KR20230044259A - Curable resin composition, cured product, laminate, method for producing cured product, semiconductor device, and compound - Google Patents

Abstract

A polyimide precursor, a polybenzoxazole precursor, a polyamideimide precursor, at least one resin selected from the group consisting of polyimide, polybenzoxazole, and polyamideimide, a polymerization inhibitor having an alkoxysilyl group, a polymerizable compound, and A curable resin composition containing a photopolymerization initiator, a cured product obtained by curing the curable resin composition, a laminate including the cured product, a method for producing the cured product, and a semiconductor device including the cured product or the laminate .

Description

Curable resin composition, cured product, laminate, method for producing cured product, semiconductor device, and compound

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

Since polyimide, polybenzoxazole, or polyamideimide is excellent in heat resistance, insulation, and the like, it is applied to various applications. Although it does not specifically limit as said use, If the semiconductor device for mounting is given as an example, the material of an insulating film or sealing material, or use as a protective film is mentioned. Moreover, it is also used as a base film or cover lay of a flexible substrate.

For example, in the above-mentioned use, the polyimide, polybenzoxazole or polyamideimide is composed of a polyimide precursor, a polybenzoxazole precursor, a polyamideimide precursor, a polyimide, a polybenzoxazole and a polyamideimide. It is used in the form of a curable resin composition containing at least one resin selected from the group.

Such a curable resin composition is applied to a base material by, for example, coating to form a resin film, and thereafter, a cured product is formed on the base material by performing exposure, development, heating, etc. as necessary. can

The polyimide precursor, the polybenzoxazole precursor, and the polyamideimide precursor are cyclized by, for example, heating, and become polyimide, polybenzoxazole, and polyamideimide, respectively, in the cured product.

Since the curable resin composition can be applied by a known coating method or the like, it is said that the curable resin composition to be applied is excellent in manufacturing adaptability, for example, with a high degree of freedom in designing the shape, size, application position, etc. at the time of application. can do. In addition to the high performance possessed by polyimide, polybenzoxazole, polyamideimide, etc., industrial application development of the curable resin composition described above is increasingly expected from the viewpoint of excellent adaptability in manufacturing.

For example, in Patent Document 1, (A) an alkoxysilane compound having an arylamino group or a pyridyl group in its molecular structure, (B) a heat-resistant resin having a phenolic hydroxyl group or a carboxyl group in its molecular structure, or precursors thereof, (C ) a photosensitive resin composition containing a photoactive component selected from the group consisting of a photopolymerization initiator and a quinonediazide compound, and (D) a diluting solvent.

In Patent Literature 2, (a) a polyimide precursor having an absorbance of 0.1 or more and 0.8 or less at 308 nm when heated at 350°C for 1 hour to obtain a polyimide resin film having a film thickness of 0.1 μm, and (b) 0.001% by mass of NMP A resin composition characterized by containing an alkoxysilane compound having an absorbance of 308 nm when used as a solution at a thickness of 1 cm of the solution is 0.1 or more and 1.0 or less is described.

Patent Document 1: Japanese Unexamined Patent Publication No. 2002-258485 Patent Document 2: Japanese Unexamined Patent Publication No. 2019-094499

Curable resin compositions are required to suppress footing in patterns obtained after development.

Footing means that in the deep part of the film made of curable resin composition (the area on the substrate side of the film made of curable resin composition), even in the unexposed area, the area where the film is not removed by development remains, and the pattern obtained is This protruding shape means that the footing is suppressed means that the length of the footing is shortened in the formed pattern.

The present invention provides a curable resin composition in which footing of a pattern obtained after development is suppressed, a cured product formed by curing the curable resin composition, a layered product including the cured product, a method for producing the cured product, and the cured product or the cured product. It is an object of the present invention to provide a semiconductor device including a laminate.

Moreover, an object of this invention is to provide a novel compound.

Examples of representative embodiments of the present invention are shown below.

<1> at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, polyimides, polybenzoxazoles, and polyamideimides;

A polymerization inhibitor having an alkoxysilyl group;

polymerizable compounds, and

A curable resin composition comprising a photopolymerization initiator.

<2> The curable resin composition according to <1>, wherein the polymerization inhibitor contains at least one structure selected from the group consisting of an aminooxy radical structure, a phenol structure, a nitrobenzene structure, and a benzoquinone structure.

<3> The curable resin composition according to <1> or <2>, in which the polymerization inhibitor contains at least one structure selected from the group consisting of an amide structure and a urea structure.

<4> Curable resin composition in any one of <1>-<3> containing compound B which is a compound which has a polymeric group and an azole group.

Curable resin composition in any one of <1>-<4> containing compound C which is a compound which does not have a <5> polymeric group but has an azole group.

<6> The curable resin composition according to <5>, wherein the compound C is a compound represented by the following formula (C-1) or the following formula (C-2);

[Formula 1]

In formula (C-1), each of Z ¹ to Z ⁴ independently represents =CR ⁷ - or a nitrogen atom, R ¹ represents a hydrogen atom or a monovalent organic group, and R ⁷ represents a hydrogen atom or a monovalent organic group. and does not contain a polymerizable group in the structure represented by formula (C-1);

In formula (C-2), Z ⁵ to Z ⁶ each independently represent =CR ⁸ - or a nitrogen atom, R ² to R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and R ⁸ is A hydrogen atom or a monovalent organic group is shown, and a polymerizable group is not included in the structure represented by formula (C-2).

<7> The curable resin composition according to any one of <1> to <6>, further comprising a silane coupling agent having no azole group as a silane coupling agent different from the polymerization inhibitor having an alkoxysilyl group.

<8> The curable resin composition according to any one of <1> to <7>, which is used for forming an interlayer insulating film for a redistribution layer.

<9> A cured product formed by curing the curable resin composition according to any one of <1> to <8>.

<10> A laminate comprising two or more layers of layers made of the cured material according to <9>, and including a metal layer between any one of the layers made of the cured material.

<11> A method for producing a cured product including a film formation step of applying the curable resin composition according to any one of <1> to <8> on a substrate to form a film.

<12> The method for producing a cured product according to <11>, including an exposure step of selectively exposing the film and a developing step of forming a pattern by developing the film using a developing solution.

<13> The method for producing a cured product according to <11> or <12>, including a heating step of heating the film at 50 to 450°C.

<14> A semiconductor device comprising the cured product according to <9> or the laminate according to <10>.

<15> A compound having an aminooxy radical structure and an alkoxysilyl group.

According to the present invention, a curable resin composition in which footing of a pattern obtained after development is suppressed, a cured product obtained by curing the curable resin composition, a laminate including the cured product, a method for producing the cured product, and the cured product or A semiconductor device including the laminate is provided.

Moreover, according to this invention, a novel compound is provided.

EMBODIMENT OF THE INVENTION Hereinafter, the main embodiment of this invention is described. However, the present invention is not limited to the specific embodiments.

In this specification, the numerical range represented by the symbol "-" means the range which includes the numerical value described before and after "-" as a lower limit value and an upper limit value, respectively.

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

In the notation of a group (atomic group) in this specification, the notation that does not describe substitution and unsubstitution includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

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

In the present specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)acryl" refers to "acryl" and "methacryl". “(meth)acryloyl” means either or both of “acryloyl” and “methacryloyl”.

In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In this specification, the 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 is the mass percentage of other components except a solvent with respect to the total mass of a composition.

In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values, unless otherwise specified. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, using HLC-8220GPC (manufactured by Tosoh Co., Ltd.), and as a column, guard column HZ-L, TSKgel Super HZM- M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (above, manufactured by Tosoh Co., Ltd.) are connected in series and used. These molecular weights shall be measured using THF (tetrahydrofuran) as an eluent unless otherwise specified. However, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as an eluent, such as when the solubility is low. In addition, detection in the GPC measurement assumes that a detector with a wavelength of 254 nm of UV rays (ultraviolet rays) is used unless otherwise specified.

In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", the reference layer among a plurality of layers of interest It is only necessary if there is another layer on the upper or lower side. That is, a third layer or element may be further interposed between the layer serving as the standard and the other layer, and the layer serving as the standard and the other layer need not be in contact with each other. In addition, unless otherwise specified, the direction in which layers are laminated with respect to the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "upper", The opposite direction is referred to as "lower". Note that the setting of such a vertical direction is for convenience in this specification, and in an actual aspect, there may be cases where the “upper” direction in this specification is different from vertically upward.

In this specification, as long as there is no special description, a composition may also contain two or more types of compounds corresponding to the component as each component contained in a composition. In addition, unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.

In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

In this specification, a combination of preferable aspects is a more preferable 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, a polybenzoxazole precursor, a polyamideimide precursor, a polyimide, a polybenzoxazole, and a polyamideimide (hereinafter referred to as “specific resin”). It is also referred to as ".), a polymerization inhibitor having an alkoxysilyl group (hereinafter, also referred to as "specific polymerization inhibitor"), a polymerizable compound, and a photopolymerization initiator.

It is preferable that the curable resin composition of this invention is a negative curable resin composition.

A negative curable resin composition refers to a composition in which, when a layer formed of the curable resin composition is exposed, an unexposed portion (non-exposed portion) is removed by a developing solution.

According to the curable resin composition of the present invention, footing of a pattern obtained after development is suppressed.

Although the mechanism by which the said effect is obtained is unknown, it is guessed as follows.

Conventionally, when a photosensitive film made of a curable resin composition containing a photopolymerization initiator and a polymerizable compound is partially cured by pattern exposure, polymerization is less likely to be inhibited by oxygen or the like in the deep portion of the film, and the influence of reflected light by the base material, etc. Since polymerization proceeds easily by this, there was a case where the pattern obtained by development became a footing shape.

However, the curable resin composition of the present invention contains a specific polymerization initiator.

Therefore, in the photosensitive film obtained from the composition of the present invention, a large amount of the polymerization inhibitor having an alkoxysilyl group is present in the vicinity of the substrate (ie, the interface side between the substrate and the composition film) in the photosensitive film, and excessive polymerization in the deep portion of the photosensitive film. Since this is suppressed, it is thought that footing is suppressed.

In addition, when a specific resin is used as the resin, it is conceivable to use a cured product composed of a curable resin composition as an insulating film, but there is a demand for forming a thick cured product from the viewpoint of insulation and the like. Here, it is presumed that the effect of suppressing the footing is particularly remarkable when the thickness of the photoresist film is thick (for example, 10 μm or more, preferably 15 μm or more, etc.).

Moreover, according to the curable resin composition of this invention, since excessive polymerization in a core part is suppressed as mentioned above, it is estimated that resolution and exposure latitude are also excellent.

In addition, since the polymerization inhibitor is unevenly distributed in the deep part of the film and the amount of the polymerization inhibitor present on the surface is relatively small, it is estimated that the cured product is also excellent in chemical resistance.

Here, in patent document 1 or 2, there is neither description nor suggestion about the curable resin composition containing a specific resin, a specific polymerization inhibitor, a polymeric compound, and a photoinitiator.

Hereinafter, components included in the curable resin composition of the present invention will be described in detail.

<specific resin>

The curable resin composition (hereinafter, simply referred to as “resin composition”) of the present invention is from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyamideimide precursor, a polyimide, a polybenzoxazole, and a polyamideimide. At least one selected resin (specific resin) is included.

It is preferable that curable resin composition of this invention contains a polyimide or a polyimide precursor as a specific resin, and it is more preferable that a polyimide precursor is included.

Moreover, it is preferable that specific resin has a polymeric group.

As a polymerizable group in a specific resin, well-known polymerizable groups, such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxymethyl group, are mentioned.

As the radical polymerizable group, a group having an ethylenically unsaturated bond is preferable.

Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group bonded directly to an aromatic ring such as a vinyl group, an allyl group, and a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and the like. and a (meth)acryloyloxy group is preferable.

It is preferable that specific resin has, as a polymeric group, the polymeric group in the compound B mentioned later, and the polymeric group which can superpose|polymerize.

As a combination of polymerizable groups capable of polymerization, a specific resin has a radical polymerizable group and compound B has a radical polymerizable group, or a specific resin has an epoxy group and compound B has an epoxy group. can be heard

According to the above aspect, the polymerizable group in the specific resin and the polymerizable group in the compound B are polymerized in the cured product, the bond between the specific resin and the compound B is strengthened, and the resulting cured product has improved adhesion to metal. I think it does.

Moreover, it is preferable that specific resin contains a radical polymerizable group.

When the specific resin has a radical polymerizable group, the curable resin composition preferably contains a photo-radical polymerization initiator described later as a polymerization initiator, and further includes a photo-radical polymerization initiator described later as a polymerization initiator, and also radical polymerization described later. It is more preferable to contain a compound, and as a polymerization initiator, a radical photopolymerization initiator described later is included, and a radical polymerizable compound described later is included, and it is more preferable that a sensitizer described later is included. A negative photosensitive layer is formed from such a curable resin composition, for example.

Moreover, specific resin may have a polarity converter, such as an acid-decomposable group.

When specific resin has an acid-decomposable group, it is preferable that curable resin composition contains the photo-acid generator mentioned later as a photosensitizer. A negative photosensitive layer is formed from such a curable resin composition.

[Polyimide precursor]

The polyimide precursor used in the present invention is not particularly defined such as its kind, but preferably contains a repeating unit represented by the following formula (2).

[Formula 2]

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

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

R ¹¹¹ in Formula (2) represents a divalent organic group. Examples of the divalent organic group include a straight-chain or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group, and examples include a straight-chain or branched aliphatic group of 2 to 20 carbon atoms, a cyclic aliphatic group of 3 to 20 carbon atoms, and a group containing 3 carbon atoms. An aromatic group of ~20 or a group comprising a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a reduced hydrocarbon group substituted with a group containing a hetero atom. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- are exemplified, and groups represented by -Ar-L-Ar- are particularly preferred. However, Ar is each independently an aromatic group, L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or a group consisting of a combination of two or more of the above. These preferred ranges are as described above.

R ¹¹¹ is preferably derived from diamine. As diamine used for manufacture of a polyimide precursor, linear or branched aliphatic, cyclic aliphatic, or aromatic diamine, etc. are mentioned. As for diamine, only 1 type may be used and 2 or more types may be used.

Specifically, it is preferably a diamine containing a group consisting of a straight-chain or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, It is more preferable that it is a diamine containing a C6-C20 aromatic group. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a reduced hydrocarbon group substituted with a group containing a hetero atom. Examples of the group containing an aromatic group include the following.

[Formula 3]

In the formula, A represents a single bond or a divalent linking group, and 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- , -SO ₂ -, -NHCO-, or a group selected from combinations thereof, preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O) More preferably, a group selected from -, -S-, or -SO ₂ -, -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or More preferably -C(CH ₃ ) ₂ -.

In the formula, * represents a binding site with another structure.

As diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexyl three; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane phosphorus and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl Ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-di Aminodiphenylsulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4 '-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl ) Hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2, 2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) )sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4 -aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy) ) Benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis (4-aminophenoxy) benzene, 1 ,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3' -Dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2 ,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetra Aminobiphenyl, 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, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3 ,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl ) Octamethylpentasiloxane, 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)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl] Hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-di Methylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino -2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoro Romethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy) C) diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ', 5,5'-tetramethyl-4 ,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluoro and at least one type of diamine selected from tolidine and 4,4'-diaminoquaterphenyl.

Moreover, Paragraph 0030 of International Publication No. 2017/038598 - the diamine (DA-1) of 0031 - (DA-18) are also preferable.

Moreover, the diamine which has 2 or more alkylene glycol units of Paragraph 0032 of International Publication No. 2017/038598 - 0034 in a main chain is also used preferably.

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

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

formula (51)

[Formula 4]

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, or a trifluoromethyl group; * Each independently represents a bonding site with a nitrogen atom in Formula (2).

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

[Formula 5]

In Formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to a nitrogen atom in Formula (2).

As the diamine giving the structure of formula (51) or (61), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2 2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. are mentioned. You may use these by 1 type or in combination of 2 or more types.

R ¹¹⁵ in Formula (2) 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.

In formula (5) or formula (6), * each independently represents a binding site with another structure.

[Formula 6]

In Formula (5), R ¹¹² is a single bond or a divalent linking group, and is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-; It is preferably a group selected from -SO ₂ -, -NHCO-, and combinations thereof, and is preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S more preferably a group selected from - and -SO ₂ -, -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and A divalent group selected from the group consisting of -SO ₂ - is more preferred.

Specific examples of R ¹¹⁵ include tetracarboxylic acid residues remaining after removal of the anhydride group from tetracarboxylic dianhydride. The polyimide precursor may contain only one type or two or more types of tetracarboxylic dianhydride residues as a structure corresponding to R ¹¹⁵ .

Tetracarboxylic dianhydride is preferably represented by the following formula (O).

[Formula 7]

In Formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ has the same meaning as that of R ¹¹⁵ in Formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride. Water, 3,3',4,4'-diphenylsulfotetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane Intertetracarboxylic 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 dianhydride, 2, 2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8 -Naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4- dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and C1-C6 alkyl and C1-C6 alkoxy derivatives thereof.

Moreover, tetracarboxylic dianhydride (DAA-1) of Paragraph 0038 of International Publication No. 2017/038598 - (DAA-5) are also mentioned as a preferable example.

In formula (2), at least one of R ¹¹¹ and R ¹¹⁵ may have an OH group. More specifically, as R ¹¹¹ , residues of bisaminophenol derivatives are exemplified.

R ¹¹³ and R ¹¹⁴ in Formula (2) each independently represent a hydrogen atom or a monovalent organic group. As a monovalent organic group, what contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group is preferable. Moreover, it is preferable that at least one of ^R113 and ^R114 contains a polymeric group, and it is more preferable that both contain a polymerizable group. It is also preferable that at least one of R ¹¹³ and R ¹¹⁴ contains two or more polymerizable groups. As the polymerizable group, it is a group capable of undergoing a crosslinking reaction by the action of heat, a radical, or the like, and a radical polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a block isocyanate group, and an amino group. As the radical polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (eg, vinylphenyl group, etc.), and (meth)acrylamide group. , (meth)acryloyloxy group, group represented by the following formula (III), and the like, and the group represented by the following formula (III) is preferable.

[Formula 8]

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), * represents a binding site with another structure.

In Formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, a cycloalkylene group, or a polyalkyleneoxy group.

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

In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.

When the polyalkyleneoxy group includes a plurality of types of alkyleneoxy groups from which the alkylene groups differ, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be random arrangement, block arrangement, alternating arrangement, etc. It may be an array having a pattern of

The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, and 2 to 5 More preferably, 2 to 4 is more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.

Moreover, the said alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. are mentioned.

Moreover, 2-20 are preferable, as for the number of alkyleneoxy groups (repeating number of polyalkyleneoxy groups) contained in a polyalkyleneoxy group, 2-10 are more preferable, and 2-6 are still more preferable.

As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded It is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in patterns such as alternation. Preferred aspects of the number of repeats such as ethyleneoxy groups in these groups are as described above.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor may form a relative salt with the tertiary amine compound having an ethylenically unsaturated bond. As an example of the tertiary amine compound which has such an ethylenically unsaturated bond, N,N- dimethylaminopropyl methacrylate is mentioned.

In Formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity converter such as an acid decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes under the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxy group. Acetal group, ketal group, silyl group, silylether group, tertiary alkyl An ester group or the like is preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.

Specific examples of acid decomposable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-bu A toxycarbonylmethyl group, a trimethylsilyl ether group, etc. are mentioned. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

Moreover, it is also preferable that a polyimide precursor has a fluorine atom in a structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and is preferably 20% by mass or less.

Moreover, for the purpose of improving adhesion to a substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, an aspect using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like is exemplified as the diamine.

It is preferable that the repeating unit represented by Formula (2) is a repeating unit represented by Formula (2-A). That is, it is preferable that at least 1 sort(s) of the polyimide precursor used by this invention is a precursor which has a repeating unit represented by Formula (2-A). When a polyimide precursor contains the repeating unit represented by Formula (2-A), it becomes possible to widen the width|variety of exposure latitude more.

Formula (2-A)

[Formula 9]

In formula (2-A), A ¹ and A ² represent oxygen atoms, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom. Alternatively, it is preferably a monovalent organic group, at least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and both are groups containing a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same meaning as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in Formula (2), and the preferred ranges are also the same. do.

R ¹¹² has the same meaning as R ¹¹² in Formula (5), and the preferred range is also the same.

The polyimide precursor may contain one type of repeating unit represented by Formula (2) or may contain two or more types. Moreover, structural isomers of the repeating unit represented by Formula (2) may be included. In addition, it goes without saying that the polyimide precursor may also contain other types of repeating units in addition to the repeating units of the formula (2).

As one Embodiment of the polyimide precursor in this invention, the aspect whose content of the repeating unit represented by Formula (2) is 50 mol% or more of all repeating units is mentioned. As for the said total content, it is more preferable that it is 70 mol% or more, it is still more preferable that it is 90 mol% or more, and it is especially preferable that it is more than 90 mol%. The upper limit of the said total content is not specifically limited, All the repeating units in the polyimide precursor except for the terminal may be repeating units represented by Formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. Moreover, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.

The degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. Although the upper limit of the degree of dispersion of the molecular weight of the polyimide precursor is not particularly set, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and still more preferably 6.0 or less.

In the present specification, the degree of dispersion of molecular weight is a value calculated by weight average molecular weight/number average molecular weight.

Moreover, when a resin composition contains multiple types of polyimide precursor as a specific resin, it is preferable that the weight average molecular weight of at least 1 type of polyimide precursor, number average molecular weight, and dispersion degree are the said range. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by calculating the plurality of types of polyimide precursors as one resin are respectively within the above ranges.

[Polyimide]

The polyimide used in the present invention may be an alkali-soluble polyimide or a soluble polyimide with respect to a developing solution containing an organic solvent as a main component.

In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more at 23 ° C. with respect to 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and is a polyimide that dissolves 0.5 g or more from the viewpoint of pattern formation. It is preferable, and it is more preferable that it is a polyimide which dissolves 1.0g or more. Although the upper limit of the amount of dissolution is not particularly limited, it is preferably 100 g or less.

Further, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain from the viewpoint of the film strength and insulating properties of the resulting organic film.

In the present specification, "main chain" refers to a relatively longest bonded chain among molecules of a polymer compound constituting a resin, and "side chain" refers to other bonded chains.

-Fluorine atom-

From the viewpoint of the film strength of the resulting organic film, the polyimide also preferably has a fluorine atom.

The fluorine atom is preferably included in R ¹³² in the repeating unit represented by formula (4) described later or R ¹³¹ in the repeating unit represented by formula (4) described later, for example. It is more preferably included as an alkyl fluoride group in R ¹³² in the repeating unit represented by formula (4) or in R ¹³¹ in the repeating unit represented by formula (4) described later.

The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and is preferably 20% by mass or less.

-silicon atom-

From the viewpoint of the film strength of the resulting organic film, the polyimide also preferably has a silicon atom.

For example, a silicon atom is preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later, and an organic modification described later in R ¹³¹ in the repeating unit represented by formula (4) described later. It is more preferable to be included as a (poly)siloxane structure.

Moreover, although the said silicon atom or the said organic modified (poly)siloxane structure may be contained in the side chain of polyimide, it is preferable that it is contained in the main chain of polyimide.

1 mass % or more is preferable and, as for the quantity of silicon atoms with respect to the total mass of polyimide, 20 mass % or less is more preferable.

-ethylenically unsaturated bonds-

From the viewpoint of the film strength of the resulting organic film, the polyimide preferably has an ethylenically unsaturated bond.

The polyimide may have an ethylenically unsaturated bond in the main chain terminal or in the side chain, but it is preferable to have it in the side chain.

It is preferable that the said ethylenically unsaturated bond has radical polymerizability.

The ethylenically unsaturated bond is preferably included in R ¹³² in the repeating unit represented by formula (4) described later or R ¹³¹ in the repeating unit represented by formula (4) described later, and the formula ( It is more preferable to be included as a group having an ethylenically unsaturated bond in R ¹³² in the repeating unit represented by 4) or R ¹³¹ in the repeating unit represented by formula (4) described later.

Among these, the ethylenically unsaturated bond is preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later, and ethylenically unsaturated in R ¹³¹ in the repeating unit represented by formula (4) described later It is more preferable to be included as a group having a bond.

Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, and a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, The group etc. which are represented by following formula (IV) are mentioned.

[Formula 10]

In Formula (IV), R ²⁰ 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 (IV), R ²¹ is an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH-, A (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3; the number of repeats is preferably 1 to 12, 1 to 6 are more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined.

Moreover, as said C2-C12 alkylene group, any of the alkylene group represented by a linear, branched chain, cyclic, or a combination thereof may be sufficient.

As said C2-C12 alkylene group, a C2-C8 alkylene group is preferable, and a C2-C4 alkylene group is more preferable.

Among these, R ²¹ is preferably a group represented by any one of formulas (R1) to (R3) below, and more preferably a group represented by formula (R1).

[Formula 11]

In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together, and X is an oxygen atom or represents a sulfur atom, * represents a bonding site to another structure, and ● represents a bonding site to an oxygen atom to which R ²¹ in formula (IV) is bonded.

In the formulas (R1) to (R3), a preferable embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the carbon number 2 in R ²¹ described above It is the same as the preferable aspect of the alkylene group of -12 or the (poly)alkyleneoxy group of 2-30 carbon atoms.

In formula (R1), X is preferably an oxygen atom.

In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.

The structure represented by formula (R1) is, for example, polyimide having a hydroxyl group such as a phenolic hydroxyl group, and a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanate It is obtained by reacting Itoethyl methacrylate etc.).

The structure represented by Formula (R2) is obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate) lose

The structure represented by Formula (R3) is, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate etc.) is obtained by reacting.

In formula (IV), * represents a bonding site with another structure, and is preferably a bonding site with the main chain of polyimide.

It is preferable that it is 0.0001-0.1 mol/g, and, as for the quantity of ethylenically unsaturated bonds with respect to the total mass of polyimide, it is more preferable that it is 0.0005-0.05 mol/g.

-Polymerizable groups other than groups having ethylenically unsaturated bonds-

The polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.

Examples of polymerizable groups other than groups having ethylenically unsaturated bonds include cyclic ether groups such as epoxy groups and oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups.

It is preferable that polymerizable groups other than the group which has an ethylenically unsaturated bond are contained in ^R131 in the repeating unit represented by Formula (4) mentioned later, for example.

It is preferable that it is 0.0001-0.1 mol/g, and, as for the quantity of polymeric groups other than the group which has an ethylenically unsaturated bond with respect to the total mass of polyimide, it is more preferable that it is 0.001-0.05 mol/g.

-Polar Transducer-

The polyimide may have a polarity converter such as an acid decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described for R ¹¹³ and R ¹¹⁴ in the formula (2) described above, and the preferred embodiments are also the same.

The polarity converter is included in, for example, R ¹³¹ , R ¹³² in a repeating unit represented by formula (4) described later, the terminal of polyimide, and the like.

-Acid value-

When the polyimide is subjected to alkali development, the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and still more preferably 70 mgKOH/g or more, from the viewpoint of improving developability.

Further, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and still more preferably 200 mgKOH/g or less.

Further, when the polyimide is subjected to development using a developing solution containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 1 to 35 mgKOH/g, and 2 to 30 mgKOH /g is more preferable, and 5-20 mgKOH/g is more preferable.

The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

Moreover, as an acidic radical contained in a polyimide, from a viewpoint of both storage stability and developability, an acidic radical with a pKa of 0-10 is preferable, and an acidic radical with 3-8 is more preferable.

The pKa is a dissociation reaction in which hydrogen ions are released from an acid, and the equilibrium constant Ka is expressed by the negative common logarithm pKa. In this specification, unless otherwise specified, pKa is a calculated value by ACD/ChemSketch (registered trademark). Alternatively, you may refer to the values published in the "Basic Edition of the 5th Edition Chemistry Handbook" edited by the Chemical Society of Japan.

In the case where the acid group is, for example, a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant.

As such an acidic radical, the polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

-Phenolic hydroxyl group-

From the viewpoint of making the development rate with an alkali developer appropriate, the polyimide preferably has a phenolic hydroxyl group.

A polyimide may have a phenolic hydroxyl group in the main chain terminal, or may have it in a side chain.

The phenolic hydroxyl group is preferably included in R ¹³² in the repeating unit represented by formula (4) described later or R ¹³¹ in the repeating unit represented by formula (4) described later.

It is preferable that it is 0.1-30 mol/g, and, as for the quantity of the phenolic hydroxyl group with respect to the total mass of polyimide, it is more preferable that it is 1-20 mol/g.

The polyimide used in the present invention is not particularly limited as long as it is a high molecular compound having an imide structure, but preferably contains a repeating unit represented by the following formula (4).

[Formula 12]

In Formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

In the case of having a polymerizable group, the polymerizable group may be located at at least one of R ¹³¹ and R ¹³² , and may be located at the terminal of the polyimide as shown in the following formula (4-1) or formula (4-2).

Formula (4-1)

[Formula 13]

In formula (4-1), R ¹³³ is a polymerizable group, and other groups have the same meaning as in formula (4).

