less, and it is still more preferable that it is 30 mass % or less.

Polymerizable compounds may be used individually, or two or more types may be mixed and used. When using two or more types together, it is preferable that the total amount falls within the above range.

<Migration inhibitor>

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

There are no particular restrictions on the migration inhibitor, but heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine) Compounds having a ring, 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 A compound having a, hindered phenol-based compound, salicylic acid derivative-based compound, and hydrazide derivative-based compound can be mentioned. 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 captures anions such as halogen ions can be used.

Other migration inhibitors include rust inhibitors described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, compounds described in paragraph 0052 of JP2011-059656, The compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, the compounds described in paragraph 0166 of International Publication No. 2015/199219, etc. can be used.

Specific examples of migration inhibitors include the following compounds.

[Formula 47]

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

The number of migration inhibitors may be one, or two or more types may be used. When there are two or more migration inhibitors, it is preferable that the total is within the above range.

<Polymerization inhibitor>

It is preferable that the curable resin composition of the present invention contains a polymerization inhibitor.

Polymerization inhibitors include, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, and 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 4-acetic 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 primary 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-tetra Methylpiperidine 1-oxyl free radical, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyl dithiocarbanate copper(II), nitrobenzene, N-nitroso- N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. are suitably used. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

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

[Formula 48]

When the curable resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor can be, 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, and 0.01 to 20.0% by mass. It is preferable that it is 5 mass %, it is more preferable that it is 0.02-3 mass %, and it is still more preferable that it is 0.05-2.5 mass %. Moreover, when storage stability of the curable resin composition solution is required, an aspect of 0.02 to 15.0 mass% is also preferably mentioned, and in that case, 0.05 to 10.0 mass% is more preferable.

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

<Metal adhesion improver>

The curable resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, Amino compounds, etc. can be mentioned.

Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, and the compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992. Examples include the compounds described, the compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 2014-191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, and the compounds described in paragraph 0055 of International Publication No. 2014/097594. You can. Additionally, it is also preferable to use two or more different types of silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358. Moreover, it is also preferable to use the following compounds as the silane coupling agent. In the formula below, Et represents an ethyl group.

[Formula 49]

Other silane coupling agents include, for example, vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxypropylmethyl. Dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxy Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxy Silane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl -3-Aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mer Captopropyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride can be mentioned. These can be used individually or in combination of two or more types.

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

[Aluminum-based adhesive aid]

Examples of the aluminum-based adhesion aid include aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), and ethyl acetoacetate aluminum diisopropylate.

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the heterocycle-containing polymer precursor. It is a range. By setting it above the above lower limit, the adhesion between the cured film and the metal layer after the curing process becomes good, and by setting it below the above upper limit, the heat resistance and mechanical properties of the cured film after the curing process become good. The number of metal adhesion improving agents may be one, or two or more types may be used. When using two or more types, it is preferable that the total is within the above range.

<Other additives>

The curable resin composition of the present invention may contain various additives, such as a thermal acid generator, a sensitizer such as N-phenyldiethanolamine, a chain transfer agent, a surfactant, and a higher grade, as necessary, within the range where the effects of the present invention can be obtained. Fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. can be mixed. When blending these additives, 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 activating radiation and becomes electronically excited. The sensitizer in an electronically excited state comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal curing accelerator, thermal radical polymerization initiator, and photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids, or bases.

Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine. In addition, benzophenone, Michler's ketone, coumarin, pyrazolazo, anilinoazo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, and pyrazolotriane. Compounds such as zoazine-based, pyridonezo-based, cyanine-based, phenocyazine-based, pyrrolopyrazolazomethane-based, xanthene-based, phthalocyanine-based, benzopyran-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'-die Ethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis( diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p- Dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis (4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-di Methylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(dimethylaminocoumarin) Ethylamino) Coumarin-3-carboxylic acid ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, Isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminosthyl Ryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-di) Examples include methylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide.

Additionally, as a sensitizer, a sensitizing dye may be used.

For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357 can be referred to, and this content is incorporated herein by reference.

When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, and more preferably 0.1 to 15% by mass, relative to the total solid content of the curable resin composition of the present invention. It is preferable, and it is more preferable that it is 0.5-10 mass %. Sensitizers may be used individually, or two or more types may be used in combination.

[Chain transfer system]

The curable resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in pages 683-684 of the Polymer Dictionary, 3rd edition (Polymer Society edition, 2005). As chain transfer agents, for example, a group of compounds having -SS-, -SO ₂ -S-, -NO-, SH, PH, SiH, and GeH in the molecule, and those used in RAFT (Reversible Addition Fragmentation chain Transfer) polymerization. Dithiobenzoate, trithiocarbonate, dithiocarbamate, and xanthate compounds having a thiocarbonylthio group are used. These can generate radicals by donating hydrogen to low-activity radicals, or by deprotonating them after being oxidized. In particular, thiol compounds can be preferably used.

Additionally, the chain transfer agent may be a compound described in paragraphs 0152 to 0153 of International Publication No. 2015/199219.

When the curable resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total solid content of the curable resin composition of the present invention. , 1 to 5 parts by mass is more preferable. There may be only one type of chain transfer agent, or two or more types may be used. When there are two or more chain transfer agents, it is preferable that the total is within the above range.

〔Surfactants〕

Each type of surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving applicability. 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. Additionally, the following surfactants are also preferred. In the formula below, parentheses indicating the repeating units of the main chain indicate the content (mol%) of each repeating unit, and parentheses indicating the repeating units of the side chain indicate the number of repetitions of each repeating unit.

[Formula 50]

Additionally, the surfactant may be a compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219.

When the curable resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the curable resin composition of the present invention. am. The number of surfactants may be one, or two or more types may be used. When there are two or more types of surfactants, it is preferable that the total is within the above range.

[Advanced fatty acid derivatives]

To prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the curable resin composition of the present invention and distributed on the surface of the curable resin composition during the drying process after application.

Additionally, 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 contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the curable resin composition of the present invention. There may be only one type of high-grade fatty acid derivative, or two or more types may be used. When there are two or more types of higher fatty acid derivatives, it is preferable that the total is within the above range.

<Restrictions on other contained substances>

From the viewpoint of the coated surface properties, the moisture 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 still more preferably less than 0.6% by mass.

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

Additionally, as a method of reducing metal impurities unintentionally contained in the curable resin composition of the present invention, raw materials with a low metal content are selected as raw materials constituting the curable resin composition of the present invention, or raw materials constituting the curable resin composition of the present invention are selected. Methods include performing filter filtration on the raw materials, lining the inside of the device with polytetrafluoroethylene, etc., and performing distillation under conditions that suppress contamination as much as possible.

Considering the use of the curable resin composition of the present invention as a semiconductor material, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass from the viewpoint of wiring corrosion. This is more preferable. Among them, the amount of the halogen ion present in the state is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass. Halogen atoms include chlorine atoms and bromine atoms. It is preferable that the sum of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, respectively, is within the above range.

As a container for containing the curable resin composition of the present invention, a conventionally known container can be used. In addition, as a storage container, for the purpose of suppressing the incorporation of impurities into the raw materials or curable resin composition, a multi-layer bottle whose inner wall is made of 6 types of 6-layer resins or a bottle with 6 types of resins in a 7-layer structure are used. It is also desirable to do so. Examples of such containers include those described in Japanese Patent Application Publication 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 redistribution layer.

Additionally, it can be used for the formation of an insulating film of a semiconductor device, the formation of a stress buffer film, etc.

(Method for producing curable resin composition)

The manufacturing method of the curable resin composition of the present invention is preferably a manufacturing method including the step of mixing each of the above-mentioned components contained in the curable resin composition. The mixing method is not particularly limited and can be performed by a conventionally known method.

In addition, the method for producing a curable resin composition of the present invention includes a step of mixing a composition containing a heterocycle-containing polymer precursor, the polymerization initiator, and the solvent (hereinafter also referred to as a precursor composition) and a specific compound. It is also desirable to have a method. The mixing method is not particularly limited and can be performed by a conventionally known method.

If necessary, the precursor composition may further contain components included in the curable resin composition of the present invention, such as the radically polymerizable compound, onium salt, and thermobase generator described above.

As the precursor composition, a composition excluding a specific compound from the curable resin composition of the present invention is preferable.

In the manufacturing method using the precursor composition, the precursor composition may be obtained through purchase or the like, and the manufacturing method further includes a step of preparing the precursor composition by mixing each component contained in the precursor composition. You can do it. The mixing method is not particularly limited and can be performed by a conventionally known method.

In the manufacturing method using the precursor composition, a specific compound can be added, for example, immediately before forming a film with the curable resin composition.

Additionally, for the purpose of removing foreign substances such as dust and fine particles in the curable resin composition, it is preferable to perform filtration using a filter. The filter pore diameter may be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and 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 previously washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected and used in series or parallel. When using multiple types of filters, filters with different pore diameters or materials may be used in combination. Additionally, various materials may be filtered multiple times. When filtering multiple times, circular filtration may be used. Additionally, filtration may be performed under pressure. When performing filtration by pressurizing, the pressurizing pressure may be, 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, more preferably 0.05 MPa or more and 0.7 MPa or less, and 0.05 MPa or more. 0.3 MPa or less is more preferable.