Formula (4-2)

[Formula 14]

At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other group has the same meaning as Formula (4).

Examples of the polymerizable group include a group containing an ethylenically unsaturated bond described above or a crosslinkable group other than the group having an ethylenically unsaturated bond described above.

R ¹³¹ represents a divalent organic group. As a divalent organic group, the same thing as ^R111 in Formula (2) is illustrated, and the preferable range is also the same.

Moreover, as ^R131 , the diamine residue which remains after the removal of the amino group of diamine is mentioned. As diamine, aliphatic, cyclic aliphatic, or aromatic diamine, etc. are mentioned. As a specific example, the example of ^R111 in Formula (2) of a polyimide precursor is mentioned.

R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain, from the viewpoint of more effectively suppressing the occurrence of warping during firing. More preferably, it is a diamine residue containing two or more of an ethylene glycol chain or a propylene glycol chain or both in one molecule, more preferably the diamine and not containing an aromatic ring. It is a min residue.

Examples of diamines containing two or more of ethylene glycol chains and propylene glycol chains in combination or both in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (above trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy) oxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc., but are not limited thereto. .

R ¹³² represents a tetravalent organic group. As a tetravalent organic group, the same thing as ^R115 in Formula (2) is illustrated, and the preferable range is also the same.

For example, four linkages of a tetravalent organic group exemplified by R ¹¹⁵ are bonded to four -C(=O)- moieties in the formula (4) to form a condensed ring.

Moreover, examples of R ¹³² include tetracarboxylic acid residues remaining after removal of the anhydride group from tetracarboxylic dianhydride. As a specific example, the example of ^R115 in Formula (2) of a polyimide precursor is mentioned. From the viewpoint of the strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable to have an OH group in at least one of R ¹³¹ and R ¹³² . More specifically, as R ¹³¹ , 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, the above (DA-1) to ( DA-18) can be cited as a preferable example, and as R ¹³² , the above (DAA-1) to (DAA-5) can be cited as more preferable examples.

Moreover, it is also preferable that a polyimide has a fluorine atom in a structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and is preferably 20% by mass or less.

In addition, for the purpose of improving adhesion to a substrate, polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as a diamine component, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, etc. are mentioned.

Further, in order to improve the storage stability of the resin composition, the main chain terminal of the polyimide is preferably sealed with a terminal blocker such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Among these, it is more preferable to use monoamines, and examples of preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, and 5-amino-8-hydroxy. Quinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-amino Naphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2 -Carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid , 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol , 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. Two or more types of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

-Imidization rate (closing rate)-

The imidation rate (also referred to as "circulation closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more from the viewpoint of film strength, insulation, etc. of the obtained organic film. .

The upper limit of the said imidization rate is not specifically limited, What is necessary is just 100% or less.

The said imidation rate is measured, for example by the following method.

The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 around 1377 cm ⁻¹ , which is an absorption peak derived from the imide structure, is determined. Next, after heat-processing the polyimide at 350°C for 1 hour, the infrared absorption spectrum is measured again, and the peak intensity P2 around 1377 cm ^-1 is determined. The imidation rate of a polyimide can be calculated|required based on the following formula using obtained peak intensity P1 and P2.

Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

The polyimide may contain repeating units represented by the formula (4), all of which contain one type of R ¹³¹ or R ¹³² , and the formula (4) containing two or more different types of R ¹³¹ or R ¹³² ) may be included. Moreover, a polyimide may also contain other types of repeating units other than the repeating unit represented by said Formula (4). As another kind of repeating unit, the repeating unit etc. represented by Formula (2) mentioned above are mentioned, for example.

The polyimide is, for example, a method of reacting tetracarboxylic dianhydride and diamine (partly substituted with a monoamine terminal capping agent) at low temperature, and tetracarboxylic dianhydride (partly acid anhydride or monoacid chloride compound or A method of reacting diamine with a terminal blocker, which is a monoactive ester compound, to obtain a diester by tetracarboxylic dianhydride and alcohol, and then diamine (partly replaced with a terminal blocker, which is a monoamine) and a condensing agent A method of reacting in the presence of a tetracarboxylic acid dianhydride and an alcohol to obtain a diester, then acid chloride of the remaining dicarboxylic acid, and a method of reacting with diamine (partially substituted with a monoamine terminal blocker), etc. A method of obtaining a polyimide precursor using a method and completely imidating this using a known imidation reaction method, or a method of stopping the imidation reaction in the middle and introducing a part of the imide structure, and furthermore, It can be synthesized using a method of introducing a part of the imide structure by blending a completely imidized polymer and the polyimide precursor. Moreover, other well-known synthesis methods of polyimides can also be applied.

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the film after curing can be improved. In order to obtain an organic film excellent in mechanical properties (for example, elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.

Moreover, the number average molecular weight (Mn) of polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.

The degree of dispersion of the molecular weight of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. The upper limit of the degree of dispersion of the molecular weight of the polyimide is not particularly set, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and still more preferably 6.0 or less.

Moreover, when a resin composition contains multiple types of polyimide as a specific resin, it is preferable that the weight average molecular weight of at least 1 type of polyimide, number average molecular weight, and dispersion degree are the said range. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by calculating the plurality of types of polyimide as one resin are respectively within the above range.

[Polybenzoxazole precursor]

The polybenzoxazole precursor used in the present invention is not particularly defined for its structure or the like, but preferably contains a repeating unit represented by the following formula (3).

[Formula 15]

In Formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In Formula (3), R ¹²³ and R ¹²⁴ each have the same meaning as R ¹¹³ in Formula (2), and the preferred ranges are also the same. That is, it is preferable that at least one is a polymeric group.

In Formula (3), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a straight-chain aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. As for the dicarboxylic acid residue, only one type may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.

As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group is preferable, and a dicarboxylic acid composed of a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH is more preferred. desirable. The number of carbon atoms in the straight-chain or branched (preferably straight-chain) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, still more preferably 4 to 15, , 5 to 10 are particularly preferred. It is preferable that a linear aliphatic group is an alkylene group.

Examples of dicarboxylic acids containing a straight-chain aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2 -Dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2, 2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonane diacid, dodecane diacid, tridecane Caine Diacid, Tetradecane Diacid, Pentadecane Diacid, Hexadecaine Diacid, Heptadecaine Diacid, Octadecaine Diacid, Nonadecaine Diacid, Eicosane Diacid, Henaicosane Diacid, Docosane Diacid, Tricosane Diacid, Tetracosane Diacid, Pentacosane Diacid, Hexacosane Diacid, Heptacosane Diacid, Octacosane Diacid, Nonacoseine Diacid, Triacontane Diacid, Hentriacontane Diacid, Dotriacontane Diacid, Digly Cholic acid, dicarboxylic acid represented by the following formula, and the like are exemplified.

[Formula 16]

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

As the dicarboxylic acid containing an aromatic group, the dicarboxylic acids having the following aromatic groups are preferable, and the dicarboxylic acids consisting only of the groups having the following aromatic groups and two -COOH are more preferable.

[Formula 17]

In the formula, A is -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ - represents a divalent group selected from the group consisting of, and * each independently represents a binding site with another structure.

Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the formula (2), and the preferred range is also the same.

R ¹²² is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4 ,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3' -Dihydroxydiphenylsulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-( 3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxy Phenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-di Amino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxy Diphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxy Roxybenzene etc. are mentioned. These bisaminophenols may be used alone or in combination.

Among the bisaminophenol derivatives, the bisaminophenol derivatives having the following aromatic groups are preferred.

[Formula 18]

In the formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, or -NHCO-, and * and # are each associated with another structure. indicates the binding site. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. Moreover, it is also preferable that R ¹²² has a structure represented by the above formula. When R ¹²² has a structure represented by the above formula, any two of the total four * and # are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, and the other two are in the formula (3 ) is preferably a bonding site to an oxygen atom to which R ¹²² in ) is bonded, two * are bonding sites to an oxygen atom to which R ¹²² in Formula (3) is bonded, and two # are bonding sites to an oxygen atom to which R 122 in Formula (3) is bonded. is a bonding site to the nitrogen atom to which R ¹²² in formula (3) is bonded, or two * is a bonding site to a nitrogen atom to which R ¹²² in formula (3) is bonded, and two #'s to R 122 in formula (3) It is more preferable that ¹²² is a bonding site to the oxygen atom to be bonded, two * in formula (3) is a bonding site to an oxygen atom to which R ¹²² is bonded, and two # is a bonding site to R in formula (3) It is more preferable that ¹²² is a bonding site with the nitrogen atom to which it is bonded.

It is also preferable that the bisaminophenol derivative is a compound represented by formula (A-s).

[Formula 19]

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

[Formula 20]

(In the formula (A-sc), * indicates bonding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the formula (A-s).)

In the above formula (As), it is considered that having a substituent at the ortho position of the phenolic hydroxy group, that is, R ₃ also brings the distance between the carbonyl carbon of the amide bond and the hydroxy group closer, and when cured at a low temperature It is particularly preferable at the point where the effect of becoming a higher conversion rate becomes higher.

Moreover, in the said Formula (As), it is preferable that R _<2> is an alkyl group and R _<3> is an alkyl group, since it can maintain high transparency with respect to i line and the effect of a high cyclization rate when hardening|curing at low temperature.

Moreover, in the formula (As), it is more preferable that R ₁ is an alkylene or a substituted alkylene. Specific examples of the alkylene and substituted alkylene for R ₁ include linear or branched alkyl groups having 1 to 8 carbon atoms, among which -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) _2- is more preferable from the viewpoint of obtaining a well-balanced polybenzoxazole precursor having sufficient solubility in solvents while maintaining the effect of high transparency to i-line and high conversion rate when cured at low temperatures.

As a method for producing the bisaminophenol derivative represented by the formula (A-s), for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Unexamined-Japanese-Patent No. 2013-256506 can be referred to. , these contents are incorporated herein by reference.

As a specific example of the structure of the bisaminophenol derivative represented by the said formula (A-s), Paragraph No. 0070 of Unexamined-Japanese-Patent No. 2013-256506 - what was described in 0080 are mentioned, These content is integrated in this specification. Of course, it goes without saying that it is not limited to these.

A polybenzoxazole precursor may also contain other types of repeating units other than the repeating unit of said Formula (3).

The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as a repeating unit of a different type from the viewpoint of being able to suppress generation of curvature due to ring closure.

[Formula 21]

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

In the formula (SL), examples of preferred Z include those in which R ^5s and R ^6s in b structure are phenyl groups. Moreover, it is preferable that it is 400-4,000, and, as for the molecular weight of the structure represented by Formula (SL), 500-3,000 are more preferable. By setting the molecular weight within the above range, the effect of lowering the elastic modulus after dehydration ring closure of the polybenzoxazole precursor and suppressing warping and the effect of improving solvent solubility can be more effectively achieved.

When the diamine residue represented by the formula (SL) is included as the other type of repeating unit, it is also preferable to further include a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic acid dianhydride as the repeating unit. As an example of such a tetracarboxylic acid residue, the example of ^R115 in Formula (2) is mentioned.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, still more preferably 22,000 to 28,000. Moreover, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.

The degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and still more preferably 1.6 or more. The upper limit of the degree of dispersion of the molecular weight of the polybenzoxazole precursor is not particularly set, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, still more preferably 2.4 or less, still more preferably 2.3 or less, and 2.2 or less. The following is more preferable.

Moreover, when a resin composition contains multiple types of polybenzoxazole precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion degree of at least 1 type of polybenzoxazole precursor are the said range. . Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by calculating the plurality of types of polybenzoxazole precursors as one resin are respectively within the above ranges.

[Polybenzoxazole]

The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and is a compound represented by the following formula (X) and has a polymerizable group. more preferable As said polymerizable group, a radical polymerizable group is preferable. Moreover, as a compound represented by following formula (X), the compound which has a polarity converter, such as an acid-decomposable group, may be used.

[Formula 22]

In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.

In the case of having a polarity converter such as a polymerizable group or an acid decomposable group, the polarity converter such as a polymerizable group or an acid decomposable group may be located at least one of R ¹³³ and R ¹³⁴ , and the following formula (X-1) or formula (X As shown in -2), you may be located at the terminal of polybenzoxazole.

Formula (X-1)

[Formula 23]

In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polarity converter such as a polymerizable group or an acid decomposable group, and when it is not a polarity converter such as a polymerizable group or acid decomposable group, it is an organic group, and the other group is It has the same meaning as Formula (X).

Formula (X-2)

[Formula 24]

In formula (X-2), R ¹³⁷ is a polarity converter such as a polymerizable group or an acid decomposable group, and other groups are substituents, and other groups have the same meaning as in formula (X).

A polarity converter such as a polymerizable group or an acid decomposable group has the same meaning as the polymerizable group described for the polymerizable group possessed by the polyimide precursor.

R ¹³³ represents a divalent organic group. As a divalent organic group, an aliphatic group or an aromatic group is mentioned. As a specific example, the example of ^R121 in Formula (3) of a polybenzoxazole precursor is mentioned. Further, preferred examples thereof are the same as those for R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. As a tetravalent organic group, the example of ^R122 in Formula (3) of a polybenzoxazole precursor is mentioned. Further, preferred examples thereof are the same as those for R ¹²² .

For example, four bonds of a tetravalent organic group exemplified as R ¹²² are bonded to the nitrogen atom and oxygen atom in the formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. In the structure below, each * represents a bonding site with a nitrogen atom or an oxygen atom in formula (X).

[Formula 25]

The polybenzoxazole preferably has an oxazolization rate of 85% or more, more preferably 90% or more. The upper limit is not particularly limited and may be 100%. When the oxazolization rate is 85% or more, film shrinkage based on ring closure that occurs during oxazolization by heating is reduced, and generation of warping can be more effectively suppressed.

The said oxazolization rate is measured, for example by the following method.

The infrared absorption spectrum of the polybenzoxazole is measured, and the peak intensity Q1 around 1650 cm ⁻¹ , which is an absorption peak derived from the amide structure of the precursor, is determined. Next, it is normalized by the absorption intensity of the aromatic ring seen around 1490 cm ^-1 . After the polybenzoxazole is heat-treated at 350°C for 1 hour, the infrared absorption spectrum is measured again, the peak intensity Q2 around 1650 cm ^-1 is determined, and the absorption intensity of the aromatic ring seen around 1490 cm ^-1 is normalized. The oxazolization rate of polybenzoxazole can be calculated|required based on the following formula using the standard value of the obtained peak intensities Q1 and Q2.

Oxazolization rate (%) = (standard value of peak intensity Q1 / standard value of peak intensity Q2) × 100

The polybenzoxazole may contain repeating units of the formula (X), all of which contain one type of R ¹³¹ or R ¹³² , and the formula (X) containing two or more different types of R ¹³¹ or R ¹³² ( It may contain the repeating unit of X). Moreover, polybenzoxazole may also contain other types of repeating units other than the repeating unit of said formula (X).

Polybenzoxazole is obtained, for example, by reacting a bisaminophenol derivative with a dicarboxylic acid containing R ¹³³ or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the dicarboxylic acid, and the like. It is obtained by obtaining a precursor and oxazolizing it using a known oxazolization reaction method.

In addition, in the case of dicarboxylic acid, in order to increase the reaction yield or the like, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used.

The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, still more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the film after curing can be improved. In order to obtain an organic film excellent in mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Moreover, when 2 or more types of polybenzoxazoles are contained, it is preferable that the weight average molecular weight of at least 1 type of polybenzoxazole is the said range.

Moreover, the number average molecular weight (Mn) of polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.

The degree of dispersion of the molecular weight of the polybenzoxazole is preferably 1.4 or more, more preferably 1.5 or more, and still more preferably 1.6 or more. The upper limit of the degree of dispersion of the molecular weight of the polybenzoxazole is not particularly set, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, still more preferably 2.4 or less, still more preferably 2.3 or less, and 2.2 or less. is more preferable.

Moreover, when a resin composition contains multiple types of polybenzoxazole as a specific resin, it is preferable that the weight average molecular weight of at least 1 type of polybenzoxazole, number average molecular weight, and dispersion degree are the said range. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated as one resin of the plurality of types of polybenzoxazoles are within the above ranges, respectively.

[Polyamide-imide precursor]

It is preferable that the polyamideimide precursor contains a repeating unit represented by the following formula (PAI-2).

[Formula 26]

In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or a monovalent organic group.

In formula (PAI-2), R ¹¹⁷ is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group; A straight-chain aliphatic group of 2 to 20 carbon atoms, a branched aliphatic group of 3 to 20 carbon atoms, a cyclic aliphatic group of 3 to 20 carbon atoms, an aromatic group of 6 to 20 carbon atoms, or a combination of two or more of these by a single bond or a linking group. One group is preferable, and a C6-C20 aromatic group or a group combining two or more C6-C20 aromatic groups by a single bond or a linking group is more preferable.

As the linking group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is preferable. And -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.

As said alkylene group, a C1-C20 alkylene group is preferable, a C1-C10 alkylene group is more preferable, and a C1-C4 alkylene group is still more preferable.

As said halogenated alkylene group, a C1-C20 halogenated alkylene group is preferable, a C1-C10 halogenated alkylene group is more preferable, and a C1-C4 halogenated alkylene group is more preferable. do. Moreover, as a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. Although the said halogenated alkylene group may have a hydrogen atom and all the hydrogen atoms may be substituted by the halogen atom, it is preferable that all the hydrogen atoms are substituted by the halogen atom. As an example of a preferable halogenated alkylene group, a (ditrifluoromethyl) methylene group etc. are mentioned.

As the arylene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.

Further, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. As said halogenation, chlorination is preferable.

In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound.

Among the three carboxy groups of the tricarboxylic acid compound, two carboxy groups may be acid anhydrided.

Examples of the tricarboxylic acid compound which may be halogenated used for production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

These tricarboxylic acid compounds may be used alone or in combination of two or more.

Specifically, as the tricarboxylic acid compound, a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or A tricarboxylic acid compound containing a group in which two or more of these are combined by a bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms, or a group containing two or more aromatic groups having 6 to 20 carbon atoms in combination by a single bond or a linking group A tricarboxylic acid compound is more preferable.

Further, specific examples of the tricarboxylic acid compound include 1,2,3-propane tricarboxylic acid, 1,3,5-pentane tricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalene tricarboxylic acid, phthalic acid (or , phthalic anhydride) and benzoic acid connected by a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - or a phenylene group; can

These compounds may be compounds in which two carboxy groups are anhydride (eg trimellitic anhydride) or compounds in which at least one carboxy group is halogenated (eg trimellitic anhydride chloride).

In formula (PAI-2), R ¹¹¹ , A ² and R ¹¹³ have the same meaning as R ¹¹¹ , A ² and R ¹¹³ in formula (2) described above, and the preferred embodiments are also the same.

The polyamide-imide precursor may further contain other repeating units.

As another repeating unit, the repeating unit represented by the above-mentioned formula (2), the repeating unit represented by the following formula (PAI-1), etc. are mentioned.

[Formula 27]

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group.

In formula (PAI-1), R ¹¹⁶ is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group; A straight-chain aliphatic group of 2 to 20 carbon atoms, a branched aliphatic group of 3 to 20 carbon atoms, a cyclic aliphatic group of 3 to 20 carbon atoms, an aromatic group of 6 to 20 carbon atoms, or a combination of two or more of these by a single bond or a linking group. One group is preferable, and a C6-C20 aromatic group or a group combining two or more C6-C20 aromatic groups by a single bond or a linking group is more preferable.

As the linking group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is preferable. And -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.

As said alkylene group, a C1-C20 alkylene group is preferable, a C1-C10 alkylene group is more preferable, and a C1-C4 alkylene group is still more preferable.

As said halogenated alkylene group, a C1-C20 halogenated alkylene group is preferable, a C1-C10 halogenated alkylene group is more preferable, and a C1-C4 halogenated alkylene group is more preferable. do. Moreover, as a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. Although the said halogenated alkylene group may have a hydrogen atom and all the hydrogen atoms may be substituted by the halogen atom, it is preferable that all the hydrogen atoms are substituted by the halogen atom. As an example of a preferable halogenated alkylene group, a (ditrifluoromethyl) methylene group etc. are mentioned.

As the arylene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.

Further, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.

In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is referred to as a dicarboxylic acid dihalide compound.

The carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.

Examples of the dicarboxylic acid compound or dicarboxylic acid dihalide compound which may be halogenated used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds. can be heard

These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

Specifically, as the dicarboxylic acid compound or dicarboxylic acid dihalide compound, a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a C 6 to 20 carbon atom group. A dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing an aromatic group or a group obtained by combining two or more thereof by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or a single bond or a linking group containing 6 carbon atoms A dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group in which two or more of ~20 aromatic groups are combined is more preferred.

Further, as specific examples of the dicarboxylic acid compound, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2 -Dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2- Dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2 ,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonane diacid, dodecane diacid, tridecane Diacid, tetradecane diacid, pentadecane diacid, hexadecane diacid, heptadecane diacid, octadecaine diacid, nonadecaine diacid, eicosane diacid, henaicosane diacid, docosane diacid, tricosane diacid, tetra Cosane Diacid, Pentacosane Diacid, Hexacosane Diacid, Heptacosane Diacid, Octacosane Diacid, Nonacoseine Diacid, Triacontane Diacid, Hentriacontane Diacid, Dotriacontane Diacid, Diglycolic Acid , phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. can be heard

As a specific example of the dicarboxylic acid dihalide compound, a compound having a structure in which two carboxyl groups in the specific examples of the dicarboxylic acid compound are halogenated is mentioned.

In formula (PAI-1), R ¹¹¹ has the same meaning as R ¹¹¹ in formula (2) described above, and the preferred embodiments are also the same.

Moreover, it is also preferable that a polyamide-imide precursor has a fluorine atom in a structure. The fluorine atom content in the polyamideimide precursor is preferably 10% by mass or more, and is preferably 20% by mass or less.

In addition, for the purpose of improving adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, an aspect using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine component is exemplified.

As an embodiment of the polyamideimide precursor in the present invention, the total content of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and the repeating unit represented by formula (2) An aspect in which this is 50 mol% or more of all repeating units is mentioned. As for the said total content, it is more preferable that it is 70 mol% or more, it is still more preferable that it is 90 mol% or more, and it is especially preferable that it is more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyamideimide precursor except for the terminal are the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and , any of the repeating units represented by formula (2) may be used.

Further, as another embodiment of the polyamideimide precursor in the present invention, the total content of the repeating unit represented by formula (PAI-2) and the repeating unit represented by formula (PAI-1) is the total of all repeating units. The aspect which is 50 mol% or more is mentioned. As for the said total content, it is more preferable that it is 70 mol% or more, it is still more preferable that it is 90 mol% or more, and it is especially preferable that it is more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor except for terminals are repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1). may be any one of

The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, 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, still more preferably 4,000 to 25,000.

The degree of dispersion of the molecular weight of the polyamideimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. The upper limit of the degree of dispersion of the molecular weight of the polyamideimide precursor is not particularly set, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and still more preferably 6.0 or less. Moreover, when a resin composition contains multiple types of polyamideimide precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion degree of at least 1 type of polyamideimide precursor are the said range. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by calculating the plurality of types of polyamideimide precursors as one resin are respectively within the above ranges.

[Polyamideimide]

The polyamide-imide used in the present invention may be an alkali-soluble polyamide-imide or a polyamide-imide soluble in a developing solution containing an organic solvent as a main component.

In the present specification, alkali-soluble polyamideimide refers to polyamideimide that dissolves at 0.1 g or more at 23° C. with respect to 100 g of 2.38 mass% tetramethylammonium aqueous solution, and from the viewpoint of pattern formation, polyamide-imide that dissolves at least 0.5 g. It is preferable that it is amideimide, and it is more preferable that it is polyamideimide which dissolves 1.0g or more. Although the upper limit of the amount of dissolution is not particularly limited, it is preferably 100 g or less.

Further, the polyamide-imide is preferably a polyamide-imide having a plurality of amide bonds and a plurality of imide structures in the main chain from the viewpoint of film strength and insulating properties of the obtained organic film.

-Fluorine atom-

From the viewpoint of the film strength of the resulting organic film, the polyamideimide preferably has a fluorine atom.

The fluorine atom is preferably included in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by formula (PAI-3) described later, for example, in the repeating unit represented by formula (PAI-3) described later. It is more preferable to be included as a fluorinated alkyl group in R ¹¹⁷ or R ¹¹¹ in .

The amount of fluorine atoms relative to the total mass of polyamideimide is preferably 5% by mass or more, and preferably 20% by mass or less.

-ethylenically unsaturated bonds-

From the viewpoint of the film strength of the resulting organic film, polyamideimide may have an ethylenically unsaturated bond.

Polyamide-imide may have an ethylenically unsaturated bond at the terminal of the main chain or at the side chain, but it is preferable to have it at the side chain.

It is preferable that the said ethylenically unsaturated bond has radical polymerizability.

The ethylenically unsaturated bond is preferably included in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later, and in the repeating unit represented by the formula (PAI-3) described later It is more preferably included as a group having an ethylenically unsaturated bond in R ¹¹⁷ or R ¹¹¹ .

The preferable aspect of the group having an ethylenically unsaturated bond is the same as the preferable aspect of the group having an ethylenically unsaturated bond in the polyimide described above.

The amount of ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.

-Polymerizable groups other than ethylenically unsaturated bonds-

Polyamide-imide may have polymeric groups other than an ethylenically unsaturated bond.

Examples of the polymerizable group other than the ethylenically unsaturated bond in polyamideimide include the same groups as the polymerizable group other than the ethylenically unsaturated bond in the polyimide described above.

A polymerizable group other than an ethylenically unsaturated bond is preferably included in R ¹¹¹ in the repeating unit represented by formula (PAI-3) described below, for example.

The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g.

-Polar Transducer-

Polyamide-imide may have a polarity converter such as an acid decomposable group. The acid-decomposable group in polyamideimide is the same as the acid-decomposable group described for R ¹¹³ and R ¹¹⁴ in the formula (2) described above, and the preferred embodiments are also the same.

-Acid value-

When polyamideimide is subjected to alkali development, from the viewpoint of improving developability, the acid value of polyamideimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and still more preferably 70 mgKOH/g or more. do.

Further, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and still more preferably 200 mgKOH/g or less.

Further, when polyamideimide is subjected to development using a developing solution containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of polyamideimide is preferably 2 to 35 mgKOH/g, and 3 ~ 30 mgKOH/g is more preferred, and 5 to 20 mgKOH/g is even more preferred.

The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

Moreover, as an acidic radical contained in polyamideimide, the same group as the acidic radical in the polyimide mentioned above is mentioned, and the preferable aspect is also the same.

-Phenolic hydroxyl group-

From the viewpoint of making the development speed with an alkaline developer appropriate, the polyamideimide preferably has a phenolic hydroxyl group.

Polyamide-imide may have a phenolic hydroxyl group at the terminal of the main chain or may have it at the side chain.

The phenolic hydroxyl group is preferably included in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by formula (PAI-3) described below, for example.

It is preferable that it is 0.1-30 mol/g, and, as for the quantity of the phenolic hydroxyl group with respect to the total mass of polyamideimide, it is more preferable that it is 1-20 mol/g.

The polyamideimide used in the present invention is not particularly limited as long as it is a high molecular compound having an imide structure and an amide bond, but one containing a repeating unit represented by the following formula (PAI-3) is preferable.

[Formula 28]

In formula (PAI-3), R ¹¹¹ and R ¹¹⁷ have the same meanings as R ¹¹¹ and R ¹¹⁷ in formula (PAI-2), and the preferred embodiments are also the same.

In the case of having a polymerizable group, the polymerizable group may be located at at least one of R ¹¹¹ and R ¹¹⁷ , or may be located at the terminal of polyamideimide.

Further, in order to improve the storage stability of the resin composition, it is preferable to seal the main chain terminals of the polyamideimide with a terminal blocker such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Preferable aspects of the terminal blocking agent are the same as those of the terminal blocking agent in the polyimide described above.

-Imidization rate (closing rate)-

The imidation rate (also referred to as “ring closure rate”) of polyamideimide is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more from the viewpoint of film strength, insulation, etc. of the resulting organic film. do.

The upper limit of the said imidization rate is not specifically limited, What is necessary is just 100% or less.

The said imidization rate is measured by the same method as the ring-closing rate of polyimide mentioned above.

The polyamideimide may contain repeating units represented by Formula (PAI-3), all of which contain one type of R ¹¹¹ or R ¹¹⁷ , and include two or more different types of R ¹³¹ or R ¹³² . It may contain the repeating unit represented by Formula (PAI-3). Moreover, polyamide-imide may also contain other types of repeating units other than the repeating unit represented by said Formula (PAI-3). As another kind of repeating unit, the repeating unit represented by the above-mentioned formula (PAI-1) or formula (PAI-2), etc. are mentioned.

Polyamideimide is, for example, a method of obtaining a polyamideimide precursor by a known method and completely imidizing it using a known imidation reaction method, or stopping the imidation reaction in the middle, and partially It can synthesize|combine using the method of introduce|transducing a de structure, and also the method of introduce|transducing a partial imide structure by blending the fully imidized polymer and the polyamideimide precursor.

The weight average molecular weight (Mw) of polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, still more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the film after curing can be improved. In order to obtain an organic film excellent in mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more.

Further, the number average molecular weight (Mn) of polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000.

The degree of dispersion of the molecular weight of the polyamideimide is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. The upper limit of the degree of dispersion of the molecular weight of polyamideimide is not particularly set, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and still more preferably 6.0 or less.

Moreover, when a resin composition contains multiple types of polyamideimide as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion degree of at least 1 type of polyamideimide are the said range. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by calculating the plurality of types of polyamideimide as one resin are within the above ranges, respectively.

[Method for Producing Polyimide Precursors, etc.]

The polyimide precursor and the like are, for example, a method of reacting tetracarboxylic dianhydride and diamine at low temperature, obtaining polyamic acid by reacting tetracarboxylic dianhydride and diamine at low temperature, and esterification using a condensing agent or an alkylating agent method, tetracarboxylic dianhydride and alcohol to obtain a diester, and then diamine and a reaction method in the presence of a condensing agent, tetracarboxylic dianhydride and alcohol to obtain a diester, and then the remaining dicarboxylic acid It can be obtained using a method such as a method of acid halogenating using a halogenating agent and reacting with diamine. Among the above production methods, a method in which a diester is obtained by using tetracarboxylic dianhydride and alcohol, and then the remaining dicarboxylic acid is acid-halogenated using a halogenating agent and reacted with diamine is more preferable.

Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, and 1,1-carbonyldioxy. -Di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, anhydrous trifluoroacetic acid, etc. are mentioned.

Examples of the alkylating agent include N,N-dimethylformamide dimethylacetal, N,N-dimethylformamide diethylacetal, N,N-dialkylformamide dialkylacetal, trimethyl orthoformate, and triethyl orthoformate. can be heard

Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride.

In the manufacturing method of a polyimide precursor etc., it is preferable to use an organic solvent in the case of reaction. 1 type may be sufficient as an organic solvent, and 2 or more types may be sufficient as it.

Although the organic solvent can be appropriately determined depending on the raw material, pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide , dimethylformamide, tetrahydrofuran, γ-butyrolactone and the like are exemplified.

In the manufacturing methods of a polyimide precursor etc., it is preferable to add a basic compound at the time of reaction. 1 type of basic compound may be sufficient as it, and 2 or more types may be sufficient as it.

The basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl- 4-aminopyridine etc. are illustrated.

-end sealant-

In the production method of the polyimide precursor or the like, in order to further improve the storage stability, it is preferable to seal the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like. When sealing the carboxylic acid anhydride and acid anhydride derivative remaining at the resin terminal, examples of the terminal blocker include monoalcohol, phenol, thiol, thiophenol, monoamine, etc. , It is more preferable to use phenols or monoamines. Preferable monoalcohol compounds include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, and the like. secondary alcohols such as tertiary alcohol, isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. there is. Preferred compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalen-1-ol, naphthalen-2-ol, and hydroxystyrene. Moreover, as a compound of preferable monoamine, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-amino Naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 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-aminobenzene Sulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiocyanate Ophenol, 3-aminothiophenol, 4-aminothiophenol, etc. are mentioned. Two or more types of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

In addition, when sealing the amino group at the terminal of the resin, it is possible to seal with a compound having a functional group capable of reacting with the amino group. Preferred sealing agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides and the like, more preferably carboxylic acid anhydrides and carboxylic acid chlorides. Acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride etc. are mentioned as a preferable compound of carboxylic acid anhydride. Further, preferred compounds of the carboxylic acid chloride include acetyl chloride, acrylate chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-a damantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride and the like.

-solid precipitation-

In the case of manufacture of a polyimide precursor etc., you may include the process of depositing solid. Specifically, after the absorption by-product of the dehydration condensation agent coexisting in the reaction solution is separated by filtration as necessary, the obtained polymer component is introduced into a poor solvent such as water, lower aliphatic alcohol, or a mixture thereof, , A polyimide precursor etc. can be obtained by precipitating a polymer component, making it precipitate as a solid, and drying. In order to improve the degree of purification, operations such as re-dissolving the polyimide precursor, re-precipitation, and drying may be repeated. Further, a step of removing ionic impurities using an ion exchange resin may be included.

〔content〕

The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and 50% by mass with respect to the total solid content of the resin composition. More than that is more preferable. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, and 97% by mass or less with respect to the total solid content of the resin composition. It is more preferable that it is mass % or less, and it is still more preferable that it is 95 mass % or less.

The resin composition of this invention may contain only 1 type of specific resin, and may contain 2 or more types. When including 2 or more types, it is preferable that a total amount becomes the said range.

Moreover, it is also preferable that the resin composition of this invention contains at least 2 types of resin.

Specifically, the resin composition of the present invention may contain a total of two or more types of specific resin and other resins described later, or may contain two or more types of specific resin, but preferably contains two or more types of specific resin. .

When the resin composition of the present invention contains two or more types of specific resin, for example, two or more types of polyimide precursors having different structures derived from dianhydride (R ¹¹⁵ in the above formula (2)) as polyimide precursors It is preferable to include.

<Other resins>

The resin composition of the present invention may also contain the specific resin described above and another resin different from the specific resin (hereinafter, simply referred to as “other resin”).

Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, A polyether resin, a polyester resin, etc. are mentioned.

For example, by further adding a (meth)acrylic resin, a resin composition excellent in applicability is obtained, and a pattern (cured product) excellent in solvent resistance is obtained.

For example, instead of the polymerizable compound described later or in addition to the polymerizable compound described later, the weight average molecular weight has a high polymerizable value of 20,000 or less (for example, the molar amount of the polymerizable group in 1g of the resin is 1 × 10 ⁻³ mol/g or more) (meth)acrylic resin can be added to the resin composition to improve the coating properties of the resin composition, the solvent resistance of the pattern (cured product), and the like.

When the resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 1% by mass or more with respect to the total solid content of the resin composition. It is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably, and even more preferably 10% by mass or more.

Further, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, with respect to the total solid content of the resin composition. , it is more preferably 60% by mass or less, and even more preferably 50% by mass or less.

Moreover, as a preferable aspect of the resin composition of the present invention, an aspect in which the content of other resins is low is also possible. In the above aspect, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and preferably 5% by mass or less with respect to the total solid content of the resin composition. It is still more preferable, and it is still more preferable that it is 1 mass % or less. The lower limit of the content is not particularly limited, and may be 0% by mass or more.

The resin composition of this invention may contain only 1 type of other resin, and may contain 2 or more types. When including 2 or more types, it is preferable that a total amount becomes the said range.

<Specific polymerization inhibitor>

Curable resin composition of this invention contains the polymerization inhibitor (specific polymerization inhibitor) which has an alkoxysilyl group.

The alkoxysilyl group may be any of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group, but from the viewpoint of suppression of footing, a trialkoxysilyl group is preferable.

As an alkoxy group in the said alkoxysilyl group, a C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and an ethoxy group is still more preferable.

Although the number of alkoxysilyl groups in a specific polymerization inhibitor is not specifically limited, It is preferable that it is 1-4, it is more preferable that it is 1 or 2, and it is still more preferable that it is 1.

It is preferable that a specific polymerization inhibitor is a radical polymerization inhibitor.

In the radical polymerization inhibitor, a stable radical-type radical polymerization inhibitor containing a stable radical in the structure (for example, a polymerization inhibitor containing an aminooxy radical structure, etc.), a growth radical and a compound that is added to form a low-reactivity Chain transfer type radical polymerization in which a chain transfer reaction is performed between an addition reaction type radical polymerization inhibitor (for example, a polymerization inhibitor containing a benzoquinone structure or a nitrobenzene structure, etc.) and a growing radical to generate stable radicals inhibitors (for example, polymerization inhibitors containing a phenol structure, etc.), and the like, and specific polymerization inhibitors may be either of these or other radical polymerization inhibitors.

In the present invention, a structure containing a stable radical in the above structure, a structure in which a compound with low reactivity is formed in addition to a growth radical, and a structure in which a chain transfer reaction is performed between the growth radical to generate a stable radical are collectively referred to as "a structure having polymerization inhibiting ability".

Among these, the specific polymerization inhibitor preferably contains at least one structure selected from the group consisting of an aminooxy radical structure, a phenol structure, a nitrobenzene structure, and a benzoquinone structure, and from the viewpoint of polymerization inhibition ability , It is more preferable to include an aminooxy radical structure.

As the aminooxy radical structure, a 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) structure is particularly preferred.

The number of structures having these polymerization inhibitory abilities contained in the specific polymerization inhibitor is not particularly limited, but is preferably 1 to 4, more preferably 1 or 2, and still more preferably 1.

Moreover, it is preferable that a specific polymerization inhibitor contains at least 1 sort(s) of structure chosen from the group which consists of an amide structure and a urea structure so that a specific polymerization inhibitor may be easily distributed in the deep part of a film|membrane.

These structures may contain only one in a specific polymerization inhibitor, and may contain two or more.

It is preferable that a specific polymerization inhibitor is a compound represented by the following formula (In-1).

[Formula 29]

In formula (In-1), Z ⁿ¹ represents a structure having polymerization inhibitory ability, X ⁿ¹ represents an alkoxysilyl group, L ⁿ¹ represents an organic group having a valence of n+m, n represents an integer greater than or equal to 1, and m represents 1 represents the integer above.

In formula (In-1), the structure having polymerization inhibitory ability in Z ⁿ¹ is at least one structure selected from the group consisting of an aminooxy radical structure, a phenol structure, a nitrobenzene structure, and a benzoquinone structure. It is preferable, and from the viewpoint of polymerization inhibitory ability, it is more preferable that it is an aminooxy radical structure. As the aminooxy radical structure, a 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) structure is particularly preferred.

In formula (In-1), the preferable aspect of the alkoxysilyl group in ^Xn1 is the same as the preferable aspect of the alkoxysilyl group in the specific polymerization inhibitor mentioned above.

In formula (In-1), L ⁿ¹ represents an n+m valent organic group, a hydrocarbon group, or a hydrocarbon group, or a hydrocarbon group, -O-, -S-, -C(=O)- , -S(=O) ₂ -, and -NR ^N -, a group that appears by bonding with at least one group selected from the group consisting of - is preferred.

Moreover, it is preferable that L ⁿ¹ contains at least 1 sort(s) of structure selected from the group which consists of an amide structure and a urea structure mentioned above.

Among these, when n = 1 and m = 1 (that is, when L ⁿ¹ is a divalent linking group), a group represented by the following formula (In-2) or the following formula (In-3) is preferable.

[Formula 30]

In formula (In-2), L ⁿ²¹ and L ⁿ²² each independently represent a single bond or a divalent linking group, R ⁿ²¹ represents a hydrogen atom or a monovalent organic group, and one of # and * represents the formula (In-1 ) ^{, the other represents the binding site with X n1 .}

In formula (In-3), L ⁿ³¹ and L ⁿ³² each independently represent a single bond or a divalent linking group, R ⁿ³¹ and R ⁿ³² each independently represent a hydrogen atom or a monovalent organic group, and among # and * One represents a binding site with ^Zn1 in formula (In-1), and the other represents a binding site with ^Xn1 .

In formula (In-2), as the divalent linking group for L ⁿ²¹ and L ⁿ²² , a hydrocarbon group or a hydrocarbon group, -O-, -S-, -C(=O)-, -S( ═O) ₂ - and -NR ^N - is preferred as a group formed by bonding with at least one group selected from the group consisting of, and a hydrocarbon group is more preferred.

In formula (In-2), R ⁿ²¹ represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom. The monovalent organic group for R ^B21 is not particularly limited, and it is possible to use a known organic group as long as the effect of the present invention is obtained, but it is preferably a hydrocarbon group or an amino group, and an alkyl group or an amino group more preferable Although the number of carbon atoms in the hydrocarbon group or alkyl group is not particularly limited, it is preferably 1 to 10, and more preferably 1 to 4. The amino group may be a substituted amino group or an unsubstituted amino group.

In formula (In-2), any of # and * may be a binding site to Z ⁿ¹ in formula (In-1), but an aspect in which # is a binding site to Z ⁿ¹ is also one of the preferred embodiments.

In addition, when # is a bonding site with Z ⁿ¹ , L ⁿ²¹ is a single bond, and L ⁿ²² is a monovalent organic group is also one of the preferred embodiments of the present invention.

In the formula (In-3), L ⁿ³¹ and L ⁿ³² have the same meaning as L ⁿ²¹ and L ⁿ²² in the formula (In-2), and the preferred embodiments are also the same.

In the formula (In-3), R ⁿ³¹ and R ⁿ³² each have the same meaning as R ⁿ²¹ in the formula (In-2), and the preferred embodiments are also the same.

In formula (In-3), any of # and * may be a binding site to Z ⁿ¹ in formula (In-1), but an aspect in which # is a binding site to Z ⁿ¹ is also one of the preferred embodiments.

In addition, when # is a bonding site with Z ⁿ¹ , L ⁿ³¹ is a single bond, and L ⁿ³² is a monovalent organic group is also one of the preferred embodiments of the present invention.

In formula (In-1), n represents an integer greater than or equal to 1, preferably an integer of 1 to 3, more preferably 1 or 2, particularly preferably 1.

In formula (In-1), m represents an integer greater than or equal to 1, and is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.

Although the molecular weight of a specific polymerization inhibitor is not specifically limited, It is preferable that it is 100-3000, and it is more preferable that it is 200-600.

As a specific example of a specific polymerization inhibitor, the compound used in the Example mentioned later is mentioned.

The content of the specific polymerization inhibitor in the curable resin composition of the present invention is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, with respect to the total solid content of the curable resin composition of the present invention, It is more preferable that it is 0.05-2.5 mass %.

1 type may be sufficient as a specific polymerization inhibitor, and 2 or more types may be sufficient as it. When there are 2 or more types of specific polymerization inhibitors, it is preferable that the sum total is the said range.

[Photoinitiator]

The resin composition of the present invention contains a photopolymerization initiator.

The photopolymerization initiator is preferably a radical photopolymerization initiator. The photo-radical polymerization initiator is not particularly limited, and can be appropriately selected from known photo-radical polymerization initiators. For example, photoradical polymerization initiators having photosensitivity to light rays in the visible range from the ultraviolet range are preferred. Moreover, it may be an activator that generates an active radical by generating some kind of action with a photoexcited sensitizer.

The photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L·mol ^-1 ·cm ^-1 within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). desirable. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using an ultraviolet and visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent.

As an optical radical polymerization initiator, a known compound can be used arbitrarily. For example, acylphosphine compounds such as halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.) and acylphosphine oxides. , oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, hydroxyacetophenone, etc. α-hydroxy ketone compounds, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, and the like. About these details, Paragraph 0165 of Unexamined-Japanese-Patent No. 2016-027357 - 0182 and Paragraph 0138 of International Publication No. 2015/199219 - description of 0151 can be considered into consideration, and this content is integrated in this specification. In addition, Paragraphs 0065 to 0111 of Unexamined-Japanese-Patent No. 2014-130173, compounds described in Japanese Patent Publication No. 6301489, MATERIAL STAGE 37-60p, vol. 19, no. 3, a peroxide-based photopolymerization initiator described in 2019, a photopolymerization initiator described in International Publication No. 2018/221177, a photopolymerization initiator described in International Publication No. 2018/110179, a photopolymerization initiator described in Japanese Unexamined Patent Publication No. 2019-043864, The photoinitiator described in Unexamined-Japanese-Patent No. 2019-044030, and the peroxide-type initiator described in Unexamined-Japanese-Patent No. 2019-167313 are mentioned, These content is also integrated in this specification.

As a ketone compound, the compound of Paragraph 0087 of Unexamined-Japanese-Patent No. 2015-087611 is illustrated, for example, This content is integrated in this specification. As a commercial item, Kayacure-DETX-S (Nippon Kayaku Co., Ltd. product) is also used suitably.

In one embodiment of the present invention, as the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Unexamined Patent Publication No. 10-291969 or an acylphosphine oxide-based initiator described in Japanese Patent Publication No. 4225898 can be used, the contents of which are described herein. is used for

As the α-hydroxyketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade name: all manufactured by BASF) can be used.

As the α-aminoketone initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: both manufactured by BASF) can be used.

As an aminoacetophenone system initiator, the compound of Unexamined-Japanese-Patent No. 2009-191179 which matched the maximum absorption wavelength to the wavelength light source of 365 nm or 405 nm etc. can also be used, The content is integrated in this specification.

Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In addition, Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins B.V.), IRGACURE-819 and IRGACURE-TPO (trade name: both manufactured by BASF) can be used.

Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF), Keycure VIS 813 (manufactured by King Brother Chem), and the like.

As an optical radical polymerization initiator, an oxime compound is mentioned more preferably. By using an oxime compound, it becomes possible to improve exposure latitude more effectively. The oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

As a specific example of an oxime compound, the compound described in Unexamined-Japanese-Patent No. 2001-233842, the compound described in Unexamined-Japanese-Patent No. 2000-080068, the compound described in Unexamined-Japanese-Patent No. 2006-342166, J. C. S. Perkin II (1979, pp 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), Japanese Unexamined Patent Publication A compound described in Japanese Patent Publication No. 2000-066385, a compound described in Japanese Patent Publication No. 2004-534797, a compound described in Japanese Patent Laid-Open No. 2017-019766, a compound described in Japanese Patent Publication No. 6065596, International Publication No. 2015/152153 A compound described in, a compound described in International Publication No. 2017/051680, a compound described in Japanese Unexamined Patent Publication No. 2017-198865, a compound described in Paragraph Nos. 0025 to 0038 of International Publication No. 2017/164127, International Publication No. 2013 /167515, etc. are mentioned, The content of this is integrated in this specification.

Preferable examples of the oxime compound include 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 resin composition of this invention, it is especially preferable to use an oxime compound (oxime type radical photopolymerization initiator) as an optical radical polymerization initiator. An oxime-based photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in its molecule.

[Formula 31]

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., optical The radical polymerization initiator 2) is also suitably used. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Trolly New Electronic Materials Co., Ltd.), Adeka Akles NCI-730, NCI-831 and Deca Arcs NCI-930 (manufactured by ADEKA Co., Ltd.) can also be used. Also, DFI-091 (manufactured by Daito Chemicals Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Moreover, the oxime compound of the following structure can also be used.

[Formula 32]

As the radical photopolymerization initiator, an oxime compound having a fluorene ring can also be used. As a specific example of the oxime compound which has a fluorene ring, the compound of Unexamined-Japanese-Patent No. 2014-137466 and the compound of Unexamined-Japanese-Patent No. 06636081 are mentioned, The content is integrated in this specification.

As the photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring among carbazole rings has become a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound of international publication 2013/083505 is mentioned, This content is integrated in this specification.

Moreover, it is also possible to use the oxime compound which has a fluorine atom. As a specific example of such an oxime compound, the compound described in Unexamined-Japanese-Patent No. 2010-262028, the compound 24, 36-40 described in Paragraph 0345 of Unexamined-Japanese-Patent No. 2014-500852, and Unexamined-Japanese-Patent No. 2013- and the compound (C-3) described in Paragraph 0101 of No. 164471, the contents of which are incorporated herein by reference.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable to use the oxime compound which has a nitro group as a dimer. As specific examples of the oxime compound having a nitro group, the compounds described in Paragraph Nos. 0031 to 0047 of Unexamined-Japanese-Patent No. 2013-114249, Paragraph Nos. 0008 to 0012, and 0070 to 0079 of Unexamined-Japanese-Patent No. 2014-137466, Japanese Patent Publication Paragraph No. 0007 of No. 4223071 - the compound described in 0025 are mentioned, The content of this is integrated in this specification. Moreover, as an oxime compound which has a nitro group, Adeka Akles NCI-831 (made by ADEKA Corporation) is also mentioned.

As the photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. As a specific example, OE-01 described in international publication 2015/036910 - OE-75 is mentioned.

As the radical photopolymerization initiator, an oxime compound having a substituent having a hydroxyl group bonded to a carbazole skeleton can also be used. As such a photoinitiator, the compound of international publication 2019/088055, etc. are mentioned, This content is integrated in this specification.

As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar ^OX1 in which an electron withdrawing group is introduced into an aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used. Examples of the electron withdrawing group possessed by the aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group, and an acyl group and A nitro group is preferable, and an acyl group is more preferable, and a benzoyl group is more preferable because it is easy to form a film having excellent light resistance. The benzoyl group may have a substituent. As the substituent, a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group, and an alkoxy group, an alkylsulfanyl group or an amino group. it is more preferable

The oxime compound OX is preferably at least one selected from compounds represented by formula (OX1) and compounds represented by formula (OX2), and more preferably is a compound represented by formula (OX2).

[Formula 33]

In the formula, R ^X1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, represents an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group;

R ^X2 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group , Representing an acyloxy group or an amino group,

R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent.

However, at least one of R ^X10 to R ^X14 is an electron withdrawing group.

In the above formula, it is preferable that R ^X12 is an electron withdrawing group, and R ^X10 , R ^X11 , R ^X13 , and R ^X14 are hydrogen atoms.

As a specific example of oxime compound OX, Paragraph No. 0083 of Japanese Patent Publication 4600600 - the compound of 0105 are mentioned, This content is integrated in this specification.

As the most preferable oxime compound, the oxime compound which has a specific substituent shown in Unexamined-Japanese-Patent No. 2007-269779, the oxime compound which has a thioaryl group shown in Unexamined-Japanese-Patent No. 2009-191061, etc. are mentioned, The content of which is incorporated herein by reference.

Radical photopolymerization initiators are, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metal Rosene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxa Compounds selected from the group consisting of diazole compounds and 3-aryl-substituted coumarin compounds are preferred.

More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium salt compounds. , A benzophenone compound, an acetophenone compound, at least one selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds A compound of the species is more preferable, and it is even more preferable to use a metallocene compound or an oxime compound.

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

[Formula 34]

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 a carbon atom having 1 to 20 carbon atoms. Alkyl group, alkoxy group of 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group of 2 to 12 carbon atoms, alkyl group of 2 to 18 carbon atoms and 1 to 4 carbon atoms interrupted by one or more oxygen atoms A phenyl group or a biphenyl group substituted with at least one of the alkyl groups of , R ^I01 is a group represented by formula (II) or the same group as R ^I00 , and R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbon atoms. , an alkoxy group having 1 to 12 carbon atoms or a halogen atom.

[Formula 35]

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

Moreover, as an optical radical polymerization initiator, Paragraph 0048 of International Publication No. 2015/125469 - the compound of 0055 can also be used, and this content is integrated in this specification.

As the radical photopolymerization initiator, a bifunctional or trifunctional or higher functional radical photopolymerization initiator may be used. Since two or more radicals generate|occur|produce from one molecule of radical photopolymerization initiator by using such a radical photopolymerization initiator, favorable sensitivity is obtained. In addition, in the case of using a compound with an asymmetric structure, crystallinity is reduced, solubility in solvents and the like is improved, and it is difficult to precipitate over time, so that the stability over time of the resin composition can be improved. As a specific example of a bifunctional or trifunctional or more than trifunctional radical photopolymerization initiator, paragraphs of Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, Japanese Patent Publication No. 2016-532675 Dimers of oxime compounds described in No. 0407 to 0412, Paragraph Nos. 0039 to 0055 of International Publication No. 2017/033680, compounds (E) and compounds (G) described in Japanese Patent Publication No. 2013-522445, Cmpd 1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiator described in Paragraph No. 0007 of Japanese Patent Publication No. 2017-523465, Paragraph Nos. 0020 to 0033 of Japanese Unexamined Patent Publication No. 2017-167399 , the photopolymerization initiator (A) described in Paragraph Nos. 0017 to 0026 of Japanese Unexamined Patent Publication No. 2017-151342, and the oxime ester photoinitiator described in Japanese Patent Publication No. 6469669, etc., this content is incorporated herein.

When a photopolymerization initiator is included, the content thereof 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 resin composition of the present invention. %, more preferably 1.0 to 10% by mass. The photoinitiator may contain only 1 type, and may contain 2 or more types. When containing 2 or more types of photoinitiators, it is preferable that the total amount is the said range.

In addition, since a photoinitiator also functions as a thermal polymerization initiator in some cases, crosslinking by the photopolymerization initiator can be further promoted by heating in an oven, a hot plate or the like in some cases.

[sensitizer]

The resin composition may contain a sensitizer. A sensitizer absorbs specific actinic radiation and becomes an electronic excited state. The sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, an optical radical polymerization initiator, and the like, and actions such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and photoradical polymerization initiator are decomposed by chemical change to generate radicals, acids or bases.

As usable sensitizers, benzophenone-based, Michler's ketone-based, coumarin-based, pyrazolazo-based, anilinoazo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyraline Compounds such as zolotriazolazo-based, pyridonazo-based, cyanine-based, phenothiazine-based, pyrrolopyrazolazomethane-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds can be used.

Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis( 4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4 '-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 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-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin ( 7-(diethylamino)coumarin-3-carboxylic acid ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morphopoly Nobenzophenone, dimethylaminobenzoate isoamyl, diethylaminobenzoate isoamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p- Dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide and the like.

Moreover, you may use another sensitizing dye.

About the detail of a sensitizing dye, Paragraph 0161 of Unexamined-Japanese-Patent No. 2016-027357 - description of 0163 can be considered into consideration, and this content is integrated in this specification.

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

[Chain transfer agent]

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

Moreover, Paragraph 0152 of International Publication No. 2015/199219 - the compound of 0153 can also be used for a chain transfer agent, and this content is integrated in this specification.

When the 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 0.1 to 10 parts by mass, and 0.5 parts by mass to 100 parts by mass of the total solid content of the resin composition of the present invention. -5 parts by mass is more preferred. 1 type of chain transfer agent may be sufficient as it, and 2 or more types may be sufficient as it. When there are 2 or more types of chain transfer agents, it is preferable that the sum total is the said range.

<Polymerizable compound>

The resin composition of the present invention contains a polymerizable compound.

As a polymeric compound, a radical crosslinking agent or another crosslinking agent is mentioned.

[Radical Crosslinking Agent]

It is preferable that the resin composition of this invention contains a radical crosslinking agent.

A radical crosslinking agent is a compound having a radical polymerizable group. As the radical polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.

Among these, as a group containing the said ethylenically unsaturated bond, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferable, and a (meth)acryloyl group is more preferable from a reactive viewpoint.

It is preferable that it is a compound which has one or more ethylenically unsaturated bonds, but, as for a radical crosslinking agent, it is more preferable that it is a compound which has two or more. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.

As the compound having two or more ethylenically unsaturated bonds, compounds having 2 to 15 ethylenically unsaturated bonds are preferable, compounds having 2 to 10 ethylenically unsaturated bonds are more preferable, and compounds having 2 to 6 this is more preferable

Further, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. .

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 900 or less. As for the lower limit of the molecular weight of a radical crosslinking agent, 100 or more are preferable.

Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof, preferably unsaturated These are esters of carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or a monofunctional or polyfunctional carboxylic acid Dehydration condensation reactants and the like are also suitably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, furthermore, a halo xeno group, a tosyloxy group, etc. Also suitable are substitution reactants of unsaturated carboxylic acid esters or amides having a leaving substituent with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers and the like instead of the above unsaturated carboxylic acids. As a specific example, Paragraph 0113 of Unexamined-Japanese-Patent No. 2016-027357 - description of 0122 can be considered into consideration, and these content is integrated in this specification.

Moreover, the radical crosslinking agent is also preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, 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, hexanedioldi(meth)acrylate, trimethylolpropane tri(acryloyl Compound obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as oxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin or trimethylolethane, and then (meth)acrylated compounds, Japan Urethane (meth)acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication Polyester acrylates described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490, epoxy acrylic which is a reaction product of epoxy resin and (meth)acrylic acid Polyfunctional acrylates and methacrylates, such as lates, and mixtures thereof are exemplified. Moreover, Paragraph 0254 of Unexamined-Japanese-Patent No. 2008-292970 - the compound of 0257 are also suitable. Moreover, the polyfunctional (meth)acrylate obtained by making the compound which has a cyclic ether group, such as glycidyl (meth)acrylate, and an ethylenically unsaturated bond react with polyfunctional carboxylic acid, etc. are mentioned.

In addition, as preferred radical crosslinking agents other than those described above, those described in Japanese Unexamined Patent Publication No. 2010-160418, Japanese Unexamined Patent Publication No. 2010-129825, Japanese Patent Publication No. 4364216, etc., have a fluorene ring and have an ethylenically unsaturated bond. It is also possible to use compounds having two or more groups and cardo resin.

In addition, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. Hei 01-040337, and Japanese Patent Publication Hei 01-040336, and Japanese Unexamined Patent Publication Hei 02-025493 and the vinylphosphonic acid-based compounds described in No. Moreover, the compound containing the perfluoroalkyl group of Unexamined-Japanese-Patent No. 61-022048 can also be used. Also, Journal of the Japan Adhesion Association vol. 20, no. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300 to 308 (1984) can also be used.