In addition to filtration using a filter, treatment to remove impurities using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

(cured film, laminate, semiconductor device, and their manufacturing method)

Next, the cured film, the laminated body, the semiconductor device, and their manufacturing methods are explained.

The cured film of the present invention is formed 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. Additionally, the upper limit can be set to 100 μm or less, and can also be set to 30 μm or less.

The cured film of the present invention may be laminated in two or more layers, and further, in 3 to 7 layers to form a laminate. The laminated body of this invention preferably contains two or more layers of cured films, and includes a metal layer between any one of the cured films. For example, a laminated body containing at least a layer structure in which three layers of the first cured film, the metal layer, and the second cured film are laminated in this order is mentioned as a preferable one. Both the first cured film and the second cured film are cured films of the present invention, for example, an embodiment in which both the first cured film and the second cured film are films formed by curing the curable resin composition of the present invention. can be mentioned as a desirable one. 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 may be compositions with the same composition or compositions with different compositions. The metal layer in the laminate of the present invention is preferably used as a metal wiring such as a redistribution layer.

Applicable fields of the cured film of the present invention include insulating films of semiconductor devices, interlayer insulating films for redistribution layers, and stress buffer films. In addition, patterns may be formed by etching sealing films, substrate materials (base films, cover lays, and interlayer insulating films of flexible printed circuit boards), or insulating films for mounting purposes as described above. Regarding their uses, for example, Science & Technology Co., Ltd., "Highly functionalization and application technology of polyimide", April 2008, Masaaki Kakimoto/Supervision, CMC Technical Library, "Basics and development of polyimide materials", 2011. You can refer to the Japanese Polyimide and Aromatic Polymer Research Society/edit, “Latest Polyimide Basics and Applications,” N·T·S, August 2010, published in November.

In addition, the cured film in the present invention can also be used for the production of plates such as offset plates or screen plates, for use in etching of molded parts, and for the production of 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 production method of the present invention”) preferably includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film.

It is also preferable that the method for producing a cured film of the present invention includes 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 film forming step.

The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step of exposing the film, and a development step of developing the film.

Moreover, the method for producing a cured film of the present invention includes the film forming step and, if necessary, the developing step, and more preferably 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). Additionally, if necessary, the step (a') may be included before (a).

(a') Composition production process of mixing a precursor composition and a specific compound to produce the curable resin composition of the present invention

(a) Film forming process of applying a curable resin composition to a substrate to form a film (curable resin composition layer)

(b) After the film formation process, the exposure process exposes the film.

(c) developing process to develop the exposed film

(d) Heating process of heating the developed film at 50 to 450 ° C.

By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating process, for example, the above-mentioned thermobase generator is decomposed, and sufficient curability is obtained.

The manufacturing method of a laminated body according to a preferred embodiment of the present invention includes the manufacturing method of the cured film of the present invention. The manufacturing method of the laminated body of this embodiment is, after forming a cured film according to the manufacturing method of the said cured film, again the process of (a), or the process of (a)-(c), or (a)- The step (d) is further performed. In particular, it is preferable to perform each of the above steps in order, multiple times, for example, 2 to 5 times (i.e., 3 to 6 times in total). By laminating the cured film in this way, a laminate 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 addition, in the production of the laminate, it is not necessary to repeat all of the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to A cured film laminate can be obtained by performing the step (d) multiple times.

When performing the step (a) multiple times, the step (a') may be further performed before each step (a), and the curable resin composition produced in one step (a') may be used in plural times. It may be used in the process of meeting (a).

<Film formation process (layer formation process)>

The manufacturing method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which a curable resin composition is applied to a substrate to form a film (layer).

The type of substrate can be appropriately determined depending on the application, but includes semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, There are no particular restrictions, such as reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, and electrode plates of plasma display panels (PDP).

In the present invention, a semiconductor fabrication substrate is particularly preferable, and a silicone substrate and a mold resin substrate are more preferable.

Additionally, as the base material, for example, a plate-shaped base material (substrate) is used.

In addition, when forming a curable resin composition layer 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.

As a means of applying the curable resin composition to the substrate, application is preferred.

Specifically, the applied means include the dip coat method, air knife coat method, curtain coat method, wire bar coat method, gravure coat method, extrusion coat method, spray coat method, spin coat method, slit coat method, and Examples include the inkjet method. From the viewpoint of uniformity of the thickness of the curable resin composition layer, spin coating method, slit coating method, spray coating method, and inkjet method are more preferable. By appropriately adjusting the solid content concentration or application conditions according to the method, a resin layer of the desired thickness can be obtained.