In addition to the above, the compound of Paragraph 0048 of Unexamined-Japanese-Patent No. 2015-034964 - 0051, and the compound of Paragraph 0087 of International Publication No. 2015/199219 - 0131 can also be used preferably, These content is integrated in this specification.

In addition, after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described with specific examples as formula (1) and formula (2) in Japanese Unexamined Patent Publication No. 10-062986, (meth)acrylated A compound can also be used as a radical crosslinking agent.

In addition, Paragraph 0104 of Unexamined-Japanese-Patent No. 2015-187211 - the compound of 0131 can also be used as a radical crosslinking agent, These content is integrated in this specification.

As a radical crosslinking agent, dipentaerythritol triacrylate (as a commercial item, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial item, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) , A-TMMT: Shin Nakamura Chemical Industry Co., Ltd. product), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd. product), dipentaerythritol hexa (meth) ) Acrylates (commercially available, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and their (meth)acryloyl groups are ethylene glycol residues or propylene glycol residues A structure bonded via is preferable. These oligomeric types can also be used.

As a commercially available product of the radical crosslinking agent, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, and SR-209, manufactured by Sartomer, which is a bifunctional methacrylate having four ethyleneoxy chains, 231, 239, DPCA-60, a 6-functional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane Oligomer UAS-10, UAB-140 (manufactured by Nippon Seishi Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin Nakamura Kagaku Kogyo), DPHA- 40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (Nichiyu ( Note) and the like.

Examples of the radical crosslinking agent include those described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. Hei 02-032293, and Japanese Patent Publication No. Hei 02-016765. Retane acrylates, ethylene oxide systems described in Japanese Publication No. 58-049860, Japanese Publication No. 56-017654, Japanese Publication No. 62-039417, Japanese Publication No. 62-039418 Urethane compounds having a skeleton are also suitable. In addition, as a radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. Hei 01-105238 can be used. can also be used

The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphoric acid group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to have an acid group do. Particularly preferably, in a radical crosslinking agent obtained by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to have an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. am. As a commercial item, M-510, M-520 etc. are mentioned, for example as a Toagosei Co., Ltd. product polybasic acid modified acrylic oligomer.

The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, particularly preferably 1 to 100 mgKOH/g. When the acid value of the radical crosslinking agent is in the above range, the handleability in production is excellent, and furthermore, the developability is excellent. Moreover, polymerizability is good. The said acid value is measured based on description of JISK0070:1992.

For the resin composition, it is preferable to use a bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film stretchability.

As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 Diacrylate, PEG200 Dimethacrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate , neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate Rate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylic acid of bisphenol A Rate, PO (propylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified Diacrylates, isocyanuric acid-modified dimethacrylates, and other bifunctional acrylates having a urethane bond and bifunctional methacrylates having a urethane bond can be used. These can mix and use 2 or more types as needed.

In addition, for example, PEG200 diacrylate is polyethylene glycol diacrylate, and means that the formula of a polyethylene glycol chain is about 200.

In the resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of curvature suppression by controlling the modulus of elasticity of the pattern (cured product). As a monofunctional radical crosslinking agent, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, 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 mono(meth)acrylate and polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl Ether and the like are preferably used. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100°C or higher under normal pressure is also preferable.

In addition, allyl compounds, such as a diallyl phthalate and triallyl trimellitate, are mentioned as a bifunctional or more than bifunctional radical crosslinking agent.

When containing a radical crosslinking agent, it is preferable that the content is more than 0 mass % and 60 mass % or less with respect to the total solids of the resin composition of this invention. As for a lower limit, 5 mass % or more is more preferable. As for an 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.

A radical crosslinking agent may be used individually by 1 type, but may mix and use 2 or more types. When using 2 or more types together, it is preferable that the total amount becomes said range.

[Other crosslinking agents]

It is also preferable that the resin composition of this invention contains another crosslinking agent different from the radical crosslinking agent mentioned above.

In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and a covalent bond between the above-mentioned photoacid generator or photobase generator and other compounds in the composition or a reaction product thereof by photosensitization of the photoacid generator. It is preferable that the compound has a plurality of groups in the molecule that promote the reaction to form a group in the molecule that promotes the reaction of forming a covalent bond with other compounds or reaction products thereof in the composition by the action of an acid or base. A compound having a plurality of them is preferable.

The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.

As another crosslinking agent, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group is a nitrogen atom A compound having a structure directly bonded to is more preferred.

As another crosslinking agent, for example, formaldehyde or formaldehyde and alcohol are reacted with an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, benzoguanamine, etc., and the hydrogen atom of the amino group is converted to an acyloxymethyl group, methyl Compounds having a structure substituted with an all group or an alkoxymethyl group are exemplified. The manufacturing method of these compounds is not specifically limited, Any compound having the same structure as the compound manufactured by the said method is sufficient. Moreover, the oligomer formed by self condensation of the methylol groups of these compounds may be sufficient.

As the amino group-containing compound, a crosslinking agent using melamine is a melamine crosslinking agent, glycoluril, a crosslinking agent using urea or an alkylene urea is a urea crosslinking agent, a crosslinking agent using alkylene urea is an alkylene urea crosslinking agent, benzoguanamine A crosslinking agent using is called a benzoguanamine-based crosslinking agent.

Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and from the group consisting of a glycoluril-based crosslinking agent and a melamine-based crosslinking agent described later. It is more preferable to include at least one selected compound.

As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the urea structure described below, or on a triazine It can be mentioned as a structural example.

The alkoxymethyl group or acyloxymethyl group of the compound has preferably 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, still more preferably 2 carbon atoms.

The total number of alkoxymethyl groups and acyloxymethyl groups of the compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

The molecular weight of the compound is preferably 1500 or less, preferably 180 to 1200.

[Formula 36]

R ₁₀₀ represents an alkyl group or an acyl group.

R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group, and may be bonded to each other to form a ring.

Examples of the compound in which the alkoxymethyl group or acyloxymethyl group is directly substituted with an aromatic group include compounds of the following general formula.

[Formula 37]

In the formula, X represents a single bond or a divalent organic group, each R ₁₀₄ independently represents an alkyl group or an acyl group, and R ₁₀₃ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or an acid A group that is decomposed by the action and generates an alkali-soluble group (for example, a group that is desorbed by the action of an acid, a group represented by -C(R ⁴ ) ₂ COOR ⁵ (R ⁴ are each independently a hydrogen atom or a carbon number) represents an alkyl group of 1 to 4, and R ⁵ represents a group that is eliminated by the action of an acid.)).

R ₁₀₅ Each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, and a+ d is 5 or less, b+e is 4 or less, and c+f is 4 or less.

For R 5 in a group decomposed by the action of an acid to generate an alkali-soluble group, a group desorbed ^by the action of an acid, and a group represented by -C(R ⁴ ) ₂ COOR ⁵ , for example, -C( R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), and the like.

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

As said alkyl group, a C1-C10 alkyl group is preferable, and a C1-C5 alkyl group is more preferable.

The alkyl group may be linear or branched.

As said cycloalkyl group, a C3-C12 cycloalkyl group is preferable, and a C3-C8 cycloalkyl group is more preferable.

The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.

It is preferable that the said aryl group is a C6-C30 aromatic hydrocarbon group, and it is more preferable that it is a phenyl group.

As said aralkyl group, a C7-C20 aralkyl group is preferable, and a C7-C16 aralkyl group is more preferable.

The aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the above-described alkyl and aryl groups.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.

Moreover, these groups may further have a well-known substituent within the range in which the effect of this invention is acquired.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The group decomposed by the action of an acid to generate an alkali-soluble group or the group that is eliminated by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or the like. More preferably, they are a tertiary alkyl ester group and an acetal group.

As a compound which has an alkoxymethyl group, the following structures are specifically mentioned. Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compounds has been changed to an acyloxymethyl group. Although the following compounds are mentioned as a compound which has an alkoxymethyl group or acyloxymethyl in a molecule|numerator, It is not limited to these.

[Formula 38]

[Formula 39]

As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available compound may be used, or a compound synthesized by a known method may be used.

From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

Specific examples of the urea-based crosslinking agent include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxy Methylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril , triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated Glycoluril-based crosslinking agents such as glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril ;

urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, and bisbutoxymethyl urea;

monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, di Ethylene urea-based crosslinking agents such as propoxymethylated ethylene urea, monobutoxymethylated ethylene urea, or dibutoxymethylated ethylene urea;

monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, di propylene urea-based crosslinking agents such as propoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea;

1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazoli dinone etc. are mentioned.

Specific examples of the benzoguanamine-based crosslinking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, and monomethoxymethylated benzoguanamine. Namine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, Tetraethoxymethylated Benzoguanamine, Monopropoxymethylated Benzoguanamine, Dipropoxymethylated Benzoguanamine, Tripropoxymethylated Benzoguanamine, Tetrapropoxymethylated Benzoguanamine, Monobutoxymethylated Benzoguanamine, Dibu Toxymethylation benzoguanamine, tributoxymethylation benzoguanamine, tetrabutoxymethylation benzoguanamine, etc. are mentioned.

In addition, as a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring). are also suitably used.

Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, Hydroxymethylbenzoic acid Hydroxymethylphenyl, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl) Dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylbenzoic acid methoxymethylphenyl, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl) Biphenyl, 4,4',4''-ethylidentris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(tri Fluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3 ', 5,5'-tetrakis (methoxymethyl) -1,1'-biphenyl-4 , 4'-diol, etc. are mentioned.

Commercially available products may be used as other crosslinking agents, and suitable commercially available products include 46DMOC, 46DMOEP (above, manufactured by Asahi Yukizai Kogyo Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC- P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML- BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, made by Honshu Kagaku Kogyo), Nikarak ( (registered trademark, hereinafter the same) MX-290, Nikarak MX-280, Nikarak MX-270, Nikarak MX-279, Nikarak MW-100LM, Nikarak MX-750LM (above, manufactured by Sanwa Chemical Co., Ltd.), etc. there is.

Moreover, it is also preferable that the resin composition of this invention contains at least 1 sort(s) of compound selected from the group which consists of an epoxy compound, an oxetane compound, and a benzoxazine compound as another crosslinking agent.

-Epoxy compound (compound having an epoxy group)-

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

It is preferable that the epoxy compound contains a polyethylene oxide group. Thereby, the modulus of elasticity is lowered and the warpage 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 2-15.

As an example of an epoxy compound, it is bisphenol-A epoxy resin; bisphenol F-type epoxy resin; Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as diglycidyl ether and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Epoxy group-containing silicones, such as polymethyl (glycidyloxypropyl) siloxane, etc. are mentioned, but are not limited to these. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) HP-4770, 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 (above product names, manufactured by DIC Co., Ltd.), Rica Resin (registered trademark) BEO-20E, Rica Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (trade name, New Japan Rica Co., Ltd.), EP- 4003S, EP-4000S, EP-4088S, EP-3950S (above product names, manufactured by ADEKA Co., Ltd.), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, Celoxide (registered trademark) 2000, EHPE3150, Epolide (registered trademark) GT401, Epolide (registered trademark) PB4700, Epolide (registered trademark) PB3600 (above product names, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC-3000 -H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H , EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (above brand name, Nippon Kayaku Co., Ltd. product), etc. are mentioned. Moreover, the following compounds are also used suitably.

[Formula 40]

In the formula, n is an integer of 1 to 5, m is an integer of 1 to 20.

Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and elongation improvement.

-Oxetane compound (compound having an oxetanyl group)-

As the oxetane compound, a compound having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy ]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl] ester, and the like. . As a specific example, Aron Oxetane series (eg, OXT-121, OXT-221) manufactured by Toagosei Co., Ltd. can be suitably used, and these may be used alone or in combination of two or more.

-Benzoxazine compound (compound having a benzoxazolyl group)-

The benzoxazine compound is preferable in that it does not generate degassing during curing due to a crosslinking reaction derived from a ring-opening addition reaction, and also suppresses occurrence of warpage by reducing heat shrinkage.

Preferable examples of the benzoxazine compound include P-d-type benzoxazine, F-a-type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolak-type dihydrobenzene. An oxazine compound is mentioned. These may be used independently or may mix 2 or more types.

The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and preferably 1.0 to 15% by mass, based on the total solid content of the resin composition of the present invention. It is especially preferable that it is 10 mass %. Another crosslinking agent may contain only 1 type, and may contain 2 or more types. When 2 or more types of other crosslinking agents are contained, it is preferable that the sum total is the said range.

<Compound B>

The curable resin composition of the present invention preferably contains compound B which is a compound having a polymerizable group and an azole group.

[polymerizable group]

Examples of the polymerizable group in the compound B include known polymerizable groups such as a radical polymerizable group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group, and a (block) isocyanate group.

Among these, it is preferable that compound B contains at least 1 sort(s) of group selected from the group which consists of a radical polymerizable group and an alkoxysilyl group as a polymerizable group from an adhesive viewpoint with the metal of hardened|cured material.

Although any of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group may be sufficient as the said alkoxysilyl group, the trialkoxysilyl group is preferable from an adhesive viewpoint with the metal of hardened|cured material.

As an alkoxy group in the said alkoxysilyl group, a C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and an ethoxy group is still more preferable.

As the radical polymerizable group, a group having an ethylenically unsaturated bond is preferable.

Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group bonded directly to an aromatic ring such as a vinyl group, an allyl group, and a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and the like. and a (meth)acryloyloxy group is preferable.

Compound B may have only one polymerizable group, or may have two or more.

Moreover, compound B may have only 1 type of polymeric groups, and may have 2 or more types. For example, you may have a radical polymerizable group and an alkoxysilyl group.

[azole group]

The azole group in the compound B is a 5-membered heterocyclic compound containing one or more nitrogen atoms as a reduction, and a group having a structure in which one or more hydrogen atoms are removed from a 5-membered heterocyclic compound which may have a substituent or condensed ring structure. However, it is a hetero 5-membered ring compound containing only one or more nitrogen atoms and one or more carbon atoms as a reduction, and a group having a structure in which one or more hydrogen atoms are removed from the hetero5-membered ring compound which may have a substituent is preferable.

From the viewpoint of adhesion to the metal of the cured product, examples of the azole group include a pyrrole ring, a pyrazole ring, an indazole ring, an imidazole ring, a benzimidazole ring, a 1,2,3-triazole ring, and a 1,2,4-triazole ring. A ring, a benzotriazole ring, or a group having a structure in which one or more hydrogen atoms are removed from the tetrazole ring is preferable, and an imidazole ring, a benzimidazole ring, a 1,2,4-triazole ring, or a benzotriazole ring. More preferred is a group having a structure in which one or more hydrogen atoms have been removed from the azole ring.

Moreover, it is preferable that the azole group in compound B is a group represented by the following formula (B-1) or the following formula (B-2).

[Formula 41]

In formula (B-1), R ^B1 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group having no polymerizable group, and Z ^B1 to Z ^B4 are each independently =CR ^B7 - or represents a nitrogen atom, R ^B7 represents a bonding site to a structure having a polymerizable group, a hydrogen atom or a monovalent organic group having no polymerizable group, and at least one of R ^B1 and R ^B7 contained in formula (B-1) represents a bonding site with a structure having a polymerizable group;

In formula (B-2), R ^B2 to R ^B6 each independently represent a bonding site to a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group having no polymerizable group, and Z ^B5 and Z ^B6 are each independently where =CR ^B8 - or represents a nitrogen atom, R ^B8 represents a bonding site to a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group having no polymerizable group, and is included in the formula (B-2) Among R ^B2 to R ^B6 and R ^B8 , at least one represents a bonding site with a structure having a polymerizable group.

In formula (B-1), R ^B1 represents a bonding site to a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group having no polymerizable group, and is more preferably a bonding site to a structure having a polymerizable group.

The monovalent organic group for R ^B1 is not particularly limited, and it is possible to use a known organic group as long as the effect of the present invention is obtained, but it is preferably a hydrocarbon group or an amino group, and an alkyl group or an amino group it is more preferable Although the number of carbon atoms in the hydrocarbon group or alkyl group is not particularly limited, it is preferably 1 to 10, and more preferably 1 to 4.

The amino group may be a substituted amino group or an unsubstituted amino group.

In formula (B-1), each of Z ^B1 to Z ^B4 independently represents =CR ^B7 - or a nitrogen atom.

Among them, two of Z ^B1 to Z ^B4 are nitrogen atoms, two of which are =CR ^B7 -, one of Z ^B1 to Z ^B4 are nitrogen atoms, and three of them are =CR ^B7 -, or Z ^B1 to Z An aspect in which three of ^B4 are nitrogen atoms and one is =CR ^B7 - is preferable.

Also, among these, Z ^B1 and Z ^B3 are nitrogen atoms, Z ^B2 and Z ^B4 are =CR ^B7 -, Z ^B1 and Z ^B2 are nitrogen atoms, and Z ^B3 and Z ^B4 are =CR ^B7 -. , Z ^B2 is a nitrogen atom, Z ^B1 , Z ^B3 and Z ^B4 are =CR ^B7 -, or, Z ^B1 , Z ^B2 and Z ^B3 are nitrogen atoms, Z ^B4 is =CR ^B7 - is preferred and Z ^B1 and Z ^B3 are nitrogen atoms, and Z ^B2 and Z ^B4 are =CR ^B7 -.

R ^B7 is preferably a hydrogen atom or a monovalent organic group.

Further, when Z ^B1 , Z ^B2 and Z ^B3 are nitrogen atoms and Z ^B4 is =CR ^B7 -, R ^B7 is preferably a bonding site with a structure having a polymerizable group.

The preferable aspect of the monovalent organic group for R ^B7 is the same as the preferable aspect of the monovalent organic group for R ^B1 described above.

It is preferable that at least one of R ^B1 and R ^B7 contained in Formula (B-1) represents a bonding site to a structure having a polymerizable group, and at least R ^B1 represents a bonding site to a structure having a polymerizable group. Further, in the formula (B-1), an aspect in which only R ^B1 represents a bonding site to a structure having a polymerizable group and each of R ^B7 independently represents a hydrogen atom or a monovalent organic group is also one of the preferred embodiments of the present invention. .

In formula (B-2), Z ^B5 and Z ^B6 each independently represent =CR ^B8 - or a nitrogen atom.

Among them, an aspect in which both Z ^B5 and Z ^B6 represent a nitrogen atom or an aspect in which Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 - are preferred.

In the formula (B-2), when both Z ^B5 and Z ^B6 represent a nitrogen atom, it is preferable that R ^B6 represents a bonding site with a structure having a polymerizable group. Further, in the formula (B-2), an embodiment in which both Z ^B5 and Z ^B6 represent a nitrogen atom and only R ^B6 represents a bonding site to a structure having a polymerizable group is also one of the preferred embodiments of the present invention.

In the formula (B-2), when Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 -, it is preferable that R ^B8 represents a bonding site with a structure having a polymerizable group. Further, in the formula (B-2), Z ^B5 represents a nitrogen atom, Z ^B6 represents =CR ^B8 -, and only R ^B8 represents a bonding site with a structure having a polymerizable group, according to the present invention. is one of the preferred aspects of

In formula (B-2), it is preferable that each of R ^B2 to R ^B5 independently represents a hydrogen atom or a monovalent organic group having no polymerizable group. The preferable aspect of the monovalent organic group in R ^B2 to R ^B5 is the same as the preferable aspect of the monovalent organic group in R ^B1 described above.

In formula (B-2), when Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 -, R ^B6 preferably represents a hydrogen atom or a monovalent organic group having no polymerizable group. The preferable aspect of the monovalent organic group in R ^B6 is the same as the preferable aspect of the monovalent organic group in R ^B1 described above.

In other cases, R ^B6 preferably represents a bonding site with a structure having a polymerizable group. In particular, when Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 -, it is preferable that R ^B8 represents a bonding site with a structure having a polymerizable group.

In formula (B-2), R ^B8 preferably represents a bonding site with a structure having a polymerizable group.

When both Z ^B5 and Z ^B6 represent =CR ^B8 -, it is preferable that one R ^B8 represents a bonding site to a structure having a polymerizable group and the other represents a hydrogen atom or a monovalent organic group. The preferable aspect of the monovalent organic group in R ^B8 is the same as the preferable aspect of the monovalent organic group in R ^B1 described above.

At least one of R ^B2 to R ^B6 and R ^B8 in Formula (B-2) represents a bonding site with a structure having a polymerizable group, and at least R ^B6 or R ^B8 is a bonding site with a structure having a polymerizable group. It is desirable to indicate In formula (B-2), only one of R ^B6 and R ^B8 represents a bonding site with a structure having a polymerizable group, and the other of R ^B6 and R ^B8 and R ^B2 to R ^B5 are each independently hydrogen. An aspect showing an atom or a monovalent organic group is also one of the preferable aspects of the present invention.

Among these, the azole group is preferably a group represented by any of the following formulas (B-3) to (B-6).

[Formula 42]

In formulas (B-3) to (B-6), R ^B9 to R ^B20 each independently represent a hydrogen atom or a monovalent organic group having no polymerizable group, and * is a bonding site to a structure having a polymerizable group. indicates

In formulas (B-3) to (B-6), preferred embodiments of the monovalent organic group for R ^B9 to R ^B20 are the same as those described above for the monovalent organic group for R ^B1 .

It is preferable that compound B has at least 1 sort(s) of group selected from the group which consists of an amide group, a urethane group, and a urea group from an adhesive viewpoint with the metal of the hardened|cured material obtained.

When compound B has at least one group selected from the group consisting of amide group, urethane group and urea group, interaction between compound B and specific resin is promoted and adhesion between cured product and metal is estimated to be improved.

The amide group, urethane group and urea group may be directly bonded to the azole group or may be bonded through a linking group.

As the linking group, at least one selected from the group consisting of a hydrocarbon group, a hydrocarbon group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, and -NR ^N - A group represented by a bond with a group of is preferable, and a hydrocarbon group is more preferable.

R ^N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

As said hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable and an alkylene group is more preferable.

2-20 are preferable and, as for carbon number of the said hydrocarbon group or alkylene group, 2-10 are more preferable.

When compound B has an amide group, urethane group or urea group, compound B has a structure containing the azole group and an amide group, urethane group or urea group, and is represented by the following formulas (B-7) and (B-8) Or what has a structure represented by Formula (B-9) is preferable.

[Formula 43]

In formula (B-7), X ¹ represents an azole group, L ¹ represents a single bond or a divalent linking group, R ^B21 represents a hydrogen atom or a monovalent organic group, and * is a bonding site with a structure having a polymerizable group. indicates

In formula (B-8), X ² represents an azole group, L ² represents a single bond or a divalent linking group, R ^B22 represents a hydrogen atom or a monovalent organic group, and * is a bonding site with a structure having a polymerizable group. indicates

In formula (B-9), X ³ represents an azole group, L ³ represents a single bond or a divalent linking group, R ^B23 and R ^B24 each independently represent a hydrogen atom or a monovalent organic group, and * represents a polymerizable group. represents a binding site with a structure having

In formula (B-7), the preferred aspect of the azole group for X ¹ is as described above. The above-mentioned bonding site with the structure having a polymerizable group in the azole group corresponds to the bonding site with L ¹ in formula (B-7).

In formula (B-7), as the divalent linking group for L ¹ , a hydrocarbon group or a hydrocarbon group, -O-, -S-, -C(=O)-, -S(=O) A group formed by bonding with at least one group selected from the group consisting of _2- and -NR ^N- is preferable, and a hydrocarbon group is more preferable.

The R ^N is as described above.

As said hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable and an alkylene group is more preferable.

2-20 are preferable and, as for carbon number of the said hydrocarbon group or alkylene group, 2-10 are more preferable.

In formula (B-7), R ^B21 represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom. Preferred aspects of the monovalent organic group in R ^B21 are the same as those for R ^B1 described above.

In formula (B-8), X ² is X ¹ in formula (B-7), L ² is L ¹ in formula (B-7), and R ^B22 is R ^B21 in formula (B-7), respectively. It is the same meaning, and a preferable aspect is also the same.

In formula (B-9), X ³ is X ¹ in formula (B-7), L ³ is L ¹ in formula (B-7), R ^B23 and R ^B24 are each independently It has the same meaning as R ^B21 in 7), and the preferred embodiment is also the same.

Compound B may be a compound having a molecular weight of less than 2,000 (hereinafter also referred to as "low molecular weight compound B") or a resin (hereinafter also referred to as "resin B").

Moreover, it is also preferable that curable resin composition contains both the low molecular weight compound B and resin B from an adhesive viewpoint with the metal of hardened|cured material.

[Low Molecular Compound B]

The molecular weight of the low molecular weight compound B is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.

The number of polymerizable groups in the low molecular compound B is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

The number of azole groups in the low molecular weight compound B is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, still more preferably 1 or 2, still more preferably 1.

It is preferable that the low molecular weight compound B is a compound represented by the following formula (BL-1).

[Formula 44]

In formula (BL-1), X ^LA represents an azole group, L ^LA represents a single bond or an m+1 valent linking group, X ^LB represents a polymerizable group, n represents an integer greater than or equal to 1, and m represents an integer greater than or equal to 1 indicates

In formula (BL-1), the preferred aspect of the azole group in X ^LA is as described above.

In formula (BL-1), L ^LA is a single bond, a hydrocarbon group, or a hydrocarbon group, -O-, -S-, -C(=O)-, -S(=O) ₂ - and - A group represented by bonding with at least one group selected from the group consisting of NR ^N - is preferred.

The R ^N is as described above.

As said hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable and an alkylene group is more preferable.

2-20 are preferable and, as for carbon number of the said hydrocarbon group or alkylene group, 2-10 are more preferable.

Moreover, in formula (BL-1), an aspect in which L ^LA is a group represented by the following formula (L-1) or formula (L-2) is also one of the preferred aspects of the present invention.

[Formula 45]

In formula (L-1), L ¹ represents a single bond or a divalent linking group, R ^B21 represents a hydrogen atom or a monovalent organic group, L ³ represents an n1+monovalent linking group, and n1 represents an integer greater than or equal to 1. , # represents a bonding site with an azole group, and * represents a bonding site with a polymerizable group.

In formula (L-2), L ² represents a single bond or a divalent linking group, R ^B22 and R ^B23 each independently represent a hydrogen atom or a monovalent organic group, L ⁴ represents an n2+ monovalent linking group, n2 represents an integer greater than or equal to 1, # represents a bonding site with an azole group, and * represents a bonding site with a polymerizable group.

In formula (L-1), L ¹ and R ^B21 each have the same meaning as L ¹ and R ^B21 in formula (B-7), and preferred embodiments are also the same.

In formula (L-1), L ³ is a hydrocarbon group, or a hydrocarbon group, -O-, -S-, -C(=O)-, -S(=O) ₂ - and -NR ^N - A group that appears by bonding with at least one group selected from the group consisting of is preferred.

The R ^N is as described above.

As said hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable and an alkylene group is more preferable.

2-20 are preferable and, as for carbon number of the said hydrocarbon group or alkylene group, 2-10 are more preferable.

In formula (L-1), n1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, still more preferably 1 or 2, particularly preferably 1.

In formula (L-2), L ² , R ^B22 and R ^B23 have the same meanings as L ² , R ^B22 and R ^B23 in formula (B-8), and preferred embodiments are also the same.

In formula (L-2), L ⁴ has the same meaning as L ³ in formula (L-1), and the preferable aspect is also the same.

In formula (L-2), n2 is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, still more preferably 1 or 2, particularly preferably 1.

In Formula (BL-1), the preferable aspect of the polymeric group in X ^LB is as the above-mentioned.

In formula (BL-1), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, still more preferably 1 or 2, particularly preferably 1.

When n is 2 or more, a plurality of L ^LA and X ^LB contained in the formula (BL-1) may be the same or different.

In Formula (BL-1), m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, still more preferably 1 or 2, particularly preferably 1.

When m is 2 or more, a plurality of X ^LBs contained in formula (BL-1) may be the same or different.

[Resin B]

The resin B is preferably a resin having a repeating unit containing an azole group and a repeating unit containing a polymerizable group, or a resin having a repeating unit containing an azole group and a polymerizable group, and a repeating unit containing an azole group. And it is more preferable that it is resin which has a repeating unit containing a polymeric group.

The weight average molecular weight of Resin B is preferably 2,000 to 100,000, more preferably 3,000 to 70,000, still more preferably 5,000 to 50,000.

Moreover, it is preferable that resin B is an acrylic resin.

It is preferable that resin B contains the repeating unit represented by following formula (BA-1) as a repeating unit containing an azole group.

[Formula 46]

In formula (BA-1), L ³ represents a single bond or a divalent linking group, X ³ represents an azole group, and R represents a hydrogen atom or a methyl group.

In Formula (BA-1), L ³ represents a single bond or a divalent linking group.

The divalent linking group is selected from the group consisting of a hydrocarbon group, a hydrocarbon group, -O-, -S-, -C(=O)-, -S(=O) ₂ - and -NR ^N - A group represented by a bond with at least one group is preferred, and a hydrocarbon group is more preferred.

The R ^N is as described above.

As said hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable and an alkylene group is more preferable.

2-20 are preferable and, as for carbon number of the said hydrocarbon group or alkylene group, 2-10 are more preferable.

Among these, L ³ is preferably a single bond, a group represented by the following formula (BA-1-1), or a group represented by the following formula (BA-1-2).

[Formula 47]

In formula (BA-1-1) or formula (BA-1-2), L ⁴ represents a divalent linking group, L ⁵ represents a single bond or a divalent linking group, L ⁶ represents a divalent linking group, and L ⁷ represents a single bond or a divalent linking group, * represents a bonding site with a carbonyl group in formula (BA-1), A ¹ and A ² represent -O- or -NR ^N -, # represents (BA -1) shows the binding site with X ³ .

In formula (BA-1-1), L ⁴ is a hydrocarbon group, or a hydrocarbon group, -O-, -S-, -C(=O)-, -S(=O) ₂ - and -NR A group formed by bonding with at least one group selected from the group consisting of ^N - is preferable, and a hydrocarbon group is more preferable.

The R ^N is as described above.

As said hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable and an alkylene group is more preferable.

2-20 are preferable and, as for carbon number of the said hydrocarbon group or alkylene group, 2-10 are more preferable.

In formula (BA-1-1), L ⁵ is preferably a single bond. When L ⁵ is a divalent linking group, the preferable aspect of L ⁵ is the same as the preferable aspect when L ¹ is a divalent linking group in the above formula (B-7).

In formula (BA-1-2), L ⁶ has the same meaning as L ⁴ in formula (BA-1-1), and the preferable aspect is also the same.

In formula (BA-1-2), L ⁷ is preferably a divalent linking group. When L ⁷ is a divalent linking group, the preferable aspect of L ⁷ is the same as the preferable aspect when L ² is a divalent linking group in the above formula (B-8).

In formula (BA-1-1) or formula (BA-1-2), A ¹ and A ² represent -O- or -NR ^N -, and -O- is preferable. R ^N is as described above.

In formula (BA-1), the preferred aspect of the azole group for X ³ is as described above. The bonding site with the structure having a polymerizable group in the azole group described above corresponds to the bonding site with L ³ in formula (BA-1).

Resin B may contain only 1 type of repeating unit represented by Formula (BA-1), and may also contain 2 or more types.

It is preferable that resin B contains the repeating unit represented by the following formula (BA-2) as a repeating unit containing a polymeric group.

[Formula 48]

In formula (BA-2), A ³ represents -O- or -NR ^N -, L ^P1 represents a divalent linking group, X ^P1 represents a polymerizable group, and R represents a hydrogen atom or a methyl group.

In formula (BA-2), A ³ represents -O- or -NR ^N -, and -O- is preferable. R ^N is as described above.

In formula (BA-2), L ^P1 represents a divalent linking group, a hydrocarbon group, or a hydrocarbon group, -O-, -S-, -C(=O)-, -S(=O) ₂ A group formed by bonding with at least one group selected from the group consisting of - and -NR ^N - is preferable, and a hydrocarbon group is more preferable.

The R ^N is as described above.

As said hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable and an alkylene group is more preferable.

2-20 are preferable and, as for carbon number of the said hydrocarbon group or alkylene group, 2-10 are more preferable.

X ^P1 represents a polymerizable group, preferably an alkoxysilyl group, an epoxy group, an oxetanyl group or a radical polymerizable group, more preferably an alkoxysilyl group. Preferred embodiments of the alkoxysilyl group and the radical polymerizable group are as described above.

Resin B may contain only 1 type of repeating unit represented by Formula (BA-2), and may also contain 2 or more types.

In particular, it is one of the preferable aspects of this invention that resin B contains the repeating unit represented by multiple types of formula (BA-2) with different polymerizable groups. In the above aspect, the resin B is a repeating unit represented by formula (BA-2) containing an alkoxysilyl group as a polymerizable group and a repeating unit represented by formula (BA-2) containing a group different from an alkoxysilyl group as a polymerizable group It is preferable to include

Moreover, resin B may further have another repeating unit different from the repeating unit represented by Formula (BA-1) or Formula (BA-2) mentioned above.

[specific example]

Specific examples of compound B include, but are not limited to, compounds used in Examples.

〔content〕

The content of compound B is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, and even more preferably 0.15 to 2% by mass with respect to the total solid content of the curable resin composition of the present invention.

Curable resin composition of this invention may contain only 1 type of compound B, and may contain 2 or more types. When containing 2 or more types of compound B, it is preferable that the total amount is the said range.

<Compound C>

From the viewpoint of the adhesion of the obtained cured product to metal, the curable resin composition of the present invention preferably further contains compound C, which is a compound having an azole group without a polymerizable group.

The preferable aspect of the azole group in compound C is the same as the preferable aspect of the azole group in compound B mentioned above.

In addition, although the compound C is a compound which does not have a polymerizable group, the detail of a polymerizable group has the same meaning as the polymerizable group in compound B mentioned above.

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

[Formula 49]

In formula (C-1), each of Z ¹ to Z ⁴ independently represents =CR ⁷ - or a nitrogen atom, R ¹ represents a hydrogen atom or a monovalent organic group, and R ⁷ represents a hydrogen atom or a monovalent organic group. and does not contain a polymerizable group in the structure represented by formula (C-1);

In formula (C-2), Z ⁵ to Z ⁶ each independently represent =CR ⁸ - or a nitrogen atom, R ² to R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and R ⁸ is A hydrogen atom or a monovalent organic group is shown, and a polymerizable group is not included in the structure represented by formula (C-2).

In Formula (C-1), Z ¹ to Z ⁴ each independently represents =CR ⁷ - or a nitrogen atom.

Among them, one of Z ¹ to Z ⁴ is a nitrogen atom, three of which are =CR ⁷ -, an aspect of Z ¹ to Z ⁴ in which two are nitrogen atoms, and two of which are =CR ⁷ -, or Z ¹ to Z An aspect in which 3 of ⁴ are nitrogen atoms and 1 is =CR ⁷ - is preferable.

Also, among these, an aspect in which Z ¹ and Z ³ are nitrogen atoms, Z ² and Z ⁴ are =CR ⁷ -, an aspect in which Z ¹ and Z ² are nitrogen atoms, and Z ³ and Z ⁴ are =CR ⁷ -. , or, preferably, Z ¹ , Z ² and Z ³ are nitrogen atoms, Z ⁴ is =CR ⁷ -, Z ¹ and Z ³ are nitrogen atoms, and Z ² and Z ⁴ are =CR ^B7 - An aspect or an aspect in which Z ¹ , Z ² and Z ³ are nitrogen atoms and Z ⁴ is =CR ⁷ - is more preferable.

In formula (C-1), R ¹ is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

As for carbon number of the said hydrocarbon group or alkyl group, it is preferable that it is 1-20, it is more preferable that it is 1-10, and it is still more preferable that it is 1-4.

In formula (C-1), the preferred aspect of R ⁷ is the same as that of R ¹ .

In formula (C-2), Z ⁵ and Z ⁶ each independently represents =CR ⁸ - or a nitrogen atom.

Among them, an aspect in which both Z ⁵ and Z ⁶ represent a nitrogen atom or an aspect in which Z ⁵ represents a nitrogen atom and Z ⁶ represents =CR ⁸ - are preferred.

In formula (C-2), R ² to R ⁶ and R ⁸ are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

〔Molecular Weight〕

It is preferable that it is 67-500, and, as for the molecular weight of compound C, it is more preferable that it is 68-300.

[specific example]

Specific examples of Compound C include, but are not limited to, compounds used in Examples.

〔content〕

The content of compound C is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, and even more preferably 0.15 to 2% by mass with respect to the total solid content of the curable resin composition of the present invention.

Curable resin composition may contain only 1 type of compound C, and may contain 2 or more types. When 2 or more types of compound C are contained, it is preferable that the total amount is the said range.

<Other silane coupling agents>

The curable resin composition of the present invention preferably contains a silane coupling agent having no azole group (also referred to as "another silane coupling agent") as a silane coupling agent different from the polymerization inhibitor having an alkoxysilyl group. do.

As the silane coupling agent, Compound D, which is a silane coupling agent having a polymerizable group different from an alkoxysilyl group and having no azole group, or a compound which is a silane coupling agent having neither a polymerizable group different from an alkoxysilyl group nor an azole group E can be heard.

[Compound D]

Curable resin composition of this invention may further contain compound D which is a silane coupling agent which has a polymeric group different from an alkoxysilyl group and does not have an azole group.

It is preferable that compound D is a compound containing an alkoxysilyl group and a polymeric group different from an alkoxysilyl group.

The preferable aspect of the alkoxysilyl group in compound D is the same as the preferable aspect of the alkoxysilyl group in compound B mentioned above.

In addition, although compound D is a compound which does not have an azole group, the detail of an azole group has the same meaning as the azole group in compound B mentioned above.

Examples of the polymerizable group different from the alkoxysilyl group in the compound D include known polymerizable groups such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group, and a (block) isocyanate group. A polymerizable group or an epoxy group is preferred.

The preferable aspect of the radical polymerizable group in the compound D is the same as the preferable aspect of the radical polymerizable group in the compound B described above.

As the compound D, a compound having a structure represented by the following formula (DA-1) is preferable.

[Formula 50]

In formula (DA-1), R ^D1 to R ^D3 each independently represent an alkyl group, L ^D1 represents a divalent linking group, and X ^D1 represents a polymerizable group.

In formula (DA-1), each of R ^D1 to R ^D3 is independently preferably an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, and more preferably an ethyl group.

In formula (DA-1), L ^D1 represents a divalent linking group, a hydrocarbon group, or a hydrocarbon group, -O-, -S-, -C(=O)-, -S(=O) ₂ A group formed by bonding with at least one group selected from the group consisting of - and -NR ^N - is preferable, and a hydrocarbon group is more preferable.

The R ^N is as described above.

An aspect having at least one group selected from the group consisting of an amide group and an urea group in L ^D1 is also one of the preferred aspects of the present invention.

In formula (DA-1), X ^D1 represents a polymerizable group, and preferred aspects of the polymerizable group are as described above.

The compound D may be a compound having a molecular weight of less than 2,000 (hereinafter also referred to as “low molecular weight compound D”) or a resin (hereinafter also referred to as “resin D”).

Moreover, it is also preferable that curable resin composition contains both the low molecular weight compound D and resin D from an adhesive viewpoint with the metal of hardened|cured material.

[Low Molecular Compound D]

The molecular weight of the low molecular weight compound D is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.

The number of polymerizable groups different from the alkoxysilyl group in the low molecular weight compound D is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, still more preferably 1 or 2.

The low molecular weight compound D is a compound represented by the formula (DA-1) described above, and is preferably a compound having a molecular weight within the range described above.

[Resin D]

The resin D is a resin having a repeating unit containing an alkoxysilyl group and a repeating unit containing a polymerizable group different from the alkoxysilyl group, or having a repeating unit containing an alkoxysilyl group and a polymerizable group different from the alkoxysilyl group. It is preferable that it is resin, and it is more preferable that it is resin which has a repeating unit containing an alkoxysilyl group, and a repeating unit containing a polymeric group different from an alkoxysilyl group.

The weight average molecular weight of Resin D is preferably 2,000 to 100,000, more preferably 3,000 to 70,000, still more preferably 5,000 to 50,000.

Moreover, it is preferable that resin D is an acrylic resin.

As a repeating unit containing an alkoxysilyl group in resin D, and a repeating unit containing a polymerizable group different from an alkoxysilyl group, the repeating unit represented by Formula (BA-2) mentioned above is mentioned preferably.

Moreover, resin D may further have another repeating unit different from the repeating unit represented by Formula (BA-2) mentioned above.

[specific example]

Specific examples of compound D include, but are not limited to, compounds used in Examples.

〔content〕

The content of compound D is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, and even more preferably 0.15 to 2% by mass with respect to the total solid content of the curable resin composition of the present invention.

Curable resin composition may contain only 1 type of compound D, and may contain 2 or more types. When containing 2 or more types of compound D, it is preferable that the total amount is the said range.

<Compound E>

It is preferable that the curable resin composition of this invention further contains compound E which is a silane coupling agent which has neither a polymeric group nor an azole group different from an alkoxysilyl group.

As the compound E, a compound having an alkoxysilyl group and not having a polymerizable group different from the alkoxysilyl group and an azole group is preferable.

The compound E is a compound having no polymerizable group different from the alkoxysilyl group, but the details of the polymerizable group different from the alkoxysilyl group are the same as the polymerizable group different from the alkoxysilyl group in the above-mentioned compound D.

Although compound E is a compound which does not have an azole group, the detail of an azole group has the same meaning as the azole group in compound B mentioned above.

As an example of compound E, the compound described in Paragraph 0167 of International Publication No. 2015/199219, the compound described in Paragraphs 0062 to 0073 of Unexamined-Japanese-Patent No. 2014-191002, and the compound described in Paragraphs 0063 to 0071 of International Publication No. 2011/080992 , the compound described in paragraphs 0060 to 0061 of Japanese Laid-open Patent Publication No. 2014-191252, the compound described in paragraphs 0045 to 0052 of Japanese Laid-Open Patent Publication No. 2014-041264, the compound described in paragraph 0055 of International Publication No. 2014/097594, Japanese Laid-Open Patent Paragraph 0067 of Publication No. 2018-173573 - the compound of 0078 are mentioned, These content is integrated in this specification. Moreover, it is also preferable to use 2 or more types of silane coupling agents different as Paragraph 0050 of Unexamined-Japanese-Patent No. 2011-128358 - 0058 describe. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the formulas below, Me represents a methyl group and Et represents an ethyl group.

[Formula 51]

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 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 acid anhydride. These can be used individually by 1 type or in combination of 2 or more types.

〔content〕

The content of compound E is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, and still more preferably 0.15 to 2% by mass with respect to the total solid content of the curable resin composition of the present invention.

Curable resin composition may contain only 1 type of compound E, and may contain 2 or more types. When containing 2 or more types of compound E, it is preferable that the total amount is the said range.

<Solvent>

It is preferable that the resin composition of this invention contains a solvent.

A well-known solvent can be used arbitrarily as a solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

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, alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methoxy methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionate alkyl esters (e.g., 3-alkyloxymethylpropionate, 3-alkyloxy Ethyl propionate and the like (eg, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, etc.), 2-alkyloxypropionate alkyl esters (eg For example, 2-alkyloxymethylpropionate, 2-alkyloxyethylpropionate, 2-alkyloxypropylpropionate, etc. (e.g., 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2-methoxypropylpropionate, 2 -methyl ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g. 2-methoxy-2-methylpropionate) methyl, 2-ethoxy-2-methylethylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, Ethyl heptanoate, dimethyl malonate, diethyl malonate and the like are mentioned as suitable ones.

As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol Lycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl Cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, Propylene glycol dimethyl 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, dipropylene glycol dimethyl ether, etc. are mentioned as suitable ones.

Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, and the like. can

As the cyclic hydrocarbons, suitable examples thereof include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.

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

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl Formamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetyl Morpholine etc. are mentioned as a suitable thing.

As ureas, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, etc. are mentioned as suitable ones.

As alcohols, 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, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol, etc. are mentioned.

As for the solvent, a form in which two or more types are mixed is also preferable 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 one, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and One solvent selected from propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more kinds is preferred. A combination of dimethyl sulfoxide and γ-butyrolactone or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

The content of the solvent is preferably an amount such that the total solid concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, from the viewpoint of applicability. It is more preferable to set it to 70 mass %, and it is more preferable to set it as 20 to 70 mass %. What is necessary is just to adjust solvent content according to the desired thickness of a coating film, and a coating method.

The resin composition of this invention may contain only 1 type of solvent, and may contain 2 or more types of solvents. When containing 2 or more types of solvents, it is preferable that the sum total is the said range.

[mine generator]

It is preferable that the resin composition of this invention contains a photo-acid generator.

A photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid when irradiated with light of 200 nm to 900 nm. Light to be irradiated is preferably light with a wavelength of 300 nm to 450 nm, more preferably light with a wavelength of 330 nm to 420 nm. In the case where the photoacid generator is used alone or in combination with a sensitizer, it is preferably a photoacid generator capable of generating an acid by photosensitization.

Examples of acids generated include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivative, phosphorus derivative, antimony derivative, halogen peroxide, sulfonamide, etc. may be preferred.

Examples of the photoacid generator used in the resin composition of the present invention include quinonediazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, and onium salt compounds.

From the viewpoints of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and oxime esters are preferred from the viewpoint of the mechanical properties of the formed film.

Examples of the quinonediazide compound include those in which sulfonic acid of quinonediazide is ester bonded to a monovalent or polyvalent hydroxy compound, those in which sulfonic acid of quinonediazide is sulfonamide bonded to a monovalent or polyvalent amino compound, and polyhydroxypolyamino compounds and those in which sulfonic acid of quinonediazide is bonded to an ester bond and/or a sulfonamide bond. All functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds do not have to be substituted with quinonediazide, but it is preferable that 40 mol% or more of the total functional groups on average are substituted with quinonediazide. . By containing such a quinonediazide compound, a resin composition sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are general ultraviolet rays, can be obtained.

Specific examples of the hydroxy compound include phenol, trihydroxybenzophenone, 4methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4 HBPA , TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylentris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP , Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP , HML-TPPHBA, HML-TPHAP (above, brand name, made by Honshu Kagaku High School), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4 PC, BIR -BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade names, manufactured by Asahi Yukizai Kogyo), 2,6-dimethoxymethyl-4-t-butylphenol, 2, 6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name , Honshu Chemical Co., Ltd.), novolak resin, etc., but are not limited thereto.

Specifically as amino compounds, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4 , 4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, and the like, but are not limited thereto.

In addition, specific examples of the polyhydroxypolyamino compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine. not limited to these

Among these, as a quinonediazide compound, what contains the ester of a phenol compound and 4-naphthoquinone diazide sulfonyl group is preferable. This makes it possible to obtain higher sensitivity to i-line exposure and higher resolution.

The content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the resin. By making content of a quinonediazide compound into this range, when contrast of an exposed part and an unexposed part is obtained, since higher sensitivity can be aimed at more, it is preferable. You may further add a sensitizer etc. as needed.

The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, simply referred to as "oxime sulfonate compound").

The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is represented by the following formula (OS-1), the later-described formula (OS-103), the formula (OS-104), or the formula (OS-105). It is preferable that it is an oxime sulfonate compound shown.

[Formula 52]

In Formula (OS-1), X ³ represents an alkyl group, an alkoxy group, or a halogen atom. When a plurality of X ³ are present, they may be the same or different. The alkyl group and alkoxy group in X ³ may have a substituent. As the alkyl group for X ³ , a straight-chain or branched alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group for X ³ , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable. As a halogen atom in said X ^<3> , a chlorine atom or a fluorine atom is preferable.

In Formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X ³ may be the same or different.

In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, and is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a halogen having 1 to 5 carbon atoms. It is preferably a substituted alkoxy group, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms , an aryl group having 6 to 20 carbon atoms, and a halogenated aryl group having 6 to 20 carbon atoms.

In formula (OS-1), m3 is 3, X ³ is a methyl group, the substituted position of X ³ is an ortho position, R ³⁴ is a linear alkyl group having 1 to 10 carbon atoms, and 7,7-dimethyl-2- A compound having an oxonobonylmethyl group or a p-tolyl group is particularly preferred.

As a specific example of the oxime sulfonate compound represented by Formula (OS-1), the following compounds described in Paragraph Nos. 0064-0068 of Unexamined-Japanese-Patent No. 2011-209692 and Paragraph No. 0158-0167 of Unexamined-Japanese-Patent No. 2015-194674 are illustrated. and these contents are incorporated herein.

[Formula 53]

In formulas (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group, or a heteroaryl group, and R ^s2 , which may be present in a plurality thereof, is each independently a hydrogen atom, an alkyl group, an aryl group, or a Represents a rosen atom, R ^s6 , which may exist in plural numbers, each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer from 0 to 6.

In formulas (OS-103) to (OS-105), an alkyl group (preferably 1 to 30 carbon atoms), an aryl group (preferably 6 to 30 carbon atoms), or a heteroaryl group (preferably 4 to 30 carbon atoms) represented by R ^s1 This preferable) may have a known substituent within the range in which the effect of this invention is acquired.

In formulas (OS-103) to (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms), or an aryl group (preferably 6 to 30 carbon atoms), and hydrogen It is more preferably an atom or an alkyl group. Among R ^s2 that may exist in two or more in a compound, one or two are preferably an alkyl group, an aryl group, or a halogen atom, more preferably one is an alkyl group, an aryl group, or a halogen atom, and one is an alkyl group , and it is particularly preferred that the remainder are hydrogen atoms. The alkyl group or aryl group represented by R ^s2 may have a known substituent within the range where the effect of the present invention is obtained.

In Formula (OS-103), Formula (OS-104), or Formula (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a reduction is a 5- or 6-membered ring.

In formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is 2 desirable.

In formulas (OS-103) to (OS-105), the alkyl group (preferably 1 to 30 carbon atoms) and the alkyloxy group (preferably 1 to 30 carbon atoms) represented by R ^s6 may have a substituent.

In formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, particularly preferably 0.

In addition, the compound represented by the formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), and the formula (OS-104 ) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the formula (OS-105) is represented by the following formula (OS-108) or formula (OS-109) Compounds are particularly preferred.

[Formula 54]

In formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group, or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, and R ^t8 represents a hydrogen atom and 1 to 10 carbon atoms. 8 represents an alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ^t2 is represents a hydrogen atom or a methyl group.

In formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

In formulas (OS-106) to (OS-111), R ^t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or Represents a chlorophenyl group, preferably an alkyl group, a halogen atom or a phenyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly a methyl group desirable.

In formulas (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

R ^t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

Moreover, in the said oxime sulfonate compound, about the three-dimensional structure (E, Z) of an oxime, either one may be sufficient and a mixture may be sufficient as it.

As a specific example of the oxime sulfonate compound represented by the said Formula (OS-103) - Formula (OS-105), Paragraph No. 0088 of Unexamined-Japanese-Patent No. 2011-209692 - 0095, Paragraph No. 0168 - of Unexamined-Japanese-Patent No. 2015-194674 - The compounds described in 0194 are exemplified, and these contents are incorporated herein by reference.

As another suitable aspect of the oxime sulfonate compound containing at least one oxime sulfonate group, the compound represented by the following formula (OS-101) and formula (OS-102) is mentioned.

[Formula 55]

In Formula (OS-101) or Formula (OS-102), R ^u9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, or a cyano group. group, aryl group or heteroaryl group. An aspect in which R ^u9 is a cyano group or an aryl group is more preferable, and an aspect in which R ^u9 is a cyano group, a phenyl group or a naphthyl group is still more preferable.

In formula (OS-101) or formula (OS-102), R ^u2a represents an alkyl group or an aryl group.

In Formula (OS-101) or Formula (OS-102), Xu is -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, -CR ^u6 H- or CR ^u6 R ^u7 -, and R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In Formula (OS-101) or Formula (OS-102), R ^u1 to R ^u4 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, represents an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an aryl group. Two of R ^u1 to R ^u4 may be bonded to each other to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom or an alkyl group is preferable, and an aspect in which at least two of R ^u1 to R ^u4 bond to each other to form an aryl group is also preferable. Among them, an aspect in which all of R ^u1 to R ^u4 are hydrogen atoms is preferable. All of the substituents described above may further have a substituent.

It is more preferable that the compound represented by the formula (OS-101) is a compound represented by the formula (OS-102).

Moreover, in the said oxime sulfonate compound, about the steric structure (E, Z, etc.) of an oxime and a benzothiazole ring, either one may be sufficient respectively, and a mixture may be sufficient as it.

As a specific example of the compound represented by formula (OS-101), Paragraph No. 0102 of Unexamined-Japanese-Patent No. 2011-209692 - 0106, and Paragraph No. 0195 of Unexamined-Japanese-Patent No. 2015-194674 - the compound of 0207 are illustrated, These contents are incorporated herein by reference.

Among the above compounds, the following b-9, b-16, b-31 and b-33 are preferable.

[Formula 56]

Commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Chemical Co., Ltd.), and the like. .

Moreover, the compound represented by the following structural formula is also mentioned as a preferable example.

[Formula 57]

As an organic halogenated compound, specifically, Wakabayashi et al. "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281, Japanese Laid-Open Patent Publication 55-32070, Japanese Laid-Open Patent Publication 60-239736, Japanese Laid-Open Patent Publication 61-169835, Japanese Laid-Open Patent Publication 61-169837, Japanese Laid-Open Patent Publication 62-58241, Japanese Unexamined Patent Publication No. 62-212401, Japanese Unexamined Patent Publication No. 63-70243, Japanese Unexamined Patent Publication No. 63-298339, M. P. Hutt "Jurnal of Heterocyclic Chemistry" 1 (No3), (1970 ), and the like, the contents of which are incorporated herein by reference. In particular, oxazole compounds in which a trihalomethyl group is substituted: S-triazine compounds are exemplified as preferred examples.

More preferably, s-triazine derivatives in which at least one mono, di, or trihalogen substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6-tris (monochloro Methyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4, 6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)- 4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4, 6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s- Triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine , 2-(p-i-propyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tri Azine, 2-(4-nathoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine , 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribe lomomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis(tribromomethyl)-s-triazine, etc. can be heard

As an organic borate compound, Unexamined-Japanese-Patent No. 62-143044, Unexamined-Japanese-Patent No. 62-150242, Unexamined-Japanese-Patent No. 9-188685, Unexamined-Japanese-Patent No. 9-188686, Japan, for example Japanese Unexamined Patent Publication No. 9-188710, Japanese Unexamined Patent Publication No. 2000-131837, Japanese Unexamined Patent Publication No. 2002-107916, Japanese Patent Publication No. 2764769, Japanese Unexamined Patent Publication No. 2002-116539, etc., and Kunz, Martin " Rad Tech '98. Proceeding April 19-22, 1998, Chicago" and the like, organic borates described in Japanese Unexamined Patent Publication No. Hei 6-157623, Japanese Unexamined Patent Publication No. Hei 6-175564, Japanese Unexamined Patent Publication No. Hei 6-175561 The organic boron sulfonium complex or organoboron oxosulfonium complex described in, Japanese Unexamined Patent Publication No. 6-175554, Organic boron iodonium complex described in Japanese Unexamined Patent Publication No. Hei 6-175553, Japanese Unexamined Patent Publication Hei 9- 188710, an organoboron phosphonium complex described in Japanese Patent Application Laid-Open No. 6-348011, Japanese Patent Laid-Open No. 7-128785, Japanese Patent Laid-Open No. 7-140589, Japanese Patent Laid-Open No. 7-306527, Organoboron transition metal coordination complexes, such as Unexamined-Japanese-Patent No. 7-292014, etc. are mentioned as a specific example, These content is integrated in this specification.

As a disulfone compound, the compound and diazodisulfone compound described in Unexamined-Japanese-Patent No. 61-166544, Japanese Patent Application No. 2001-132318, etc. are mentioned.

As the onium salt compound, for example, S. I. Schlesinger, Photogr. Sci. Eng., 18,387 (1974), T. S. Bal et al, Polymer, 21,423 (1980) diazonium salts, US Patent Publication No. 4,069,055, ammonium salts described in Japanese Unexamined Patent Publication Hei 4-365049, etc., US Patent Publication No. 4,069,055 4,069,056, European Patent No. 104,143, U.S. Patent No. 339,049, each specification of No. 410,201, Japanese Unexamined Patent Publication No. 2-150848, Japanese Unexamined Patent Publication Hei 2 Iodonium salt described in -296514, European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, US Patent Nos. 4,933,377, 161,811, 410,201, 339,049 , 4,760,013, 4,734,444, 2,833,827, German Patent Publication Nos. 2,904,626, 3,604,580, and 3,604,581 sulfonium salts, J. V. Crivello et al, Macromolecules, 10(6), 1307 (1977) , J. V. Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17,1047 (1979) selenium salts, C. S. Wen et al, Teh, Proc. Conf. Rad. and onium salts such as arsonium salts and pyridinium salts described in Curing ASIA, p478 Tokyo, Oct (1988), and the like, and the names of these are incorporated herein by reference.

Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III).

[Formula 58]

In the formula (RI-I), Ar ₁₁ represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferable substituents include an alkyl group of 1 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, and a carbon atom group of 2 to 12 carbon atoms. an alkynyl group, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, An alkylamide group having 1 to 12 carbon atoms in an alkyl group or an arylamide group having 6 to 20 carbon atoms in an aryl group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a carbon number 1 to 12 The thioaryl group of 12 is mentioned. Z ₁₁ ^- represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, a sulfate ion, and in terms of stability A perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, and a sulfinic acid ion are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group of 1 to 12 carbon atoms and an alkene of 2 to 12 carbon atoms. Diary, C2-12 alkynyl group, C1-12 aryl group, C1-12 alkoxy group, C1-12 aryloxy group, halogen atom, C1-12 monoalkylamino group, alkyl group A dialkylamino group having 1 to 12 carbon atoms each independently, an alkylamide group or arylamide group having 1 to 12 carbon atoms in the alkyl group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a cyano group having 1 to 12 carbon atoms An oalkyl group and a thioaryl group having 1 to 12 carbon atoms are exemplified. Z ₂₁ ^- represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, and a sulfate ion, and has stability and reactivity. For cotton, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred. In formula (RI-III), R ₃₁ , R ₃₂ , R ₃₃ each independently represent an aryl group or alkyl group having 6 to 20 carbon atoms, which may have 1 to 6 substituents, an alkenyl group, or an alkynyl group, preferably From the viewpoint of reactivity and stability, an aryl group is preferred. Preferred substituents include an alkyl group of 1 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, an alkynyl group of 2 to 12 carbon atoms, an aryl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, and an aryloxy group of 1 to 12 carbon atoms. Group, halogen atom, monoalkylamino group having 1 to 12 carbon atoms, dialkylamino group having 1 to 12 carbon atoms in the alkyl group independently, alkylamide group or arylamide group having 1 to 12 carbon atoms in the alkyl group, carbonyl group , a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₃₁ ^- represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, and a sulfate ion, and has stability and reactivity. For cotton, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred.