Additionally, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet methods are preferable, and for rectangular substrates, slit coating, spray coating, or inkjet methods are preferable. etc. are preferable. In the case of the spin coat method, for example, it can be applied for 10 to 180 seconds at a rotation speed of 300 to 3,500 rpm, and can be applied for about 10 seconds to 1 minute at a rotation speed of 500 to 2,000 rpm. . Additionally, in order to achieve uniformity in film thickness, application may be performed by combining a plurality of rotations.

Additionally, a method of transferring the coating film previously formed by applying it on a temporary support according to the above-mentioned application method onto a substrate can also be applied.

Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can be suitably used in the present invention.

<Drying process>

The manufacturing method of the present invention may include a drying step to remove the solvent after forming the film (curable resin composition layer) and then forming the film (layer forming step). The preferred drying temperature is 50°C to 150°C, more preferably 70°C to 130°C, and more preferably 90°C to 110°C. Examples of the drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes. When the amount of solvent in the curable resin composition solution is large, vacuum drying and heat drying can also be combined. Heating drying uses a hot plate, hot air oven, etc., and is not particularly limited.

<Exposure process>

The manufacturing method of the present invention may include an exposure step of exposing the film (curable resin composition layer). The exposure amount is not particularly determined as long as it can cure the curable resin composition, 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 irradiate 200 to 8,000 mJ/cm ² It is more desirable to do so.

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

The exposure wavelength is related to the light source: (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436nm), h line (wavelength 405nm), i-line (wavelength 365nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ₂ excimer Laser (wavelength 157 nm), (5) extreme ultraviolet; Examples include EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser with a second harmonic of 532 nm and a third harmonic of 355 nm. For the curable resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferable, and exposure with i-line is especially preferable. Thereby, particularly high exposure sensitivity can be obtained. Also, from the viewpoint of handling and productivity, a broad (3 wavelengths of g, h, and i lines) light source such as a high-pressure mercury lamp or a 405 nm semiconductor laser are also suitable.

<Development process>

The manufacturing method of the present invention may include a development step of performing development on the exposed film (curable resin composition layer) (developing the film). By performing development, the unexposed portion (non-exposed portion) is removed. The development method is not particularly limited as long as the desired pattern can be formed, and for example, development methods such as puddle, spray, immersion, and ultrasonic waves can be adopted.

Development is performed using a developing solution. The developer can be used without particular restrictions as long as it removes the unexposed portion (non-exposed portion).

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

Organic solvents include esters, such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and methyl lactate. , ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methoxyacetic acid) Methyl, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (e.g., 2-alkyl Methyl oxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate) , ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, 2-ethyl) ethyl oxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethers, for example For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol. Colmonomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl. -2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene, and dimethyl sulfoxide as sulfoxides. It can be lifted appropriately.

In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred.

Additionally, the developer may contain a surfactant.

It is preferable that 50 mass% or more of the developing solution is an organic solvent, more preferably 70 mass% or more of an organic solvent, and even more preferably 90 mass% or more of an organic solvent. Additionally, 100% by mass of the developer may be an organic solvent.

The developing time is preferably 10 seconds to 5 minutes. The temperature of the developing solution during development is not particularly determined, but can usually be carried out at 20 to 40°C.

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

<Heating process>

The manufacturing method of the present invention preferably includes a step of heating the developed film at 50 to 450° C. (heating step).

The heating process is preferably included after the film forming process (layer forming process), the drying process, and the developing process. In the heating process, for example, the above-described thermal base generator decomposes to generate a base, and the cyclization reaction of the heterocycle-containing polymer precursor progresses. In addition, the curable resin composition of the present invention may contain radically polymerizable compounds other than the heterocycle-containing polymer precursor, but curing of radically polymerizable compounds other than the unreacted heterocycle-containing polymer precursor can also be carried out in this step. . The heating temperature (maximum heating temperature) of the layer in the heating process is preferably 50°C or higher, more preferably 80°C or higher, more preferably 140°C or higher, still more preferably 150°C or higher, and 160°C or higher. It is even more preferable, and it is even more preferable that it is 170°C or higher. The upper limit is preferably 500°C or lower, more preferably 450°C or lower, more preferably 350°C or lower, still more preferably 250°C or lower, and even more preferably 220°C or lower.

Heating is preferably performed at a temperature increase rate of 1 to 12°C/min from the temperature at the start of heating to the highest heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the temperature increase rate to 1°C/min or more, excessive volatilization of amine can be prevented while ensuring productivity, and by setting the temperature increase rate to 12°C/min or less, residual stress in the cured film can be alleviated.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and still 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 a curable resin composition is applied to a substrate and then dried, the temperature of the film (layer) after drying is, for example, 30 to 200°C lower than the boiling point of the solvent contained in the curable resin composition. It is desirable to gradually increase the temperature from then on.

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

In particular, when forming a multilayer laminate, the heating temperature is preferably 180°C to 320°C, and more preferably 180°C to 260°C, from the viewpoint of adhesion between the layers of the cured film. Although the reason is not clear, it is thought that by setting this temperature, a crosslinking reaction is occurring between the ethyneyl groups of the heterocycle-containing polymer precursor between layers.

Heating may be performed in stages. For example, a pretreatment process such as raising the temperature from 25°C to 180°C at 3°C/min, holding at 180°C for 60 minutes, raising the temperature at 2°C/min from 180°C to 200°C, and holding at 200°C for 120 minutes. You can do it. The heating temperature as a pretreatment process 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 process while irradiating ultraviolet rays as described in U.S. Patent Publication No. 9159547. It is possible to improve the properties of the membrane through this pretreatment process. The pretreatment process may be performed in a short period of time, such as 10 seconds to 2 hours, and 15 seconds to 30 minutes is more preferable. The pretreatment may be performed in two or more steps, for example, pretreatment step 1 may be performed in the range of 100 to 150°C, and then pretreatment step 2 may be performed in the range of 150 to 200°C.

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

The heating process is preferably performed in an atmosphere with low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon under vacuum, in order to prevent decomposition of the heterocycle-containing polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

<Metal layer formation process>

The manufacturing method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the film (curable resin composition layer) after development.

As the metal layer, there is no particular limitation, and existing metal species can be used, examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, copper and aluminum are more preferable, and copper is still more preferable. .

The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, and Japanese Patent Application Publication No. 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and methods combining these are contemplated. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned.

The thickness of the metal layer is preferably 0.1 to 50 μm, and more preferably 1 to 10 μm in the thickest part.

<Laminating process>

The manufacturing method of the present invention preferably further includes a lamination process.

The lamination process refers to the processes of (a) film formation process (layer formation process), (b) exposure process, (c) development process, and (d) heating process again on the surface of the cured film (resin layer) or metal layer. It is a series of processes that involve performing them in sequence. However, only the film forming process (a) may be repeated.

Additionally, the heating step (d) may be performed all at once at the end or in the middle of lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, followed by the heating in (d), thereby curing the laminated curable resin composition layers all at once. In addition, after the developing process (c), the metal layer forming process (e) may be included, and in this case, the heating in (d) may be performed each time, or the heating in (d) may be performed all at once after stacking a predetermined number of times. do. It goes without saying that the lamination process may further include the above drying process, heating process, etc. as appropriate.

When further performing the lamination process after the lamination process, a surface activation treatment process may be further performed after the heating process, the exposure process, or the metal layer formation process. An example of surface activation treatment is plasma treatment.

The lamination process is preferably performed 2 to 5 times, and is more preferably performed 3 to 5 times.

For example, a structure such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably comprised of 3 to 7 layers, and more preferably 3 to 5 layers.

In the present invention, it is particularly preferable to form a cured film (resin layer) of the curable resin composition to cover the metal layer after providing the metal layer. Specifically, (a) film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, (d) heating process are repeated in this order, or (a) film formation process. , (b) exposure process, (c) development process, and (e) metal layer formation process are repeated in this order, and (d) heating process is provided at the end or in the middle. By alternately performing the lamination process of laminating the curable resin composition layer (resin layer) and the metal layer formation process, the curable resin composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses a semiconductor device containing the cured film or laminate of the present invention. As a specific example of a semiconductor device using the curable resin composition of the present invention for forming an interlayer insulating film for a redistribution layer, the description in paragraphs 0213 to 0218 of Japanese Patent Application Laid-Open No. 2016-027357 and the description in FIG. 1 can be referred to. It is used herein.

Example

The present invention will be described in more detail below with reference to examples. Materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. “Part” and “%” are based on mass, unless otherwise specified.

<Synthesis Example 1>

[A-1: Polyimide precursor resin A-1 from oxydiphthalic dianhydride, 4,4'-biphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether synthesis〕

While removing moisture in a dry reactor equipped with a flat-bottom joint equipped with a stirrer, condenser, and internal thermometer, 9.49 g (32.25 mmol) of 4,4'-biphthalic anhydride and 10.0 g (32.25 mmol) of oxydiphthalic dianhydride were added. ) 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 continuously added, and stirred at a temperature of 60°C for 18 hours. Next, the mixture was 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. Next, the mixture was warmed to room temperature and stirred for 2 hours, then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 1 hour to the obtained transparent liquid. Next, 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. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was collected by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure. The weight average molecular weight of the obtained polyimide precursor A-1 was 24,800 and the number average molecular weight was 10,500.