Specific examples of preferable photoacid generators include the following.

[Formula 59]

[Formula 60]

[Formula 61]

[Formula 62]

The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably in an amount of 0.5 to 18% by mass, more preferably in an amount of 0.5 to 10% by mass, and preferably in an amount of 0.5 to 10% by mass, based on the total solid content of the resin composition. It is more preferable to use 3% by mass, and it is even more preferable to use 0.5 to 1.2% by mass.

A photoacid generator may be used individually by 1 type, and may be used in the combination of multiple types. In the case of a combination of a plurality of types, it is preferable that the total amount thereof is within the above range.

Moreover, in order to impart photosensitivity with respect to a desired light source, it is also preferable to use together with a sensitizer.

<Thermal acid generator>

The composition of the present invention may also contain a thermal acid generator.

The thermal acid generator generates an acid by heating and causes a polymerization reaction of at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound. has a stimulating effect.

The thermal decomposition start temperature of the thermal acid generator is preferably 50°C to 270°C, and more preferably 50°C to 250°C. In addition, acid is not generated during drying (prebaking: about 70 to 140° C.) after coating the composition on a substrate, and at the time of final heating (curing: about 100 to 400° C.) after patterning by subsequent exposure and development. Selecting an acid-generating agent as the thermal acid generator is preferable because the decrease in sensitivity during development can be suppressed.

The thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak having the lowest temperature when the thermal acid generator is heated up to 500°C at 5°C/min in a pressure-resistant capsule.

Q2000 (made by TA Instruments) etc. are mentioned as a device used when measuring the thermal decomposition start temperature.

The acid generated from the thermal acid generator is preferably a strong acid, and examples thereof include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, and alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid. Haloalkylsulfonic acids, such as phonic acid or trifluoromethanesulfonic acid, etc. are preferable. As an example of such a thermal acid generator, the thing of Unexamined-Japanese-Patent No. 2013-072935 Paragraph 0055 is mentioned.

Among them, it is more preferable to generate an alkylsulfonic acid having 1 to 4 carbon atoms or a haloalkylsulfonic acid having 1 to 4 carbon atoms from the viewpoint of reducing the physical properties of the organic film due to a small amount of residue in the organic film, and methanesulfonic acid (4- Hydroxyphenyl)dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, methanesulfonic acid benzyl (4-hydroxyphenyl)methylsulfonium, methanesulfonic acid benzyl (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium, methanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium, trifluoromethanesulfonic acid (4-hydroxy oxyphenyl)dimethylsulfonium, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, trifluoromethanesulfonic acid benzyl(4-hydroxyphenyl)methylsulfonium , trifluoromethanesulfonic acid benzyl (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl)methyl ((2-methylphenyl)methyl)sulfonium , 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-iridene)-2-(o-tolyl)propanenitrile, 2,2-bis(3- (Methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane is preferred as the thermal acid generator.

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

The content of the thermal acid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin. By containing 0.01 parts by mass or more, the polymerization reaction is accelerated, so the mechanical properties and solvent resistance of the organic film can be further improved. Moreover, from a viewpoint of the electrical insulating property of an organic film, 20 mass parts or less is preferable, 15 mass parts or less is more preferable, and 10 mass parts or less are still more preferable.

<Base generator>

The resin composition of the present invention may also contain a base generator. Here, a base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.

In particular, when the resin composition contains a precursor of a cyclization resin, it is preferable that the resin composition contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be accelerated by, for example, heating, and the mechanical properties and chemical resistance of the cured product are improved, for example, for a redistribution layer included in a semiconductor package. The performance as an interlayer insulating film becomes good.

The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.

The base generator according to the present invention is not particularly limited, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, and nitrobenzylcarbamate compounds. , sulfonamide compound, imidazole derivative compound, amineimide compound, pyridine derivative compound, α-aminoacetophenone derivative compound, quaternary ammonium salt derivative compound, pyridinium salt, α-lactone ring derivative compound, amineimide compound, phthal Imide derivative compounds, acyloxyimino compounds and the like can be used.

As a specific compound of a nonionic base generator, the compound represented by a formula (B1), a formula (B2), or a formula (B3) is mentioned.

[Formula 63]

In formulas (B1) and (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom. However, there is no case where Rb ¹ and Rb ² simultaneously become a hydrogen atom. In addition, none of Rb ¹ , Rb ² and Rb ³ have a carboxy group. In addition, in this specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the bonded carbon atom is a carbon atom constituting a carbonyl group, that is, when an amide group is formed together with a nitrogen atom, it is not limited thereto.

In formulas (B1) and (B2), as for Rb ¹ , Rb ² and Rb ³ , it is preferable that at least one of these includes a cyclic structure, and it is more preferable that at least two of these include a cyclic structure. As the cyclic structure, either a monocycle or a condensed ring may be used, and a monocycle or a condensed ring in which two monocycles are condensed is preferable. The monocyclic ring is preferably a 5- or 6-membered ring, more preferably a 6-membered ring. As for a monocyclic 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 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, , 2 to 18 are more preferred, 3 to 12 are more preferred), an aryl group (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, and 6 to 10 are more preferred), or an arylalkyl group ( It is preferably 7 to 25 carbon atoms, more preferably 7 to 19, more preferably 7 to 12). These groups may have a substituent within the range of exhibiting the effect of the present invention. Rb ¹ and Rb ² may be bonded to each other to form a ring. As the ring 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 which may have a substituent (preferably 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12). , It is more preferably a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18, and still more preferably 3 to 12) which may have a substituent, and a cyclohexyl group that may have a substituent is more preferable do.

As Rb ³ , an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18, and still more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, 6-10 are more preferable), an alkenyl group (C2-24 are preferable, 2-12 are more preferable, 2-6 are more preferable), an arylalkyl group (C7-23 are preferable, 7-12 are more preferable) 19 is more preferable, and 7 to 12 are more preferable), an arylalkenyl group (C 8 to 24 is preferable, 8 to 20 are more preferable, and 8 to 16 are more preferable), an alkoxyl group (C 1 to C 16 is preferable) 24 is preferable, 2 to 18 are more preferable, 3 to 12 are more preferable), aryloxy group (C6 to 22 are preferable, 6 to 18 are more preferable, 6 to 12 are still more preferable) , or an arylalkyloxy group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). Especially, a cycloalkyl group (C3-C24 is preferable, 3-18 are more preferable, and 3-12 are still more preferable), an arylalkenyl group, and an arylalkyloxy group are preferable. Rb ³ may further have a substituent within the range showing the effect of the present invention.

It is preferable that the compound represented by Formula (B1) is a compound represented by the following formula (B1-1) or the following formula (B1-2).

[Formula 64]

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

Rb ¹³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still 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 (C6-22 is preferable, 6-18 are more preferable, 6-12 are still more preferable), arylalkyl group (C7-23 is preferable, 7-19 is more preferable, and 7 to 12 are 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 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms) and, 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), an arylalkyl group ( 7-23 carbon atoms are preferable, 7-19 are more preferable, and 7-11 are still 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, more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3-8 are more preferable), aryl group (C6-22 are preferable, 6-18 are more preferable, 6-12 are more preferable), arylalkyl group (C7-23 are preferable, 7-18 are more preferable) 19 is more preferable, and 7 to 12 are more preferable), and an aryl group is preferable.

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

[Formula 65]

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 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms and 2 to 6 carbon atoms) More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and still more preferably 6 to 10), an arylalkyl group (7 to 23 carbon atoms) preferably, 7 to 19 are more preferable, and 7 to 11 are still more preferable), and a hydrogen atom or a methyl group is preferable.

Rb ¹⁷ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 3 to 8), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and 3 -8 is more preferable), aryl group (C6-22 is preferable, 6-18 are more preferable, 6-12 are still more preferable), arylalkyl group (C7-23 is preferable, 7-19 is more preferable, and 7 to 12 are more preferable), and among them, an aryl group is preferable.

[Formula 66]

In formula (B3), L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of a link chain connecting adjacent oxygen atoms and carbon atoms, and is a hydrocarbon having 3 or more atoms on the path of the link chain represents a flag. Further, R ^N1 and R ^N2 each independently represent a monovalent organic group.

In this specification, "linked chain" refers to linking these linking objects in the shortest (minimum number of atoms) among atomic chains on a path connecting between two atoms or groups of atoms to be linked. For example, in the compound represented by the following formula, L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group, the linked chain is composed of 4 carbon atoms, and the number of atoms on the path of the linked chain ( That is, the number of atoms constituting the linked chain, hereinafter also referred to as “linked chain length” or “linked chain length”) is 4.

[Formula 67]

It is preferable that the number of carbon atoms in L in the formula (B3) (including carbon atoms other than carbon atoms in the link chain) is 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. As for a lower limit, it is more preferable that it is 4 or more. From the viewpoint of rapidly advancing the intramolecular cyclization reaction, the upper limit of the link chain length of L is preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 5 or less. In particular, the length of the linked chain of L is preferably 4 or 5, and most preferably 4. As a specific preferable compound of a base generator, the compound of Paragraph No. 0102 - 0168 of International Publication No. 2020/066416, and the compound of Paragraph No. 0143 - 0177 of International Publication No. 2018/038002 are also mentioned, for example. .

Moreover, it is also preferable that the base generator contains a compound represented by the following formula (N1).

[Formula 68]

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, R ^C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, preferably a divalent organic group. It is preferable that it is 1 or more, and, as for the length of the linked chain of a linking group, it is more preferable that it is 2 or more. As an upper limit, it is preferably 12 or less, more preferably 8 or less, and still more preferably 5 or less. Linked chain length is the number of atoms present in the atomic arrangement that forms the shortest path between two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and a hydrocarbon group. (C1-24 is preferable, 1-12 are more preferable, and 1-10 are more preferable), and specifically, an aliphatic hydrocarbon group (C1-24 is preferable, 1-12 is more preferable, more preferably 1 to 10) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), and aliphatic carbonization Hydrogen groups are preferred. As R ^N1 and R ^N2 , it is preferable to use an aliphatic hydrocarbon group because the basicity of the generated base is high. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain or in the aromatic ring or in the substituent. In particular, an aspect in which an aliphatic hydrocarbon group has an oxygen atom in a hydrocarbon chain is exemplified.

Examples of the aliphatic hydrocarbon group constituting R ^N1 and R ^N2 include a straight-chain or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The straight-chain or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18, and still more preferably 3 to 12. The straight chain or branched chain alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an isopropyl group, Isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group, etc. are mentioned.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

The group relating to the combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, still more preferably 4 to 12 carbon atoms. Examples of the group related to the combination of a chain alkyl group and a cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.

The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, still more preferably 2 to 4. The alkyl group having an oxygen atom in its chain may be chain or cyclic, or may be straight or branched.

Among them, from the viewpoint of increasing the boiling point of the decomposition product base described later, R ^N1 and R ^N2 are preferably alkyl groups having 5 to 12 carbon atoms. However, in formulations that place importance on adhesion when stacking with a layer of metal (for example, copper), a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.

R ^N1 and R ^N2 may be connected to each other to form a cyclic structure. In forming a cyclic structure, you may have an oxygen atom etc. in a chain|strand. Further, the cyclic structure formed by R ^N1 and R ^N2 may be a monocyclic or condensed ring, but a monocyclic structure is preferable. As the cyclic structure formed, a 5- or 6-membered ring containing a nitrogen atom in formula (N1) is preferable, and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, and an imidazolidine ring. , A pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc. are mentioned, A pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring are mentioned preferably.

R ^C1 represents a hydrogen atom or a protecting group, and a hydrogen atom is preferable.

As the protecting group, a protecting group decomposed by the action of an acid or a base is preferable, and a protecting group decomposed by an acid is preferably used.

Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. As a chain or cyclic alkyl group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group, etc. are mentioned. Examples of the chain-like alkyl group having an oxygen atom in the chain include, specifically, an alkyloxyalkyl group, and more specifically, a methyloxymethyl (MOM) group and an ethyloxyethyl (EE) group. Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl (THP) group.

The divalent linking group constituting L is not particularly defined, but is preferably a hydrocarbon group and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may have an atom of a type other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or an oxygen atom in the chain A group related to a combination of a divalent aliphatic hydrocarbon group that may have a divalent aromatic hydrocarbon group is more preferable, and a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain is more preferable. It is preferable that these groups do not have an oxygen atom.

The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12, still more preferably 2 to 6. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, still more preferably 2 to 4. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, still more preferably 6 to 10. The group related to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and more preferably 7 to 10 desirable.

As the linking group L, specifically, a straight chain or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenyl A rene group, a cyclic alkenylene group, an arylene group, and an arylene alkylene group are preferable.

The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4.

The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.

The group relating to the combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12, still more preferably 4 to 6.

The alkylene group having an oxygen atom in its chain may be chain or cyclic, and may be straight or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and still more preferably 1 to 3.

The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, still more preferably 2 to 3. The number of C=C bonds in the linear or branched alkenylene group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 3.

The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The number of C=C bonds in the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 2.

The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and still more preferably 6 to 10.

The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and still more preferably 7 to 11.

Among them, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propanediyl group (especially 1 ,3-propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cisvinylene group), phenylene group (1,2-phenylene group), phenylene methylene A group (particularly a 1,2-phenylenemethylene group) and an ethyleneoxyethylene group (particularly a 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.

Examples of the base generator include the following examples, but the present invention is not construed as being limited thereto.

[Formula 69]

The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and still more preferably 500 or less. As a lower limit, it is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.

As a specific preferable compound of an ionic base generator, Paragraph No. 0148 of International Publication No. 2018/038002 - the compound of 0163 are also mentioned, for example.

Although the following compounds are mentioned as a specific example of an ammonium salt, this invention is not limited to these.

[Formula 70]

Although the following compounds are mentioned as a specific example of an iminium salt, this invention is not limited to these.

[Formula 71]

When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, may be 5 parts by mass or less, or may be 4 parts by mass or less.

1 type or 2 or more types can be used for a base generator. When using 2 or more types, it is preferable that the total amount is the said range.

<Polymerization inhibitor>

It is preferable that curable resin composition of this invention contains another polymerization inhibitor different from the specific polymerization inhibitor mentioned above.

Examples of other polymerization inhibitors include phenolic compounds, quinone-based compounds, amino-based compounds, N-oxyl free radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic compounds, and metal compounds.

Specific compounds of other polymerization inhibitors include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, and p-tert-butyl. Catechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl- 6-tert-butylphenol), N-nitrosophenylhydroxyamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthyl Amine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycoletherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso- 8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-knight Rosso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3 -Hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6, 6-Tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picryl Suitable hydrazyl, dibutyldithiocarbanate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. it is used Moreover, the polymerization inhibitor of Unexamined-Japanese-Patent No. 2015-127817, Paragraph 0060, and Paragraph 0031 of International Publication No. 2015/125469 - the compound of 0046 can also be used, The content is integrated in this specification.

When the resin composition of the present invention has other polymerization inhibitors, the content of the other polymerization inhibitors is preferably 0.01 to 20% by mass, and preferably 0.02 to 15% by mass with respect to the total solid content of the resin composition of the present invention. It is more preferable, and it is more preferable that it is 0.05-10 mass %.

1 type of other polymerization inhibitors may be sufficient, and 2 or more types may be sufficient as them. When there are 2 or more types of polymerization inhibitors, it is preferable that the sum total is the said range.

<Metal Adhesion Improver>

The resin composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to metal materials used for electrodes, wiring, and the like. Examples of the metal adhesion improving agent include aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like. can

[Aluminum-based adhesive aid]

Examples of aluminum-based adhesive aids include aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

Moreover, as other metal adhesion improving agents, the compound described in Paragraph 0046 of Unexamined-Japanese-Patent No. 2014-186186 - 0049, and the sulfide-type compound of Paragraph 0032 - 0043 of Unexamined-Japanese-Patent No. 2013-072935 can also be used, These content is incorporated herein.

The content of the metal adhesion improving agent is preferably 0.1 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the specific resin. By using the above lower limit or more, the adhesion between the pattern and the metal layer becomes good, and by using the above upper limit or less, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be one type or two or more types. When using 2 or more types, it is preferable that the sum total is the said range.

<Diffusion scavenger>

The resin composition of the present invention preferably contains an acid trapping agent in order to reduce the change in performance over time from exposure to heating. Here, the acid scavenger refers to a compound capable of trapping a generated acid by being present in the system, and is preferably a compound with low acidity and high pKa. As the acid trapping agent, a compound having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, etc. are preferable, and a primary amine, a secondary amine, a tertiary amine, and an ammonium salt are preferable. And, secondary amines, tertiary amines, and ammonium salts are more preferable.

As the acid scavenger, a compound having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or ether bond, and a hydroxyl group and/or ether bond aniline derivatives having When it has an onium structure, the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid having a lower acidity than the acid generated by the acid generator. it is desirable

Examples of the acid trapping agent having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. As the acid trapping agent having a diazabicyclo structure, 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, 1, 8-diazabicyclo[5,4,0]undec-7-ene etc. are mentioned. As the acid scavenger having an onium structure, tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide oxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, etc. can be heard Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of the acid trapping agent having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of the acid trapping agent having a pyridine structure include pyridine and 4-methylpyridine. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. As an aniline derivative which has a hydroxyl group and/or ether bond, N,N-bis (hydroxyethyl) aniline etc. are mentioned.

Specific examples of preferred acid trapping agents include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethyl Amine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene) ), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N -Methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6 -hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2 -Dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazole zoline, aminomorpholine, aminoalkylmorpholine and the like.

These acid trapping agents may be used individually by 1 type, or may be used in combination of 2 or more types.

The composition according to the present invention may or may not contain a dust trapping agent, but when it is contained, the content of the dust trapping agent is usually 0.001 to 10% by mass based on the total solids of the composition, preferably. is 0.01 to 5% by mass.

The use ratio of the acid generator and the acid scavenger is preferably acid generator/sand scavenger (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and preferably 300 or less from the viewpoint of suppressing the decrease in resolution due to the thickening of the relief pattern with the passage of time from exposure to heat treatment. The acid generator/dispersion complexing agent (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

<Other additives>

The resin composition of the present invention may contain various additives, for example, surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, and antioxidants, as necessary, within the range where the effects of the present invention are obtained. , aggregation inhibitors, phenolic compounds, other high molecular compounds, plasticizers, and other auxiliary agents (eg, antifoaming agents, flame retardants, etc.) can be blended. By appropriately containing these components, properties such as membrane properties can be adjusted. These components are, for example, described in paragraph No. 0183 of Japanese Laid-open Patent Publication No. 2012-003225 (paragraph No. 0237 of corresponding US Patent Application Publication No. 2013/0034812), paragraph No. 2008-250074 Reference can be made to descriptions of 0101 to 0104 and 0107 to 0109, the contents of which are incorporated herein by reference. When blending these additives, the total compounding amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

〔Surfactants〕

As surfactant, various surfactants, such as a fluorochemical surfactant, a silicone type surfactant, and a hydrocarbon type surfactant, can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By incorporating a surfactant into the photosensitive resin composition of the present invention, the liquid properties (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property can be further improved. That is, in the case of forming a film using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is lowered, the wettability to the surface to be coated is improved, and the applicability to the surface to be coated is reduced. It improves. For this reason, it is possible to more suitably form a film having a uniform thickness with little thickness unevenness.

Examples of the fluorine-based surfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, and F143. F482, F554, F780, RS-72-K (above, manufactured by DIC Co., Ltd.), Fluorad FC430, copper FC431, copper FC171, Novec FC4430, copper FC4432 (above, manufactured by 3M Japan Co., Ltd.), West Front S-382, East SC-101, East SC-103, East SC-104, East SC-105, East SC-1068, East SC-381, East SC-383, East S-393, East KH-40 ( As mentioned above, Asahi Glass Co., Ltd. product), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA), etc. are mentioned. The compound described in Paragraph 0015 of Unexamined-Japanese-Patent No. 2015-117327 - 0158, and Paragraph 0117 of Unexamined-Japanese-Patent No. 2011-132503 - the compound of 0132 can also be used for a fluorochemical surfactant, The content of these is integrated in this specification. . A block polymer can also be used as a fluorochemical surfactant, and as a specific example, the compound of Unexamined-Japanese-Patent No. 2011-89090 is mentioned, for example, These content is integrated in this specification.

The fluorine-based surfactant is a (meth)acrylate compound having 2 or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group and a propyleneoxy group). ) A fluorine-containing high molecular compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[Formula 72]

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000.

As the fluorochemical surfactant, a fluoropolymer having an ethylenically unsaturated group in the side chain may be used as the fluorochemical surfactant. As a specific example, Paragraph 0050 of Unexamined-Japanese-Patent No. 2010-164965 - 0090 and Paragraph 0289 - the compound of 0295 are mentioned, This content is integrated in this specification. Moreover, as a commercial item, DIC Corporation Megafac RS-101, RS-102, RS-718K etc. are mentioned, for example.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of the uniformity of the thickness of the coating film and liquid saving, and has good solubility in the composition.

As the silicone surfactant, for example, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) product), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials Co., Ltd.), KP-341, KF6001, KF6002 (above, Shin-Etsu Silicone Co., Ltd.) ) agent), BYK307, BYK323, BYK330 (above, manufactured by Big Chemie Co., Ltd.), and the like.

Examples of hydrocarbon surfactants include Pionin A-76, New Cargen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T (above, Takemoto Yushi Co., Ltd.), etc. are mentioned.

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (for example, glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl Ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate , sorbitan fatty acid ester, etc. are exemplified. As commercially available products, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 ( Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (made by Wako Junyaku Kogyo Co., Ltd.), Pionein D-6112, D-6112-W, D-6315 (Yushi Takemoto) Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (Nisshin Chemical Co., Ltd. product), etc. are mentioned.

As the cationic surfactant, specifically, organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, no. 77, no. 90, no. 95 (made by Kyoeisha Chemical Co., Ltd.), W001 (made by Yusho Co., Ltd.), etc. are mentioned.

Specifically as anionic surfactant, W004, W005, W017 (made by Yusho Co., Ltd.), Sandet BL (made by Sanyo Kasei Co., Ltd.), etc. are mentioned.

Surfactant may use only 1 type, and may combine 2 or more types.

The content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[Higher Fatty Acid Derivatives]

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

Moreover, as a higher fatty acid derivative, the compound of Paragraph 0155 of International Publication No. 2015/199219 can also be used, and this content is integrated in this specification.

When the resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the resin composition of the present invention. 1 type of higher fatty acid derivative may be sufficient as it, and 2 or more types may be sufficient as it. When two or more types of higher fatty acid derivatives are used, it is preferable that the total is within the above range.

[Thermal polymerization initiator]

The resin composition of the present invention may contain a thermal polymerization initiator, and particularly may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy to initiate or accelerate a polymerization reaction of a polymerizable compound. Since the polymerization reaction of resin and a polymeric compound can also advance by adding a thermal radical polymerization initiator, solvent resistance can be improved more. In addition, the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

As a thermal radical polymerization initiator, specifically, the compound described in Paragraph 0074 of Unexamined-Japanese-Patent No. 2008-063554 - 0118 is mentioned, This content is integrated in this specification.

When a thermal polymerization initiator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 0.5 to 15% by mass with respect to the total solid content of the resin composition of the present invention. is mass %. The thermal polymerization initiator may contain only 1 type, and may contain 2 or more types. When containing 2 or more types of thermal polymerization initiators, it is preferable that the total amount is the said range.

[Inorganic Particles]

The resin composition of the present invention may also contain inorganic particles. Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass and the like.

The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, still more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.

The said average particle diameter of an inorganic particle is a primary particle diameter, and is also a volume average particle diameter. The volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).

When the above measurement is difficult, it can also be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction/scattering method.

[Ultraviolet rays absorber]

The composition of the present invention may contain a ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate type, benzophenone type, benzotriazole type, substituted acrylonitrile type, and triazine type can be used.

Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-t-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydride Roxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy- 4-methoxy benzophenone, 2,4-dihydroxy benzophenone, 2-hydroxy-4-octoxy benzophenone, etc. are mentioned. In addition, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy- 3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole , 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole azoles, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, and the like.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate and the like. Further, as an example of the triazine-based ultraviolet absorber, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-di Methylphenyl) -1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4 -Dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, etc. Mono (hydroxyphenyl) triazine compounds of; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3 -Methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6 bis(hydroxyphenyl)triazine compounds such as -(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2- Hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]- and tris(hydroxyphenyl)triazine compounds such as 1,3,5-triazine.

In this invention, the said various ultraviolet absorbers may be used individually by 1 type, and may be used in combination of 2 or more types.

The composition of the present invention may or may not contain a ultraviolet absorber, but when it is included, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less with respect to the total solid mass of the composition of the present invention, It is more preferable that it is 0.01 mass % or more and 0.1 mass % or less.

[organic titanium compound]

The resin composition of the present embodiment may contain an organic titanium compound. By containing the organic titanium compound in the resin composition, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Examples of usable organic titanium compounds include those in which an organic group is bonded to a titanium atom through a covalent bond or an ionic bond.

Specific examples of organic titanium compounds are shown in I) to VII) below:

I) Titanium chelate compound: Especially, the titanium chelate compound which has 2 or more alkoxy groups is more preferable at the point from which the storage stability of a resin composition is favorable and a favorable curing pattern is obtained. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-phen theindionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.

II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium Tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyl oxide, titanium tetrakis[bis{2] ,2-(allyloxymethyl)butoxide}] and the like.

III) titanocene compounds: eg pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl ) titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

IV) Monoalkoxy titanium compounds: For example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide and the like.

V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.

VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate and the like.

VII) Titanate coupling agent: For example, isopropyl tridodecylbenzenesulfonyl titanate and the like.

Among them, the viewpoint that the organic titanium compound is at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound, which exhibits better chemical resistance. preferred in In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro Rho-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

When blending an organic titanium compound, the compounding amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the specific resin. When the compounding amount is 0.05 parts by mass or more, favorable heat resistance and chemical resistance are more effectively expressed in the resulting cured pattern, while when it is 10 parts by mass or less, the storage stability of the composition is more excellent.

[Antioxidant]

The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, elongation characteristics of the film after curing and adhesion to a metal material can be improved. As an antioxidant, a phenol compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the substituent described above, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Moreover, a phosphorus antioxidant can also be used suitably as an antioxidant. As the phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-6- yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl) oxy]ethyl]amine, phosphorous acid ethylbis(2,4-di-tert-butyl-6-methylphenyl), and the like. As a commercial item of an antioxidant, Adeka Stab AO-20, Adeka Stab AO-30, Adeka Stab AO-40, Adeka Stab AO-50, Adeka Stab AO-50F, for example, Adeka Stab AO-60, Adeka Stab AO-60G, Adeka Stab AO-80, Adeka Stab AO-330 (above, made by ADEKA Co., Ltd.), etc. are mentioned. Moreover, the antioxidant can also use the compound of Paragraph No. 0023 of Unexamined-Japanese-Patent No. 6268967 - 0048, The content of this is integrated in this specification. Moreover, the composition of this invention may contain a latent antioxidant as needed. As the latent antioxidant, the site functioning as an antioxidant is a compound protected by a protecting group, and the protecting group is released by heating at 100 to 250° C. or heating at 80 to 200° C. in the presence of an acid/base catalyst to function as an antioxidant. compounds can be mentioned. As a latent antioxidant, the compound of international publication 2014/021023, international publication 2017/030005, and Unexamined-Japanese-Patent No. 2017-008219 is mentioned, The content of this is integrated in this specification. As a commercial item of a latent antioxidant, Adeka Akles GPA-5001 (made by ADEKA Corporation) etc. are mentioned.

Examples of preferable antioxidants include compounds represented by 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and Formula (3).

[Formula 73]

In the general formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R ⁶ represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). . R ⁷ represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer from 1 to 4;

The compound represented by formula (3) suppresses oxidative deterioration of the aliphatic group or phenolic hydroxyl group of the resin. In addition, metal oxidation can be suppressed by the rust-preventive effect on the metal material.

Since it can act simultaneously on the resin and the metal material, k is more preferably an integer of 2 to 4. Examples of R ⁷ include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, what combined them, etc. are mentioned, You may have a substituent further. Among these, from the viewpoint of solubility in a developing solution and metal adhesion, those having an alkyl ether group and -NH- are preferable, and -NH- is more preferable from the viewpoint of interaction with resin and metal adhesion due to metal complexation. .

Although the following are mentioned as an example of the compound represented by General formula (3), It is not limited to the following structure.

[Formula 74]

[Formula 75]

[Formula 76]

[Formula 77]

The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin. By setting the addition amount to 0.1 parts by mass or more, the effect of improving the elongation properties and adhesion to metal materials is easily obtained even in a high-temperature, high-humidity environment, and by setting it to 10 parts by mass or less, for example, by interaction with the photosensitive agent, The sensitivity of the composition is improved. Antioxidant may use only 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that those total amounts become the said range.

[anti-agglomeration agent]

The resin composition of this embodiment may contain an aggregation inhibitor as needed. As an aggregation inhibitor, sodium polyacrylate etc. are mentioned.

In this invention, an aggregation inhibitor may be used individually by 1 type, and may be used in combination of 2 or more type.

The composition of the present invention may or may not contain an aggregation inhibitor, but when it is included, the content of the aggregation inhibitor is preferably 0.01% by mass or more and 10% by mass or less with respect to the total solid mass of the composition of the present invention, It is more preferable that it is 0.02 mass % or more and 5 mass % or less.

[phenolic compound]

The resin composition of this embodiment may contain a phenolic compound as needed. As the phenolic compound, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS -2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (above, product name, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR- BIPC-F (above, brand name, Asahi Yukizai Kogyo Co., Ltd. product), etc. are mentioned.

In this invention, a phenol type compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The composition of the present invention may or may not contain a phenolic compound, but when it is included, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less with respect to the total solid mass of the composition of the present invention and more preferably 0.02% by mass or more and 20% by mass or less.

[Other high molecular compounds]

Examples of other high molecular compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolak resins, resole resins, polyhydroxystyrene resins, copolymers thereof, and the like. The other high molecular compound may be a modified body into which a crosslinking group such as a methylol group, an alkoxymethyl group, or an epoxy group has been introduced.

In the present invention, the other high molecular compounds may be used singly or in combination of two or more.

The composition of the present invention may or may not contain other high molecular compounds, but in the case where they are included, the content of the other high molecular compounds is preferably 0.01% by mass or more and 30% by mass or less with respect to the total solid mass of the composition of the present invention. and more preferably 0.02% by mass or more and 20% by mass or less.

<Characteristics of Resin Composition>

The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm ² /s to 12,000 mm ² /s are preferred, 2,000 mm ² /s to 10,000 mm ² /s are more preferred, and 3,000 mm ² /s to 8,000 ^{mm 2} /s are preferred. more preferable If it is the said range, it becomes easy to obtain a coating film with high uniformity. At 1,000 mm ² /s or less, it is difficult to apply the film to a film thickness required as, for example, an insulating film for rewiring, and at 12,000 mm ² /s or more, the coated surface shape may deteriorate.

<Restrictions on Materials Contained in Resin Composition>

The moisture content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and still more preferably less than 1.0% by mass. At 2.0% or more, there is a possibility that the storage stability of the resin composition is impaired.

As a method of maintaining the content of water, adjustment of humidity in storage conditions, reduction of the porosity of the container at the time of storage, etc. are mentioned.

From an insulating viewpoint, the metal content of the 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 the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When a plurality of metals are included, it is preferable that the sum of these metals is within the above range.

In addition, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention, or a raw material constituting the resin composition of the present invention For example, a method of performing filter filtration on the substrate, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible is exemplified.

In the resin composition of the present invention, considering the use 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 more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosiveness. more preferable Especially, as for what exists in the state of a halogen ion, less than 5 mass ppm is preferable, less than 1 mass ppm is more preferable, and less than 0.5 mass ppm is still more preferable. As a halogen atom, a chlorine atom and a bromine atom are mentioned. 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 method of adjusting the content of halogen atoms, ion exchange treatment or the like is preferably used.

A conventionally well-known container can be used as a container for the resin composition of the present invention. In addition, as the storage container, for the purpose of suppressing the mixing of impurities into the raw materials or the resin composition of the present invention, a multi-layered bottle in which the inner wall of the container is made of 6 types of 6-layer resin, and a bottle in which 6 types of resin are used in a 7-layer structure It is also preferable to use As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<cured product of resin composition>

By curing the resin composition of the present invention, a cured product of this resin composition can be obtained.

The cured product of the present invention is a cured product formed by curing the resin composition of the present invention.

Curing of the resin composition is preferably performed by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and more preferably in the range of 170°C to 350°C. What is within the range is particularly preferred. The shape of the cured product of the resin composition is not particularly limited, and may be selected according to the application, such as a film shape, a rod shape, a spherical shape, or a pellet shape. In this invention, it is preferable that this hardened|cured material is film-like. In addition, by pattern processing of the resin composition, according to the application, such as formation of a protective film on the wall surface, formation of via holes for conduction, adjustment of impedance, capacitance or internal stress, imparting a heat dissipation function, The shape of this cured product can also be selected. It is preferable that the film thickness of this hardened|cured material (film|membrane consisting of hardened|cured material) is 0.5 micrometer or more and 150 micrometer or less.

The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less. Here, the shrinkage rate refers to the percentage of the volume change before and after curing of the resin composition, and can be calculated from the following formula.

Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

<Characteristics of cured product of resin composition>

The imidation reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. If less than 70%, there is a possibility that the mechanical properties of the cured product are inferior.

The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more.

The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and still more preferably 230°C or higher.

<Preparation of resin composition>

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

For the mixing, mixing by stirring blades, mixing by a ball mill, mixing by rotating the tank itself, or the like can be employed.

The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign matters such as dust and fine particles in the resin composition of the present invention. As for the filter hole diameter, the aspect which is 5 micrometers or less is mentioned, for example, 1 micrometer or less is preferable, 0.5 micrometer or less is more preferable, and 0.1 micrometer or less is still more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferably HDPE (high density polyethylene). As the filter, one previously washed with an organic solvent may be used. In the filter filtration process, you may connect and use multiple types of filters in series or parallel. In the case of using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. As a connection aspect, the aspect which connected the HDPE filter with a pore diameter of 1 micrometer as a 1st stage|stage, and the HDPE filter with a pore diameter of 0.2 micrometer as a 2nd stage|stage was connected in series, for example. Moreover, you may filter various materials multiple times. When filtering multiple times, circulation filtration may be sufficient. Moreover, you may perform filtration by pressurizing. In the case of filtering by pressurization, the pressurized 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 0.5 MPa or less is more preferable.

In addition to filtration using a filter, an impurity removal treatment 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. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

After filtration using a filter, the resin composition filled in the bottle may be further subjected to a step of degassing under reduced pressure.

(Method of producing cured product)

The method for producing a cured product of the present invention preferably includes a film forming step of forming a film by applying the resin composition onto a substrate.

In addition, the method for producing a cured product of the present invention includes an exposure step of selectively exposing the film formed by the film formation process and the film formation process, and a phenomenon of developing the film exposed by the exposure process using a developer to form a pattern. It is more preferable to include a process.

The method for producing a cured product of the present invention includes the film forming step, the exposure step, the developing step, and the heating step of heating the pattern obtained by the developing step and the post-development exposure step of exposing the pattern obtained by the developing step. It is particularly preferable to include at least one.

Moreover, it is also preferable that the manufacturing method of this invention includes the said film formation process and the process of heating the said film|membrane.

Hereinafter, the detail of each process is demonstrated.

<Film formation process>

The resin composition of the present invention can be used in a film formation step of forming a film by applying it on a substrate.

The method for producing a cured product of the present invention preferably includes a film forming step of forming a film by applying the resin composition onto a substrate.

〔write〕

The type of base material can be appropriately determined depending on the application, but semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, Ni , metal substrates such as Cu, Cr, and Fe (for example, a substrate formed of metal and a substrate in which a metal layer is formed, for example, by plating or vapor deposition), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, electrode plates of plasma display panels (PDP), and the like, are not particularly limited. In the present invention, semiconductor fabrication substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

In addition, layers such as an adhesion layer or an oxide layer by hexamethyldisilazane (HMDS) or the like may be provided on the surface of these substrates.

In addition, the shape of the substrate is not particularly limited, and may be circular or rectangular.

As the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is a rectangular shape, the length of a short side is 100-1000 mm, for example, Preferably it is 200-700 mm.

Moreover, as a base material, for example, a plate shape, preferably a panel shape base material (substrate) is used.

In the case of forming a film by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured material) or the surface of a metal layer, the resin layer or metal layer serves as the base material.

As a means for applying the resin composition of the present invention onto a substrate, application is preferable.

As the means to be applied, specifically, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, ink jet law, etc. From the viewpoint of uniformity of film thickness, more preferably a spin coating method, a slit coating method, a spray coating method, or an inkjet method. From the viewpoint of uniformity of film thickness and productivity, the spin coating method and the slit coating method are preferred. do. A film having a desired thickness can be obtained by adjusting the solid content concentration of the resin composition and application conditions according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, and inkjet methods are preferable, and for rectangular substrates, slit coating, spray coating, and inkjet methods are preferred. etc. are preferred. In the case of the spin coating method, it can be applied for about 10 seconds to 3 minutes at a rotational speed of 500 to 3,500 rpm, for example.

Moreover, a method of transferring onto a base material a coating film applied and formed on a temporary support body in advance by the above application method can also be applied.

Regarding the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP2006-023696 and paragraphs 0096 to 0108 of JP2006-047592 can be suitably used in the present invention.

Moreover, you may perform the process of removing an excess film|membrane in the edge part of a base material. Examples of such a process include edge bead rinse (EBR), back rinse, and the like.

Alternatively, a pre-wet process may be employed in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve wettability of the substrate, and then the resin composition is applied.

<Drying process>

The film may be subjected to a step of drying the formed film (layer) in order to remove the solvent after the film formation step (layer formation step) (drying step).

That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film formation step.

Moreover, it is preferable that the said drying process is performed after a film formation process and before an exposure process.

The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70°C to 130°C, still more preferably 90°C to 110°C. Moreover, you may dry by reduced pressure. As drying time, 30 seconds - 20 minutes are illustrated, 1 minute - 10 minutes are preferable, and 2 minutes - 7 minutes are more preferable.

<Exposure process>

The film may be subjected to an exposure step of selectively exposing the film.

That is, the manufacturing method of the hardened|cured material of this invention may also include the exposure process of selectively exposing the film|membrane formed by the film formation process.

Exposing selectively means exposing a part of the film. Further, by selective exposure, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed in the film.

The exposure amount is not particularly determined as long as the resin composition of the present invention can be cured, but is preferably 50 to 10,000 mJ/cm ² , and 200 to 8,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, for example. more preferable

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

Regarding the exposure wavelength, in relation to the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), broad (three wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm) , F ₂ excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength: 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, and the like. Regarding the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and exposure by i-line is particularly preferred. In this way, a particularly high exposure sensitivity can be obtained.

In addition, the method of exposure is not particularly limited, and any method is sufficient as long as at least a part of the film made of the resin composition of the present invention is exposed, but exposure using a photomask, exposure by a laser direct imaging method, and the like are exemplified.

<Post-exposure heating process>

The film may be subjected to a step of heating after exposure (post-exposure heating step).

That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.

The post-exposure heating step can be performed after the exposure step and before the developing step.

It is preferable that it is 50 degreeC - 140 degreeC, and, as for the heating temperature in the heating process after exposure, it is more preferable that it is 60 degreeC - 120 degreeC.

30 seconds - 300 minutes are preferable, and, as for the heating time in a heating process after exposure, 1 minute - 10 minutes are more preferable.

The temperature increase rate in the post-exposure heating step is preferably 1 to 12°C/minute, more preferably 2 to 10°C/minute, and still more preferably 3 to 10°C/minute from the temperature at the start of heating to the maximum heating temperature.

Moreover, you may change the temperature increase rate suitably in the middle of heating.

The heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.

Moreover, it is also preferable to carry out in the atmosphere of low oxygen concentration by flowing an inert gas, such as nitrogen, helium, and argon, at the time of heating.

<Development process>

The film after exposure may be subjected to a developing step in which a pattern is formed by developing using a developing solution.

That is, the method for producing a cured product of the present invention may include a developing step of forming a pattern by developing the film exposed in the exposure step using a developing solution. By carrying out development, one of the exposed part and the non-exposed part of the film|membrane is removed, and a pattern is formed.

Here, a phenomenon in which an unexposed portion of a film is removed by a developing process is referred to as a negative-type phenomenon, and a phenomenon in which an exposed portion of a film is removed by a developing process is referred to as a positive-type phenomenon.

〔developer〕

As a developing solution used in the developing process, an aqueous alkali solution or a developing solution containing an organic solvent is exemplified.

When the developing solution is an aqueous alkali solution, examples of basic compounds that the aqueous alkali solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, and TMAH (tetramethyl ammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethyl Amine, Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide, Tetrapentylammonium Hydroxide, Tetrahexylammonium Hydroxide, Tetraoctylammonium Hydroxide Hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyl dipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide Side, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferred, and TMAH is more preferred. The content of the basic compound in the developing solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developing solution, for example, when TMAH is used. .

When the developing solution contains an organic solvent, the organic solvent is an ester, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, beauty Ethyl lactate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetic acid alkyls such as methyl alkyloxyacetate, ethyl alkyloxyacetate, alkyloxyacetic acid butyl (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g. 3-alkyloxypropionic acid Methyl, 3-alkyloxyethylpropionate, etc. (eg, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, etc.), 2-alkyloxypropionic acid Alkyl esters (e.g., 2-alkyloxymethylpropionate, 2-alkyloxyethylpropionate, 2-alkyloxypropylpropionate, etc. (e.g., 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2-methoxy propyl propionate, 2-ethoxymethylpropionate, 2-ethoxyethylpropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g. 2-methoxy- 2-methylmethylpropionate, 2-ethoxy-2-methylethylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. , And, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl Cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol col monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentane On, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, limonene Cyclic terpenes such as sulfoxides, dimethyl sulfoxide as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol as alcohols , methyl isobutyl carbinol, triethylene glycol, etc., and, as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are mentioned suitably.

When the developing solution contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred. A developing solution containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone and dimethyl sulfoxide is more preferable, and a developing solution containing cyclopentanone is most preferable.

When the developing solution contains an organic solvent, the content of the organic solvent relative to the total mass of the developing solution is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass It is particularly preferable that it is above. Moreover, 100 mass % may be sufficient as the said content.

The developing solution may further contain other components.

As another component, a well-known surfactant, a well-known antifoaming agent, etc. are mentioned, for example.

[Supply Method of Developer]

The method of supplying the developer is not particularly limited as long as a desired pattern can be formed. A method of immersing a film-formed substrate in a developer, a puddle phenomenon in which a developer is supplied to a film formed on a substrate using a nozzle, or a developer is continuously applied. There is a way to supply. The type of nozzle is not particularly limited, and examples thereof include straight nozzles, shower nozzles, and spray nozzles.

From the viewpoints of penetrability of the developer, removability of the non-image portion, and manufacturing efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferable, and from the viewpoint of penetrability of the developer into the image portion, the spray The method of supplying with a nozzle is more preferable.

Alternatively, after continuously supplying the developing solution with a straight nozzle, the base material is spun to remove the developing solution from the base material, and after spin drying, a step of continuously supplying the developing solution with the straight nozzle again and then spinning the base material to remove the developing solution from the base material may be employed. , You may repeat this process multiple times.

Further, as a method for supplying the developing solution in the developing step, a step in which the developing solution is continuously supplied to the substrate, a step in which the developing solution is maintained on the substrate in a substantially stationary state, a step in which the developing solution is vibrated on the substrate with ultrasonic waves or the like, and a process in which they are combined. etc. can be employed.

As development time, 10 second - 10 minutes are preferable and 20 second - 5 minutes are more preferable. The temperature of the developing solution at the time of development is not particularly determined, but is preferably 10 to 45°C, more preferably 18°C to 30°C.

In the developing step, after the treatment using the developing solution, the pattern may be further washed (rinsed) with a rinsing solution. Moreover, you may employ|adopt the method of supplying a rinsing liquid while the developing solution which touches on a pattern is not completely dry.

[rinse liquid]

When the developing solution is an aqueous alkali solution, water can be used as a rinse solution, for example. When the developing solution is a developing solution containing an organic solvent, for example, a solvent different from the solvent contained in the developing solution (eg, water, an organic solvent different from the organic solvent contained in the developing solution) can be used as the rinsing solution. there is.

Examples of the organic solvent in case the rinse liquid contains an organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetate (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, alkyloxy butyl acetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g. 3-alkyloxy Methyl propionate, 3-alkyloxyethylpropionate, etc. (eg, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, etc.), 2-alkyloxy Alkyl esters of propionic acid (e.g., 2-alkyloxymethylpropionate, 2-alkyloxyethylpropionate, 2-alkyloxypropylpropionate, etc. (e.g., 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2-methoxypropionate, Propyl oxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylmethylpropionate and 2-alkyloxy-2-methylethylpropionate (e.g. 2-methoxy -2-methylmethylpropionate, 2-ethoxy-2-methylethylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate etc., and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, Ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol Lycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclo Pentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and aromatic hydrocarbons such as toluene, xylene, anisole, etc. as cyclic hydrocarbons; Cyclic terpenes such as limonene, dimethyl sulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, and propylene glycol as alcohols , methyl isobutyl carbinol, triethylene glycol, etc., and, as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are mentioned suitably.

When the rinse liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, and cyclopentanone, γ-butyrolactone, dimethylsulfoxide Side, PGMEA, and PGME are more preferable, and cyclohexanone and PGMEA are still more preferable.

When the rinsing liquid contains an organic solvent, the rinsing liquid preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and more preferably 90% by mass or more of an organic solvent do. Moreover, 100 mass % of the rinse liquid may be an organic solvent.

The rinse liquid may further contain other components.

As another component, a well-known surfactant, a well-known antifoaming agent, etc. are mentioned, for example.

[How to supply rinse liquid]

The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and there are methods of immersing the substrate in the rinsing liquid, supplying the rinsing liquid to the substrate by raising the liquid, and supplying the rinsing liquid to the substrate by showering. There is a method of continuously supplying a rinsing liquid onto a substrate by means of a straight nozzle or the like.

From the viewpoint of permeability of the rinse liquid, removability of the non-image area, and manufacturing efficiency, there is a method of supplying the rinse liquid to a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying the rinse liquid to the spray nozzle is preferable, and the image area From the viewpoint of permeability of the rinsing liquid to the water, a method of supplying through a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples thereof include straight nozzles, shower nozzles, and spray nozzles.

That is, the rinsing step is preferably a step of supplying a rinsing liquid to the film after exposure through a straight nozzle or continuously supplying the rinsing liquid to the film after exposure, and more preferably a process of supplying the rinsing liquid through a spray nozzle.

Further, as a method for supplying the rinsing liquid in the rinsing step, a process in which the rinsing liquid is continuously supplied to the substrate, a process in which the rinsing liquid is maintained on the substrate in a substantially stationary state, a process in which the rinsing liquid is vibrated on the substrate with ultrasonic waves, and A process or the like combining them is employable.

As rinse time, 10 seconds - 10 minutes are preferable, and 20 seconds - 5 minutes are more preferable. The temperature of the rinsing liquid at the time of rinsing is not particularly determined, but is preferably 10 to 45°C, more preferably 18°C to 30°C.

<Heating process>

The pattern obtained by the developing step (pattern after rinsing in the case of performing the rinsing step) may be subjected to a heating step of heating the pattern obtained by the above development.

That is, the manufacturing method of the hardened|cured material of this invention may also include the heating process of heating the pattern obtained by the image development process.

Further, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method or a film obtained by the film forming step without performing the developing step.

In the heating step, resins such as polyimide precursors are cyclized to become resins such as polyimide.

Further, crosslinking of unreacted crosslinkable groups in specific resins or crosslinking agents other than specific resins also proceeds.

The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ° C, more preferably 150 to 350 ° C, still more preferably 150 to 250 ° C, still more preferably 160 to 250 ° C, 160 ° C ~230°C is particularly preferred.

The heating step is preferably a step of accelerating the cyclization reaction of the polyimide precursor in the pattern by the action of a base or the like generated from the base generator by heating.

The heating in the heating step is preferably performed at a temperature rising rate of 1 to 12°C/min from the temperature at the start of heating to the highest heating temperature. The temperature increase rate is more preferably 2 to 10°C/minute, more preferably 3 to 10°C/minute. By setting the temperature increase rate to 1 ° C./min or more, excessive volatilization of the acid or solvent can be prevented while securing productivity, and by setting the temperature increase rate to 12 ° C./min or less, residual stress of the cured product can be relaxed.

Further, in the case of an oven capable of rapid heating, heating is performed at a heating rate of 1 to 8°C/sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec. desirable.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, still more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the time of starting the process of heating to the highest heating temperature. For example, when the resin composition of the present invention is applied on a substrate and then dried, the temperature of the film (layer) after this drying is, for example, 30 to higher than the boiling point of the solvent contained in the resin composition of the present invention. It is preferable to raise the temperature from a temperature as low as 200°C.

The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and still more preferably 15 to 240 minutes.

In particular, in the case of forming a multilayer laminate, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, still more preferably 100°C or higher, and particularly preferably 120°C or higher, from the viewpoint of adhesion between layers. .

The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and still more preferably 240°C or lower.

Heating may be performed stepwise. As an example, a process such as raising the temperature from 25 ° C to 120 ° C at 3 ° C / min, holding at 120 ° C for 60 minutes, raising the temperature from 120 ° C to 180 ° C at 2 ° C / min and holding at 180 ° C for 120 minutes You can do it. Moreover, it is also preferable to process while irradiating an ultraviolet-ray as described in US Patent Publication No. 9159547. It is possible to improve the properties of the film by such a pretreatment process. What is necessary is just to perform a pretreatment process in a short time of about 10 second - about 2 hours, and 15 second - 30 minutes are more preferable. The pretreatment may be carried out in two or more stages, for example, a first stage pretreatment step may be performed in the range of 100 to 150 ° C., followed by a second stage pretreatment step in the range of 150 to 200 ° C.

Moreover, you may cool after heating, and as a cooling rate in this case, it is preferable that it is 1-5 degrees C/min.

The heating step is preferably carried out in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon or under reduced pressure to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

Although it does not specifically limit as a heating means in a heating process, For example, a hot plate, an infrared furnace, an electrothermal oven, a hot air oven, an infrared oven, etc. are mentioned.

<Exposure process after development>

The pattern obtained by the developing step (pattern after rinsing in the case of performing the rinsing step) may be subjected to a post-development exposure step for exposing the pattern after the developing step instead of or in addition to the heating step.

That is, the method for producing a cured product of the present invention may also include a post-development exposure step of exposing the pattern obtained by the developing step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.

In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like proceeds by photosensitization of a photobase generator, a reaction in which acid-decomposable groups are desorbed by photosensitization of a photoacid generator, etc. are promoted. can make it

In the post-development exposure process, at least a part of the pattern obtained in the development process may be exposed, but it is preferable that all of the patterns are exposed.

The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm ² , more preferably 100 to 15,000 mJ/cm ² in terms of exposure energy at a wavelength at which the photosensitive compound has sensitivity.

The post-development exposure process can be performed using, for example, the light source in the exposure process described above, and broadband light is preferably used.

<Metal layer formation process>

The pattern obtained by the developing step (preferably provided in at least one of the heating step and the post-exposure developing step) may be subjected to a metal layer forming step of forming a metal layer on the pattern.

That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern obtained by the developing step (preferably provided in at least one of the heating step and the post-development exposure step).

As the metal layer, existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals are exemplified, and copper and Aluminum is more preferred, and copper is more preferred.

The method of forming the metal layer is not particularly limited, and an existing method can be applied. For example, Japanese Unexamined Patent Publication No. 2007-157879, Japanese Publication No. 2001-521288, Japanese Unexamined Patent Publication No. 2004-214501, Japanese Unexamined Patent Publication No. 2004-101850, US Patent Publication No. 7888181B2, US Patent Publication No. The method described in 9177926B2 can be used. For example, photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electroplating, electroless plating, etching, printing, methods combining these, and the like can be considered. More specifically, a patterning method in which sputtering, photolithography and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined are exemplified. As a preferable aspect of plating, electrolytic plating using a copper sulfate or copper cyanide plating solution is exemplified.

The thickness of the metal layer is preferably 0.01 μm to 50 μm, and more preferably 1 μm to 10 μm in the thickest part.

<Use>

Examples of the manufacturing method of the cured product of the present invention or applicable fields of the cured product of the present invention include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. In addition, pattern formation of a sealing film, a substrate material (a base film or cover lay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting use as described above by etching may be used. Regarding these applications, for example, Science & Technology Co., Ltd. "Highly functional polyimide and application technology" April 2008, Masaaki Kakimoto/Supervisor, CMC Technical Library "Basics and development of polyimide materials" November 2011 Monthly publication, Japanese Polyimide/Aromatic Polymer Research Society/edition "Latest Polyimide Basics and Applications" N.T.S., August 2010, etc. can be referenced.

In addition, the production method of the cured product of the present invention or the cured product of the present invention is used for producing a plate surface such as an offset plate surface or a screen plate surface, for use in etching of molded parts, in electronics, in particular, as a protective lacquer in microelectronics, and It can also be used for production of dielectric layers and the like.

(Laminate and manufacturing method of the laminate)

The laminate of the present invention refers to a structure having a plurality of layers comprising a cured product of the present invention.

The laminate of the present invention is a laminate comprising two or more layers of cured material, and may be a laminate of three or more layers.

At least one of the two or more layers of the cured material included in the laminate is a layer made of the cured material of the present invention, and from the viewpoint of suppressing shrinkage of the cured material or deformation of the cured material due to the shrinkage, It is also preferable that all the layers made of the cured material included in the laminate are layers made of the cured material of the present invention.

That is, the manufacturing method of the laminate of the present invention preferably includes the manufacturing method of the cured product of the present invention, and more preferably includes repeating the manufacturing method of the cured product of the present invention a plurality of times.

It is preferable that the layered product of the present invention includes two or more layers of layers made of a cured product and includes a metal layer between any one of the layers made of the cured product. It is preferable that the said metal layer is formed by the said metal layer formation process.

That is, it is preferable that the manufacturing method of the laminated body of this invention further includes the metal layer formation process of forming a metal layer on the layer which consists of hardened|cured material between the manufacturing method of hardened|cured material performed multiple times. Preferred aspects of the metal layer forming process are as described above.

As the above-mentioned laminate, a laminate containing at least a layered structure in which three layers, for example, a layer made of a first cured material, a metal layer, and a layer made of a second cured material are laminated in this order, is mentioned as a preferable one. .

It is preferable that both the layer composed of the first cured material and the layer composed of the second cured material are layers made of the cured material of the present invention. The resin composition of the present invention used for forming the layer composed of the first cured material and the resin composition of the present invention used for forming the layer composed of the second cured material may be compositions having the same composition or different in composition. It may be a composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a redistribution layer.

<Laminating process>

It is preferable that the manufacturing method of the laminated body of this invention includes a lamination process.

The lamination process is, again, on the surface of the pattern (resin layer) or metal layer, (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process and post-development exposure It is a series of steps including performing one of the steps in this order. However, an aspect in which at least one of the film formation process of (a) and the heating process and post-development exposure process of (d) may be repeated. Moreover, you may include (e) metal layer formation process after at least one of (d) a heating process and a post-development exposure process. It goes without saying that the above drying step or the like may be appropriately further included in the lamination step.

When the lamination process is further performed after the lamination process, a surface activation treatment process may be further performed after the exposure process, the heating process, or the metal layer forming process. As the surface activation treatment, plasma treatment is exemplified. Details of the surface activation treatment will be described later.

It is preferable to perform the said lamination process 2 to 20 times, and it is more preferable to perform it 2 to 9 times.

For example, a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably composed of 2 or more layers and 20 or less layers, and more preferably 2 or more layers and 9 or less layers. .

Each of the above layers may be the same or different in composition, shape, film thickness, and the like.

In this invention, after providing a metal layer especially, the aspect which further forms the hardened|cured material (resin layer) of the said resin composition of this invention so that the said metal layer may be covered is preferable. Specifically, (a) a film formation step, (b) an exposure step, (c) a development step, (d) at least one of a heating step and a post-development exposure step, (e) an aspect that is repeated in the order of the metal layer formation step, Alternatively, (a) a film forming step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer forming step are repeated in this order. By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming step, the resin composition layer (resin layer) of the present invention and the metal layer can be laminated alternately.

(Surface activation treatment process)

The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a part of the metal layer and the resin composition layer to a surface activation treatment.

The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step may be performed after performing the surface activation treatment step on the resin composition layer after the above development step.

The surface activation treatment may be performed on at least a portion of the metal layer, at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region where the resin composition layer is formed on the surface of the metal layer. In this way, by performing surface activation treatment on the surface of the metal layer, adhesion to the resin composition layer (film) provided on the surface can be improved.