Moreover, 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 moisture in a dry reactor equipped 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 continuously added, and stirred at a temperature of 60°C for 18 hours. Next, the mixture was 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. Next, the mixture was warmed to room temperature and stirred for 2 hours, then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 1 hour to the obtained transparent liquid. Next, 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. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was collected by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure. The weight average molecular weight of the obtained polyimide precursor A-2 was 23,500 and the number average molecular weight was 8,800.

Moreover, the acid value of the obtained polyimide precursor A-2 was 15.8 mgKOH/g.

<Synthesis Example 3>

[A-3: Polybenzoxazole precursor A-3 from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydibenzoyl chloride synthesis〕

28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was stirred and dissolved in 200 g of N-methylpyrrolidone. Subsequently, 12.1 g (153 mmol) of pyridine was added, and 20.7 g (70.1 mmol) of 4,4'-oxydibenzoyl chloride was dissolved in 75 g of N-methylpyrrolidone while maintaining the temperature at -10 to 0°C. The 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 stirred for an additional 60 minutes. Next, the polybenzoxazole precursor resin was precipitated in 6 liters of water, and the water-polybenzoxazole precursor resin mixture was stirred at a speed 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. Next, the obtained polybenzoxazole precursor resin was dried at 45°C for 3 days under reduced pressure. The weight average molecular weight of the obtained polybenzoxazole precursor A-3 was 21,500 and the number average molecular weight was 9,500.

Moreover, the acid value of the obtained polybenzoxazole precursor A-3 was 190 mgKOH/g.

[Formula 51]

<Synthesis Example 4>

[Polyimide precursor from 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-4: Polyimide having a radical polymerizable group) Synthesis of precursor)]

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. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After completion of heat generation due to the reaction, the mixture was left to cool to room temperature and left to stand for another 16 hours.

Next, under ice cooling, a solution in which 206.3 g of dicyclohexylcarbodiimide (DCC) was dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture for 40 minutes while stirring. Subsequently, a suspension in which 93.0 g of 4,4'-diaminodiphenyl ether was suspended in 350 ml of γ-butyrolactone was added while stirring for 60 minutes. After stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour. After that, 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 liquid was added to 3 liters of ethyl alcohol to produce a precipitate consisting 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 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 2-hydroxyethyl methacrylate polyimide precursor (A-5: radical Synthesis of polyimide precursor having a polymerizable group]

The method described in Synthesis Example 4, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride. By performing the reaction in the same manner as above, polymer A-5 was obtained. 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 example described as "when preparing a solution" in the "method of adding a specific compound" column, the components shown in Table 1 or Table 2 below were mixed to obtain each curable resin composition. In addition, in each comparative example, the components shown in Table 2 below were mixed to obtain each comparative composition.

In each example described as "immediately before film formation" in the "Method for adding a specific compound" column, 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 compound shown in Table 1 or Table 2 was mixed with the precursor composition to obtain a curable resin composition.

Specifically, the content of the components listed in Table 1 was set to the amount listed in “Parts by Mass” in Table 1.

The obtained curable resin composition and comparative composition were filtered under pressure through a polytetrafluoroethylene filter with a micropore width of 0.8 μm.

In Table 1, for example, the descriptions "A-1/A-2" and "16/16" indicate that 16 parts by mass of A-1 and 16 parts by mass of A-2 are contained.

In addition, in Table 1, the description of "-" indicates that the composition does not contain the corresponding component.

[Table 1]

[Table 2]

The details of each component listed in Table 1 are as follows.

[Heterocycle-containing polymer precursor]

·A-1~A-5: A-1~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]pyrimidine

BE-8: Imidazole

BE-9: 1,2-benzopyrazole

BE-10: 5-methylpyrazole-3-carboxylic acid methyl

BE-11: N-isopropylaniline

·B-1: 3-aminopropyltriethoxysilane

Compound B-1 is a compound containing an alkoxysilyl group and does not correspond to a specific compound.

·B-2: Diethylamine

Compound B-2 is a compound that has a hydrogen atom and does not have a branched structure or a cyclic structure, and is a compound that does not correspond to 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-Beautyrolactone

·Ethyl lactate

·NMP: N-methylpyrrolidone

In Table 1, the description of DMSO/GBL indicates that DMSO and GBL were mixed at a ratio of DMSO:GBL=20:80 (mass ratio).

In Table 1, the description of NMP/ethyl lactate 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 Sartomer)

SR-231: SR-231 (manufactured by Sartomer)

SR-239: SR-239 (manufactured by Sartomer)

A-DPH: Dipentaerythritol hexaacrylate (manufactured by Shinnakamura Chemical Industry Co., Ltd.)

[Onium salt or thermobase generator]

·F-1 or F-2: Compound with the following structure.

[Formula 52]

[Polymerization inhibitor]

·G-1: 1,4-benzoquinone

·G-2: 4-methoxyphenol

·G-3: 1,4-dihydroxybenzene

G-4: 2-Nitroso-1-naphthol (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

[Metal adhesion improver]

·H-1 to H-4: The following compounds

Et represents an ethyl group.

[Formula 53]

[Migration inhibitor]

·H-1: 1H-tetrazole

〔additive〕

J-1: N-phenyldiethanolamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

In all of the curable resin compositions in the examples, the water content relative 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 coulometric titration method).

<Evaluation>

[Evaluation of ultimate strength (elongation at break)]

In each Example and Comparative Example, the curable resin composition or the comparative composition was applied on a silicon wafer by spin coating 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 with 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-line 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 exposure is heated at a temperature increase rate of 10°C/min in a nitrogen atmosphere, and after reaching the temperature described in the “curing temperature (°C)” column in Table 1, it is heated for 3 hours. did. The cured resin layer (cured film) was immersed in a 4.9 mass% aqueous hydrofluoric acid solution, and the cured film was peeled from the silicon wafer. The peeled cured film was punched using a punching machine to produce a test piece with a sample width of 3 mm and a sample length of 30 mm. The obtained test piece was measured at break in the longitudinal direction of the film in accordance with JIS-K6251 in an environment of 25°C and 65%RH (relative humidity) at a crosshead speed of 300 mm/min using a tensile tester (Tensilon). Measured. The evaluation was performed five times each, and the arithmetic average value of the elongation rate (break elongation rate) when the film was broken was used as a reference value.

The above-described reference values were evaluated according to the following evaluation criteria, and the evaluation results were described in the “Film Strength” column of Table 1. It can be said that the larger the above-mentioned index value, the better the film strength (elongation at break) of the obtained cured film.

-Evaluation standard-

A: The above indicator value was more than 60%.

B: The above indicator value was 55% or more and less than 60%.

C: The above indicator value was 50% or more and less than 55%.

D: The above indicator value was less than 50%.

[Evaluation of storage stability (membrane change rate)]

-Measurement of film thickness before aging-

In each Example and Comparative Example, the curable resin composition or the comparative composition was applied on a silicon wafer by spin coating 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 with 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 film thickness before aging. The film thickness was measured at 10 points on the coated surface with an ellipsometer (KT-22, manufactured by Foothill) and obtained as the arithmetic average value.

-Measurement of film thickness after aging-

In each Example and Comparative Example, the curable resin composition or comparative composition (precursor composition in the Example described as "immediately before film formation" in the "Method of adding a specific compound" column) was placed in a glass container and sealed, After standing for 14 days at 25°C in a light-shielding environment, the curable resin composition or comparative composition (indicate “immediately before film forming” in the “Method of adding a specific compound” column) using the same number of rotations as when calculating the film thickness before aging. In the described examples, a specific compound was mixed with the precursor composition immediately before film formation) was applied on a silicon wafer by spin coating 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 of 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 measurement method in the above-described method of measuring film thickness before aging, and this value was taken as the film thickness after aging.

-Film thickness change rate-

The film thickness change rate was calculated using the following equation.

Film thickness change rate (%)=|Film thickness before aging - Film thickness after aging|/Film thickness before aging × 100

The calculated film thickness change rate was evaluated according to the following evaluation criteria, and the evaluation results were described in the "Storage Stability" column in Table 1. It can be said that the smaller the film thickness change rate, the better the storage stability of the curable resin composition.

-Evaluation standard-

A: The film thickness change rate was less than 10%.

B: The film thickness change rate 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 (membrane change rate)]

In each Example and Comparative Example, the curable resin composition or the comparative composition was applied on a silicon wafer by spin coating 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 with a uniform thickness of 15 μm on the silicon wafer. The curable resin composition layer on the silicon wafer was exposed to i-line 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 exposed to 10 The temperature was raised at a temperature increase rate of °C/min and heated to the temperature 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: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25 mass% tetramethylammonium hydroxide (TMAH) aqueous solution.

Evaluation conditions: The resin layer was immersed in the chemical solution at 75°C for 15 minutes, the film thickness before and after was compared, and the dissolution rate (nm/min) was calculated. The film thickness was measured at 10 points on the coated surface with an ellipsometer (KT-22, manufactured by Foothill) and obtained as the arithmetic average value.

Evaluation was conducted according to the following evaluation criteria, and the evaluation results were described in the "Chemical Resistance" column in Table 1. It can be said that the smaller the value of the dissolution rate, the better the chemical resistance of the resulting cured film (resin layer).

-Evaluation standard-

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 a heterocycle-containing polymer precursor, a specific compound, a polymerization initiator, and a 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 any specific compounds. It can be seen that the curable resin compositions of Comparative Examples 1 to 6 are inferior in the film strength of the cured film.