In addition, it is preferable to perform the surface activation treatment also on a part or all of the resin composition layer (resin layer) after exposure. In this way, by subjecting the surface of the resin composition layer to surface activation treatment, adhesion to the metal layer or resin layer provided on the surface of the surface activation treatment can be improved. In particular, when the resin composition layer is cured, such as in the case of negative development, it is difficult to receive damage by surface treatment and the adhesion is easy to improve.

As the surface activation treatment, specifically, plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixture gas, argon/oxygen mixture gas, etc.), corona discharge treatment, CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ After etching treatment by /O ₂ , surface treatment by ultraviolet (UV) ozone method, and immersion in an aqueous hydrochloric acid solution to remove the oxide film, having at least one amino group and thiol group It is selected from an immersion treatment for an organic surface treatment agent containing a compound and a mechanical roughening treatment using a brush, and a plasma treatment is preferred, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J/m ² , more preferably 1000 to 100,000 J/m ² , and most preferably 10,000 to 50,000 J/m ² .

(Method of manufacturing electronic device)

In addition, the present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention.

Further, the present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing a cured product of the present invention or the method for manufacturing a laminate of the present invention. As a specific example of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a redistribution layer, the description of paragraphs 0213 to 0218 and the description of FIG. incorporated into the specification.

(compound)

The compound of the present invention has an aminooxy radical structure and an alkoxysilyl group.

Preferred embodiments of the compound of the present invention are the same as those in the case where the specific polymerization inhibitor described above has an aminooxy radical structure as the polymerization inhibitory site.

Example

The present invention will be described in more detail by way of examples below. The materials, usage amount, ratio, processing content, processing procedure, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the spirit of the present invention. Therefore, 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 BS-1: Synthesis of BS-1>

In a flask equipped with a stirrer and a condenser, 17.1 g (100 mmol) of 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was mixed with tetrahydrofuran. (manufactured by Tokyo Kasei Kogyo Co., Ltd.) It was dissolved in 100 mL and cooled at 0°C. Next, 15.52 g (100 mmol) of 3-(triethoxysilyl)propyl isocyanate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 50 mL of tetrahydrofuran (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and at 0 ° C. Dropped for 1 hour. Subsequently, the temperature was raised to 25°C, and after stirring for 2 hours, the mixture was dissolved in 800 mL of ethyl acetate and transferred to a separatory funnel. Subsequently, this was washed twice with 100 mL of water and twice with 150 mL of saturated brine, and dried over sodium sulfate. It was transferred to a one-necked flask, filtering this with filter paper, and the solvent was removed with an evaporator to obtain 26 g of BS-1. The structure of BS-1 is presumed to be the following structure.

[Formula 78]

<Synthesis Examples BS-2 to BS-7: Synthesis of BS-2 to BS-7>

BS-2 to BS-7 were synthesized in the same manner as in the synthesis of BS-1.

The structures of BS-2 to BS-7 are presumed to be the following structures, respectively.

[Formula 79]

<Synthesis Example AA-1: Synthesis of Diamine (AA-1)>

In a flask equipped with a condenser and a stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 17.4 g of dehydrated pyridine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (0.22 mol) was dissolved in 78 g of ethyl acetate and cooled to 5°C or less. Then, 48.4 g (0.21 mol) of 3,5-dinitrobenzoyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 145 g of ethyl acetate, and this solution was added dropwise into the flask for 1 hour using a dropping funnel. did. After completion of the dropping, the mixture was stirred at 10°C or less for 30 minutes, heated to 25°C, and stirred for 3 hours. Then, the reaction solution was diluted with 600 mL of ethyl acetate (CH ₃ COOEt), transferred to a separatory funnel, and washed with 300 mL of water, 300 mL of saturated sodium bicarbonate water, 300 mL of dilute hydrochloric acid, and 300 mL of saturated brine in this order. . After liquid separation and washing, drying with 30 g of magnesium sulfate, concentration using an evaporator and vacuum drying were carried out to obtain 61.0 g of a dinitro body (A-1).

In a flask equipped with a condenser and stirrer, 27.9 g (500 mmol) of reduced iron (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 5.9 g (110 mmol) of ammonium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), acetic acid (Fujifilm Wako Junyaku Co., Ltd.) 3.0 g (50 mmol) and 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (Tokyo Kasei Kogyo Co., Ltd.) 0.03 g were weighed, , 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added and stirred.

Subsequently, 16.2 g of the dinitro body (A-1) was added in small portions over 1 hour, and stirred for 30 minutes. Next, the outside temperature was raised to 85°C, stirred for 2 hours, cooled to 25°C or lower, and filtered using Celite (registered trademark). The filtrate was concentrated with a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separatory funnel, and washed twice with 300 mL of saturated sodium bicarbonate, followed by washing with 300 mL of water and 300 mL of saturated saline in that order. After liquid separation and washing, drying with 30 g of magnesium sulfate, concentration and vacuum drying were performed using an evaporator to obtain 11.0 g of diamine (AA-1). It was confirmed from the nmR spectrum that it was diamine (AA-1).

¹ H-NMR data (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane)

δ(ppm)=1.95(s, 3H), 3.68(s, 4H), 4.45-4.47(m, 2H), 4.50-4.53(m, 2H), 5.58(s, 1H), 6.14(s, 1H), 6.19-6.20(t, 1H), 6.77-6.78(d, 2H)

[Formula 80]

<Synthesis Example MA-1: Synthesis of carboxylic acid dianhydride (MA-1)>

In a flask equipped with a condenser and a stirrer, 18.5 g (0.88 mol) of anhydrous trimellitic acid chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 200 g of ethyl acetate and cooled to -10°C or lower. Next, 10.6 g (40 mmol) of diamine (AA-1) and 7.12 g (90 mmol) of pyridine were dissolved in 60 g of ethyl acetate, and this was added dropwise over 1 hour. After dripping, it stirred at -10 degreeC or less for 1 hour and 25 degreeC for 1 hour. Then, 500 mL of ethyl acetate and 300 mL of water were added, stirred for 10 minutes, transferred to a separatory funnel, washed with 300 mL of water, washed twice with 200 mL of saturated sodium bicarbonate solution, and 200 mL of dilute hydrochloric acid aqueous solution, Washed in the order of saturated saline. After drying this with magnesium sulfate and concentrating with an evaporator, the ethyl acetate solution was crystallized in hexane. This was filtered and vacuum dried to obtain 20.0 g of carboxylic acid dianhydride (anhydride (MA-1)). It was confirmed from the nmR spectrum that it was an anhydride (MA-1). The results of analyzing the anhydride (MA-1) by ¹ H-NMR are shown below.

¹ H-NMR data (deuterated dimethyl sulfoxide (DMSO), 400 MHz, internal standard: tetramethylsilane)

δ (ppm) = 1.88 (s, 3H), 4.44-4.47 (q, 2H), 4.60-4.62 (q, 2H), 5.70 (s, 2H), 6.06 (s, 1H), 8.23-8.26 (m, 4H), 8.52-8.54(d, 2H), 8.65(s, 2H), 8.82-8.83(t, 1H), 10.98(s, 2H)

[Formula 81]

<Synthesis Example PA-1: Synthesis of Polyamideimide Precursor (PA-1)>

In a flask equipped with a condenser and a stirrer, 29.3 g (47.8 mmol) of anhydride (MA-1) was suspended in 100 g of diglyme while removing moisture. 13.4 g (100 mmol) of diethylene glycol monoethyl ether and 16.8 g (132 mmol) of pyridine were successively added, and the mixture was stirred at a temperature of 60°C for 5 hours. Then, after cooling the mixture to -20°C, 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature and stirred for 2 hours, after which 30 mL of N-methylpyrrolidone (NMP) was added, and 11.3 g (43 mmol) of diamine (AA-1) was added to N-methylpyrrolidone ( NMP) was added dropwise over 1 hour. While adding the diamine, the viscosity increased. Next, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added, and the mixture was stirred for 2 hours. Then, the polyamideimide precursor resin was precipitated in 5 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyamide-imide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyamideimide precursor resin was dried under reduced pressure at 45°C for one day to obtain polyamideimide precursor PA-1. The molecular weight of this polyamideimide precursor PA-1 was Mw = 21,600 and Mn = 9,500.

The structure of PA-1 is estimated to be a structure represented by the following formula (PA-1).

[Formula 82]

<Synthesis Example PAI-1: Synthesis of polyamideimide (PAI-1)>

In a flask equipped with a condenser and a stirrer, while removing water, 11.0 g (18 mmol) of anhydride (MA-1), 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (Tokyo Kasei Kogyo Co., Ltd.) Co., Ltd.) 0.02 g was dissolved in 40.0 g of N-methylpyrrolidone (NMP). Then, 4.76 g (18 mmol) of diamine (AA-1) was added, and the mixture was stirred at 25°C for 3 hours and further stirred at 45°C for 3 hours. Then, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 37.7 g of N-methylpyrrolidone (NMP) were added, stirred at 80 ° C. for 3 hours, and N-methylpyrrolidone (NMP ) was added and diluted.

This reaction liquid was precipitated in 1 liter of methanol and stirred for 15 minutes at a speed of 3000 rpm. The resin was obtained by filtration, stirred again for 30 minutes in 1 liter of methanol, and filtered again. The obtained resin was dried under reduced pressure at 40°C for one day to obtain polyamideimide (PAI-1). The molecular weight of PAI-1 was Mw = 22,900 and Mn = 9,900.

The structure of PAI-1 is estimated to be a structure represented by the following formula (PAI-1).

[Formula 83]

<Synthesis Example PBI-1: Synthesis of Polyimide (PBI-1)>

In a flask equipped with a condenser and a stirrer, 22.2 g (50 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 2,2, 0.02 g of 6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 100.0 g of N-methylpyrrolidone (NMP). Subsequently, 11.9 g (45 mmol) of diamine (AA-1) was added, and the mixture was stirred at 25°C for 3 hours and further stirred at 45°C for 3 hours. Then, 15.8 g (200 mmol) of pyridine, 12.8 g (125 mmol) of acetic anhydride, and 50 g of N-methylpyrrolidone (NMP) were added, stirred at 80 ° C. for 3 hours, N-methylpyrrolidone (NMP) 50 g was added and diluted.

This reaction liquid was precipitated in 1 liter of methanol and stirred for 15 minutes at a speed of 3000 rpm. The resin was obtained by filtration, stirred again for 30 minutes in 1 liter of methanol, and filtered again. The obtained resin was dried under reduced pressure at 40°C for one day to obtain polyimide (PBI-1). The molecular weight of PBI-1 was Mw = 19,000 and Mn = 8,100.

The structure of PBI-1 is estimated to be a structure represented by the following formula (PBI-1).

[Formula 84]

<Synthesis Example A-1: Synthesis of Polybenzoxazole Precursor (A-1)>

[Synthesis of polybenzoxazole precursor (A-1) from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-oxydibenzoyl chloride]

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 dripped over 1 hour. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was further stirred for 60 minutes. 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 under reduced pressure at 45°C for 3 days to obtain polybenzoxazole (A-1). The molecular weight of this polybenzoxazole precursor was Mw=21500 and Mn=9500.

The structure of A-1 is estimated to be a structure represented by the following formula (A-1).

[Formula 85]

<Synthesis Example A-2: Synthesis of Polyimide Precursor (A-2)>

14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 20.4 g of (258 mmol) of pyridine and 100 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to obtain pyromellitic acid and 2-hydroxyethyl methacrylate. of diesters were prepared. Subsequently, the resulting diester was chlorinated with SOCl ₂ , and then converted into a polyimide precursor with 4,4′-diaminodiphenyl ether in the same manner as in Synthesis Example A-5, followed by the same method as in Synthesis Example A-5. Thus, a polyimide precursor (A-2) was obtained. The weight average molecular weight of this polyimide precursor was 21,000.

The structure of A-2 is estimated to be a structure represented by the following formula (A-2).

[Formula 86]

<Synthesis Example A-3: Synthesis of Polyimide Precursor (A-3)>

[Polyimide precursor from 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-3: polyimide precursor having a radical polymerizable group ) Synthesis of]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (dried at 140 ° C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone Rice paddy, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to obtain dihydrogenation of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Esters were prepared. Subsequently, the resulting diester was chlorinated with SOCl ₂ , and then converted into a polyimide precursor with 4,4′-diaminodiphenyl ether in the same manner as in Synthesis Example A-5, followed by the same method as in Synthesis Example A-5. Thus, a polyimide precursor (A-3) was obtained. The weight average molecular weight of this polyimide precursor was 19,600.

The structure of A-3 is estimated to be a structure represented by the following formula (A-3).

[Formula 87]

<Synthesis Example A-4: Synthesis of Polyimide Precursor (A-4)>

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

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (dried at 140 ° C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone Rice paddy, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to obtain dihydrogenation of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Esters were prepared. Subsequently, after chlorination of the obtained diester with SOCl ₂ , it was converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as Synthesis Example A-5, and Synthesis Example A polyimide precursor (A-4) was obtained in the same manner as in A-5. The weight average molecular weight of this polyimide precursor was 23,500.

The structure of A-4 is estimated to be a structure represented by the following formula (A-4).

[Formula 88]

<Synthesis Example A-5: Synthesis of Polyimide Precursor (A-5)>

[A-5: Polyimide precursor resin A-5 from oxydiphthalic dianhydride, 4,4'-biphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether synthesis>

9.49 g (32.25 mmol) of 4,4'-biphthalic anhydride and 10.0 g (32.25 mmol) of oxydiphthalic dianhydride were removed while removing water in a drying reactor equipped with a flat bottom joint equipped with an agitator, condenser and internal thermometer. ) 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 successively added, and the mixture was stirred at a temperature of 60°C for 18 hours. After the mixture was then cooled to -20°C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, after warming the mixture to room temperature and stirring for 2 hours, 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a clear solution. Subsequently, a solution of 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of NMP was added dropwise over 1 hour to the resulting transparent solution. Then, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Then, 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 obtained 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 to obtain a polyimide precursor (A-5). The weight average molecular weight of the obtained polyimide precursor A-5 was 23,800, and the number average molecular weight was 10,400.

[Formula 89]

<Synthesis Example A-6>

[A-6: polyimide precursor from 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-6: radical polymerizable group Synthesis of polyimide precursor) having

155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine while stirring at room temperature. After completion of heat generation due to the reaction, it was allowed to cool to room temperature and was further left still for 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 over 40 minutes while stirring. Subsequently, a suspension obtained by suspending 93.0 g of 4,4'-diaminodiphenyl ether in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. Furthermore, 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. A precipitate generated in the reaction mixture was collected by filtration to obtain a reaction liquid.

The obtained reaction liquid was added to 3 liters of ethyl alcohol to produce a precipitate composed of a crude polymer. The resulting 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 dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and vacuum dried to obtain a powdery polymer A-6. It was 24,000 as a result of measuring the weight average molecular weight (Mw) of this polymer A-6.

<Synthesis Example A-7>

[Polyimide precursor from 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-7: radical Synthesis of polyimide precursor having a polymerizable group)]

Synthesis Example A-6 except for using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride in Synthesis Example 6 instead of 155.1 g of 4,4'-oxydiphthalic dianhydride. Polymer A-7 was obtained by reacting in the same manner as described. It was 22,900 as a result of measuring the weight average molecular weight (Mw) of this polymer A-7.

<Synthesis Example M-1>

In a flask equipped with a stirrer and a condenser, 7.25 g (105 mmol) of 1,2,4-triazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 15.52 g (100 mmol) of Karenz MOI (manufactured by Showa Denko Co., Ltd.) ) and Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) 0.01 g was dissolved in 70 mL of tetrahydrofuran (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and stirred at 25°C for 1 hour. Then, after stirring at 45°C for 2 hours, it was dissolved in 600 mL of ethyl acetate and transferred to a separatory funnel. Subsequently, this was washed twice with 100 mL of water and twice with 150 mL of saturated brine, and dried over sodium sulfate. It was transferred to a one-necked flask, filtering this with filter paper, and the solvent was removed with an evaporator to obtain 18 g of M-1. The structure of obtained M-1 is presumed to be the following structure.

[Formula 90]

<Synthesis Example M-2>

In a flask equipped with a stirrer and a condenser, 15.2 g (0.22 mol) of triazole was mixed with 150 mL of methylene chloride and cooled until it became 10°C or lower. Subsequently, 10.5 g (0.1 mol) of methacrylic acid chloride was added dropwise over 1 hour, and the temperature was raised to 20 to 25°C. After stirring at 20 to 25°C for 3 hours, 200 mL of methylene chloride was added, and the generated salt was filtered with a filter paper to collect the filtrate. The filtrate was transferred to a separatory funnel, washed twice with 50 mL of water and twice with 150 mL of saturated brine, and dried over sodium sulfate. It was transferred to a one-necked flask, filtering this with filter paper, and the solvent was removed with an evaporator to obtain 20 g of M-2. The structure of the obtained M-2 is estimated to be the following structure.

[Formula 91]

<Synthesis Examples M-3 to M-5>

The following M-3 to M-5 were synthesized in the same manner as in M-1 to M-2. The obtained structures of M-3 to M-5 are presumed to be the following structures, respectively.

[Formula 92]

<Synthesis Example AP-1: Synthesis of resin AP-1 having an azole group and an alkoxysilyl group>

15 g of propylene glycol monomethyl ether was added to flask 1, and the mixture was heated to 80°C and stirred while flowing nitrogen.

Next, in an Erlenmeyer flask (Flask 2), 14.52 g (50 mmol) of 3-(triethoxysilyl)propyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 6.16 g (50 mmol) of M-3, and propylene were added. 50 g of glycol monomethyl ether and 0.46 g of polymerization initiator V-601 (manufactured by Fujifilm Wako Co., Ltd.) were added and dissolved, and the mixture was added dropwise to flask 1 over 3 hours. Subsequently, the temperature was raised to 85°C, stirred for 3 hours, and then cooled to room temperature to obtain an AP-1 solution. The solid content concentration (solid content/total mass of solution × 100) of the AP-1 solution was 24.1% by mass, and the weight average molecular weight (Mw) of AP-1 was 12,500. The structure of the obtained AP-1 is estimated to be the following structure.

[Formula 93]

<Synthesis Examples AP-2 to AP-4: Synthesis of Compounds AP-2 to AP-4>

Compounds AP-2 to AP-4 were synthesized in the same manner as in Synthesis Example AP-1.

Estimated structures of AP-2 to AP-4 are shown in the following formulas (AP-2) to (AP-4), respectively. In each structure, subscripts in parentheses indicate the molar ratio of each repeating unit.

The Mw of AP-2 was 15,800, the Mw of AP-3 was 25,000, and the Mw of AP-4 was 8,500.

[Formula 94]

<Examples and Comparative Examples>

In each Example, each curable resin composition was obtained by mixing the components described in the table below, respectively. Moreover, in each comparative example, each component for comparison was obtained by mixing the components described in the table below, respectively.

Specifically, the content of components other than the solvents listed in the table was set to the amount (parts by mass) described in the column of each "additional amount" in the table.

In addition, for AP-1 to AP-4, the solid content in the solution was added so as to be the amount (parts by mass) described in each "added amount" in the table.

The obtained curable resin composition and the comparative composition were filtered under pressure through a polytetrafluoroethylene filter having a fine pore width of 0.8 μm.

In addition, in the table|surface, description of "-" shows that the composition does not contain the component concerned.

[Table 1]

[Table 2]

The detail of each component described in the table|surface is as follows.

〔profit〕

PA-1, PAI-1, PBI-1, A-1 to A-7: PA-1, PAI-1, PBI-1, A-1 to A-7 synthesized in the above Synthesis Example

[Specific Polymerization Inhibitor]

BS-1 to BS-7: BS-1 to BS-7 synthesized in the synthesis example described above

[Polymerizable compound (all brand names)]

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 (Shin Nakamura Kagaku)

[Compound C]

C-1 to C-7: Compounds represented by the following formulas (C-1) to (C-7)

[Formula 95]

[Other Silane Coupling Agents]

D-1 to D-4: Compounds represented by the following formulas (D-1) to (D-4)

[Formula 96]

[Compound B]

AP-1 to AP-4: AP-1 to AP-4 synthesized in the synthesis example described above

[Formula 97]

[Photoinitiator (all brand names)]

・OXE-01: IRGACURE OXE 01 (manufactured by BASF)

・OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[Polymerization inhibitor]

H-1: 1,4-benzoquinone

H-2: 4-methoxyphenol

H-3: 1,4-dihydroxybenzene

H-4: the following compound

[Formula 98]

[base generator]

I-1 to I-3: Compounds with the following structures

・I-4: WPBG-27 (Fujifilm Wako Junyaku Co., Ltd.)

[Formula 99]

[Other additives]

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

〔solvent〕

DMSO: dimethyl sulfoxide

GBL: γ-butyrolactone

NMP: N-methylpyrrolidone

In the table, the description of "DMSO/GBL" indicates that a mixture of DMSO and GBL at a mixing ratio (mass ratio) of 80:20 was used.

<Evaluation of exposure latitude>

On the Si substrate, the curable resin composition was applied to form a coating film. Next, heat treatment was performed for 240 seconds using a 100°C hot plate to form a curable resin composition layer having a film thickness of 15 µm. Next, i-line (light with a wavelength of 365 nm) was applied to the curable resin composition layer by using a stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Co., Ltd.) through a pattern mask having a square bayer with a side of 15 μm. Irradiated by changing the exposure amount from ~1000 mJ/cm ² to 100 mJ/cm ² , and then, the Si substrate on which the curable resin composition layer after exposure was formed was placed in a spin shower developer (DW-30 type; manufactured by Chemitronics Co., Ltd.) was placed on a horizontal rotary table, and developed using cyclopentanone at 23° C. for 60 seconds to remove the unexposed portion from development to form a pattern. The resolution of the curable resin composition was evaluated according to the following evaluation criteria. Further, when the exposure width of the base substrate is 15 μm ± 3 μm, it is assumed that a pattern with a line width of 15 μm (a square pattern with one side measuring 15 μm) can be resolved. The evaluation result was described in the column of "exposure latitude" in a table|surface.

-Evaluation standard-

A: The difference between the maximum value and the minimum value of the exposure dose capable of resolving a pattern with a thickness of 15 μm and a line width of 15 μm is 900 mJ/cm ² or more.

B: The difference between the maximum value and the minimum value of the exposure dose capable of resolving a pattern having a thickness of 15 μm and a line width of 15 μm is 700 mJ/cm ² or more and less than 900 mJ/cm ² .

C: The difference between the maximum value and the minimum value of the exposure dose capable of resolving a pattern having a thickness of 15 μm and a line width of 15 μm is 500 mJ/cm ² or more and less than 700 mJ/cm ² .

D: The difference between the maximum value and the minimum value of the exposure dose capable of resolving a pattern with a thickness of 15 μm and a line width of 15 μm is less than 500 mJ/cm ² .

<Evaluation of limit resolution>

A curable resin composition layer was formed on the silicon wafer by the same method as the formation of the curable resin composition layer in the evaluation of exposure latitude.

The curable resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR2005 i9C). Exposure was performed with i-line, and exposure was performed at a wavelength of 365 nm and at each exposure energy of 200 mJ/cm ² from 5 μm to 25 μm using a photomask of a fuse box in units of 1 μm. The exposed curable resin composition layer was developed using cyclopentanone and propylene glycol methyl ether acetate as a developing solution. Specifically, cyclopentanone was sprayed on the exposed curable resin composition layer, then propylene glycol methyl ether acetate was sprayed, and development was carried out for 60 seconds. In the bottom part of the fuse box, the line width where the silicon wafer was exposed was measured and evaluated according to the following evaluation criteria. The smaller the line width is, the smaller the metal wiring width formed in the subsequent plating step is, indicating that it can be made finer, and a preferable result is obtained. The measurement limit is 5 μm. The evaluation result was described in the column of "limit resolution" of a table|surface.

-Evaluation standard-

A: The line width was 5 μm or less.

B: The line width was more than 5 μm and 7 μm or less.

C: The line width was more than 7 μm and 10 μm or less.

D: The line width exceeded 10 μm.

<Evaluation of putting property>

Each curable resin composition or composition for comparison was applied onto a silicon wafer by a spin coat method (3,500 rpm, 30 seconds). The silicon wafer to which the composition was applied was dried on a hot plate at 100°C for 5 minutes to form a uniform polymer layer having a thickness of 10 µm on the silicon wafer.

[exposure]

The polymer layer on the silicon wafer was exposed to light using an aligner (Karl-Suss MA150) using a photomask formed with a 1:1 line-and-space pattern in 1 μm increments from 5 μm to 25 μm in line width. Exposure was performed with a high-pressure mercury lamp, and exposure energy at a wavelength of 365 nm was measured. The exposure amount was set as the exposure amount at which the line width described later becomes the minimum.

[pattern formation]

After exposure, it was developed for 60 seconds with cyclopentanone to form a pattern, and it was set as a patterning board|substrate. Line widths capable of having good edge sharpness were evaluated according to the following evaluation criteria.

In the patterned substrate obtained by these operations, the line-and-space pattern was observed using a scanning electron microscope, and the length of the taper from the position at half the observed film thickness was evaluated as the length of the footing. The evaluation criteria are as follows. The shorter the length of the footing, the better the footing property, which is a desirable result. The evaluation result was described in the column of "putting property" of a table|surface.

-Evaluation standard-

A: The length of the footing is less than 1 μm.

B: The length of the footing is 1 μm or more and less than 3 μm.

C: The length of the footing is 3 μm or more and less than 5 μm.

D: The footing length exceeded 5 μm.

From the above results, it is understood that when the curable resin composition according to the present invention is used, footing of the pattern obtained after development is suppressed.

The compositions for comparison according to Comparative Examples 1 to 3 do not contain a specific polymerization inhibitor.

In the case of using such a composition for comparison, it can be seen that footing of the pattern obtained after development is not suppressed.

<Example 101>

The curable resin composition used in Example 1 was applied in a layer form to the surface of a copper foil layer of a resin substrate having a copper foil layer formed on the surface by a spin coating method, dried at 100°C for 4 minutes, and curable resin composition having a film thickness of 20 μm. After forming the layer, it was exposed using a stepper (manufactured by Nikon Corporation, NSR1505i6). 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 heated at 100 degreeC for 4 minutes. After the above heating, development was carried out with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.

Then, in a nitrogen atmosphere, the temperature was raised at a heating rate of 10°C/min, and after reaching 230°C, the temperature was maintained at 230°C for 3 hours to form an interlayer insulating film for a redistribution layer. This interlayer insulating film for the redistribution layer was excellent in insulating properties.

In addition, as a result of manufacturing semiconductor devices using these interlayer insulating films for redistribution layers, it was confirmed that they operated without problems.

Claims (15)

At least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, polyimides, polybenzoxazoles, and polyamideimides;
A polymerization inhibitor having an alkoxysilyl group;
polymerizable compounds, and
A curable resin composition comprising a photopolymerization initiator. The method of claim 1,
Curable resin composition in which the said polymerization inhibitor contains at least 1 sort(s) of structure selected from the group which consists of an aminooxy radical structure, a phenol structure, a nitrobenzene structure, and a benzoquinone structure. According to claim 1 or claim 2,
Curable resin composition in which the said polymerization inhibitor contains at least 1 sort(s) of structure selected from the group which consists of an amide structure and a urea structure. The method according to any one of claims 1 to 3,
A curable resin composition comprising compound B, which is a compound having a polymerizable group and an azole group. The method according to any one of claims 1 to 4,
Curable resin composition containing compound C which is a compound which has no polymeric group and has an azole group. The method of claim 5,
Curable resin composition in which the said compound C is a compound represented by following formula (C-1) or following formula (C-2);
[Formula 1]

In formula (C-1), each of Z ¹ to Z ⁴ independently represents =CR ⁷ - or a nitrogen atom, R ¹ represents a hydrogen atom or a monovalent organic group, and R ⁷ represents a hydrogen atom or a monovalent organic group. and does not contain a polymerizable group in the structure represented by formula (C-1);
In formula (C-2), Z ⁵ to Z ⁶ each independently represent =CR ⁸ - or a nitrogen atom, R ² to R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and R ⁸ is A hydrogen atom or a monovalent organic group is shown, and a polymerizable group is not included in the structure represented by formula (C-2). The method according to any one of claims 1 to 6,
Curable resin composition which further contains the silane coupling agent which does not have an azole group as a silane coupling agent different from the polymerization inhibitor which has the said alkoxysilyl group. According to any one of claims 1 to 7,
A curable resin composition used for forming an interlayer insulating film for a redistribution layer. A cured product formed by curing the curable resin composition according to any one of claims 1 to 8. A laminate comprising two or more layers of the layers made of the cured material according to claim 9, and including a metal layer between any one of the layers made of the cured material. A method for producing a cured product comprising a film formation step of applying the curable resin composition according to any one of claims 1 to 8 on a substrate to form a film. The method of claim 11,
A method for producing a cured product comprising: an exposure step of selectively exposing the film to light and a developing step of forming a pattern by developing the film using a developing solution. According to claim 11 or claim 12,
A method for producing a cured product comprising a heating step of heating the film at 50 to 450°C. A semiconductor device comprising the cured product according to claim 9 or the laminate according to claim 10. A compound having an aminooxy radical structure and an alkoxysilyl group.