<Example 101>

The curable resin composition used in Example 1 was applied in a layered manner by spin coating to the surface of the thin copper layer of the resin substrate on which the thin copper layer was formed, dried at 100°C for 5 minutes, and the film thickness was 20 μm. After forming the curable resin composition layer, it was exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line and space pattern 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.

Next, it was heated at 230°C for 3 hours to form an interlayer insulating film for the redistribution layer. This interlayer insulating film for the redistribution layer had excellent insulating properties.

Additionally, as a result of manufacturing a semiconductor device using these interlayer insulating films for the redistribution layer, it was confirmed that it operated without problems.

Claims (20)

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 salt thereof,
a polymerization initiator, and
Contains a solvent,
The basic compound or its weak salt is at least one basic compound selected from the group consisting of secondary aliphatic amines, tertiary aliphatic amines, secondary aromatic amines, tertiary aromatic amines, and nitrogen-containing heterocyclic compounds. or its weak acid salt,
The weak salt is carbonate, acetate, oxalate or borate,
The nitrogen-containing heterocyclic compound is a substituted or unsubstituted pyrazole compound, a substituted or unsubstituted benzopyrazole compound, or 1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimide. [1,2-a]pyrimidine,
Curable resin composition.
[Formula 1]

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 at least 2 of R ¹ to R ³ may be combined to form a ring structure, R ¹ to R ³ do not contain an alkoxysilyl group as a substituent, and when at least one of R ¹ to R ³ is a hydrogen atom, at least one of R ¹ to R ³ is a hydrogen atom. Represents a structure having a branched structure or a cyclic structure,
The aliphatic hydrocarbon group is an alkyl group,
When the aliphatic hydrocarbon group has a substituent, the substituent is an aromatic hydrocarbon group, an aromatic heterocyclic group, an alkoxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, or a polymerizable group, and the polymerizable group is a vinyl group, an allyl group, or (meth ) is an acrylamide group,
When the aromatic group has a substituent, the substituent is an alkyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, an alkoxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, or a polymerizable group, and the polymerizable group is a vinyl group, an allyl group, (meth ) It is an acrylamide group or a methacryloxy group, and when at least two of R ¹ to R ³ combine to form a ring structure, the ring structure is a piperidine ring structure, a piperazine ring structure, a morpholine ring structure, and a pyrimidine ring structure. It is a dine ring structure, a pyrazine ring structure, or a pyridazine ring structure, and the ring structure may further have a substituent or may be further condensed with another ring structure. delete In claim 1,
A curable resin composition wherein the basic compound or its weak acid salt is a monoamine compound or its weak acid salt. In claim 1,
A curable resin composition in which the content of the basic compound or its weak salt is 0.2 to 10% by mass based on the total solid content of the composition. In claim 1,
A curable resin composition in which the molecular weight of the basic compound or its weak salt is 60 to 200. In claim 1,
A curable resin composition wherein the resin is a polyimide precursor having a repeating unit represented by the following formula (1).
[Formula 2]

In formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each represent Independently, it represents a hydrogen atom or a monovalent organic group. In claim 6,
A curable resin composition wherein at least one of R ¹¹³ and R ¹¹⁴ contains a radical polymerizable group. In claim 1,
A curable resin composition wherein the acid value of the resin is 8 to 80 mgKOH/g. In claim 1,
A curable resin composition wherein the water content is 5% by mass or less based on the total mass of the solvent. In claim 1,
A curable resin composition further comprising a radically polymerizable compound. In claim 1,
A curable resin composition further comprising at least one member selected from the group consisting of an onium salt and a heat base generator. In claim 1,
A curable resin composition used for forming an interlayer insulating film for a redistribution layer. A method for producing the curable resin composition according to claim 1, comprising:
A method for producing a curable resin composition, comprising the step of mixing a composition containing the resin, the polymerization initiator, and the solvent, and a basic compound represented by formula (1-1) or a weak salt thereof. A cured film formed by curing the curable resin composition according to claim 1. A laminate comprising two or more layers of the cured film according to claim 14 and a metal layer between any one of the cured films. A method for producing a cured film comprising a film forming step of applying the curable resin composition according to claim 1 to a substrate to form a film. In claim 16,
A step of producing the curable resin composition by mixing a composition containing the resin, the polymerization initiator, and the solvent, and a basic compound having a structure represented by formula (1-1) or a weak salt thereof, comprising: forming the film A method for producing a cured film, including before the process. In claim 16,
A method for producing a cured film, comprising an exposure process of exposing the film and a development process of developing the film. In claim 16,
A method for producing a cured film, comprising a heating process of heating the film at 50 to 450°C. A semiconductor device comprising the cured film according to claim 14.